CN104151515B - Graphene modified furan resin and preparation method thereof - Google Patents
Graphene modified furan resin and preparation method thereof Download PDFInfo
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- CN104151515B CN104151515B CN201410397660.8A CN201410397660A CN104151515B CN 104151515 B CN104151515 B CN 104151515B CN 201410397660 A CN201410397660 A CN 201410397660A CN 104151515 B CN104151515 B CN 104151515B
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Abstract
The invention provides a graphene modified furan resin, which is prepared by reacting formaldehyde, furfuryl alcohol and graphene. The invention provides a preparation method of the graphene modified furan resin. The method comprises the following steps: performing a first reaction on the formaldehyde, urea and the furfuryl alcohol to obtain a first reaction product, wherein the pH value of the first reaction is 8-10, the temperature of the first reaction is 90-120 DEG C, and the time of the first reaction is 1-3 hours; and performing a second reaction on the first reaction product and the graphene to obtain the graphene modified furan resin, wherein the pH value of the second reaction is 3-3.5, and the time of the second reaction is 1-3 hours. The graphene is an atomic crystal of planar polycyclic aromatic hydrocarbon; the graphene modified furan resin provided by the invention has high bonding strength; and the connection among carbon atoms inside the graphene is very flexible, so that the graphene modified furan resin provided by the invention has high toughness.
Description
Technical field
The present invention relates to furane resins technical field, particularly relate to a kind of Graphene modified furan resin and
Preparation method.
Background technology
Furane resins are the polymer with furfuryl alcohol as base stock, have extensively in foundry resin binding agent
Application.The appearance of furane resins, makes foundry's core manufacturing craft of Single unit job lot production there occurs huge
Big change, it makes the workshop of Single unit job lot production can form mechanization production line balance, occurs in that
With " high-speed molding circle " the mechanization moulding line as representative.
At present, domestic self-hardening furan resin produce main use mass concentration to be 36.5% formalin,
Carbamide, furfuryl alcohol are base stock, although the technique of each manufacturer is not quite similar, but substantially include urine
Element, formaldehyde alkaline reaction, add the steps such as furfuryl alcohol acid reaction.
The Chinese patent of Application No. 201210377741.2 discloses the preparation of a kind of furan resin for casting
Method, detailed process is addition furfuryl alcohol 774Kg in reactor, starts stirring, is 15% by mass concentration
It is 8.5 that sodium hydroxide solution adjusts pH, adds lignin 56Kg, is warming up to 70 DEG C and reacts 2 hours,
Cooling, is that to adjust pH be to be dehydrated under 6.5, vacuum state to 20% oxalic acid solution by mass concentration, de-
Water stops below 1.0% to the mass content of resin aqueous, obtains lignin modification furfuryl alcohol component 794Kg,
Stand-by.In reactor, add formalin (mass concentration is 37%) 316Kg, start stirring, add
Carbamide 72Kg, after carbamide dissolves, is 7.8 with alkaline solution regulation pH value, is warming up to 85 DEG C of reactions 1 little
Time；Add lignin modification furfuryl alcohol component 294Kg, then react 1 hour；Adjust material system pH
It is 3.7, reaction temperature 95 DEG C, react 1.5 hours；Add carbamide 18Kg, adjust material system pH
Value be 7.5,75 DEG C reaction 1 hour after, by material system lower the temperature stopped reaction；It is dehydrated under vacuum
140Kg, adds residual lignin modification furfuryl alcohol component 500Kg, stirs, and blowing obtains 1060Kg
Furane resins.
Although this furane resins that prior art provides have certain intensity, but its adhesion strength and
Toughness is poor, limits the application of furane resins.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of Graphene modified furan resin, the present invention carries
The Graphene modified furan resin of confession has preferable adhesion strength and toughness.
The invention provides a kind of Graphene modified furan resin, reacted by formaldehyde, furfuryl alcohol and Graphene
Prepare.
Preferably, the mass ratio of described formaldehyde, furfuryl alcohol and Graphene is (10～25): (30～60):
(0.001～1).
Preferably, formaldehyde, furfuryl alcohol, Graphene and formaldehyde reducing agent preparing, described formaldehyde reducing agent includes second
One or more in dialdehyde, tripolycyanamide and polyvinyl alcohol.
The invention provides the preparation method of a kind of Graphene modified furan resin, comprise the following steps:
1), formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction, obtain the first product；Described first
The pH value of reaction is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, described first reaction
Time is 1 hour～3 hours；
2), described first product and Graphene are carried out the second reaction, obtain Graphene modification furan
Resin, the pH value of described second reaction is 3～3.5, and the time of described second reaction is 1 hour～3 hours.
Preferably, the raw material of preparing of described Graphene is biomass carbon source.
Preferably, the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtain producing in the middle of first
Thing, described catalyst includes in the chlorate of manganese, iron compound, cobalt compounds and nickel compounds
One or more；
2), under conditions of protective gas exists, described first intermediate product is heated up from the first temperature
Being incubated to the second temperature, obtain the second intermediate product, described first temperature is 20 DEG C～40 DEG C, described the
Two temperature are 300 DEG C～400 DEG C；
3), under conditions of protective gas exists, described second intermediate product is heated up from the second temperature
It is incubated to the 3rd temperature, obtains the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C；
4), under conditions of protective gas exists, described 3rd intermediate product is heated up from the 3rd temperature
Being incubated to the 4th temperature, obtain the 4th intermediate product, described 4th temperature is 1100 DEG C～1300 DEG C；
5), under conditions of protective gas exists, by described 4th intermediate product from the 4th greenhouse cooling
Being incubated to the 5th temperature, obtain Graphene, described 5th temperature is 900 DEG C～1000 DEG C.
Preferably, the mass ratio of described formaldehyde, carbamide, furfuryl alcohol and Graphene is (10～25): a:(30～60):
(0.001～1), 0 ＜ a≤15.
Preferably, described step 1) in the first reaction pressure be 0.15MPa～0.25MPa.
Preferably, step 1) in first reaction temperature be 95 DEG C～110 DEG C；
Described step 2) in second reaction temperature be 95 DEG C～110 DEG C.
Preferably, described step 2) in second reaction pH value be 3.2.
Preferably, described step 2) second reaction terminate after also include:
The second product obtained and formaldehyde reducing agent, silane coupler are carried out the 3rd reaction, obtains graphite
Alkene phenol-formaldehyde resin modified, described formaldehyde reducing agent include the one in Biformyl, tripolycyanamide and polyvinyl alcohol or
Several.
Preferably, the mass ratio of described formaldehyde, carbamide, furfuryl alcohol, Graphene and formaldehyde reducing agent is (10～25): b:
(30～60): (0.001～1): (0.4～1), 0 ＜ b≤15.
The invention provides a kind of Graphene modified furan resin, reacted by formaldehyde, furfuryl alcohol and Graphene
Prepare.The present invention with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, due to
Graphene is the atomic crystal of plane polycyclic aromatic hydrocarbon, and therefore the beneficially increase resin that there was added of Graphene divides
Sub-key energy, so that the Graphene modified furan resin that the present invention provides has preferable adhesion strength；With
Time carbon atom within Graphene between connection the most pliable and the toughest, the Graphene making the present invention provide is modified
The toughness of furane resins is preferable.
The invention provides the preparation method of a kind of Graphene modified furan resin, comprise the following steps: 1),
Formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction, obtains the first product, the pH of described first reaction
Value is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, and the time of described first reaction is 1 hour
～3 hours；2), described first product and Graphene are carried out the second reaction, obtain Graphene modified
Furane resins, the pH value of described second reaction is 3～3.5, and the time of described second reaction is 1 hour～3 little
Time.The Graphene modified furan resin that the method that the present invention provides prepares has preferable adhesion strength
And toughness.Additionally, the method that the present invention provides uses during preparing Graphene modified furan resin
Solid formaldehyde, produces without waste water, avoids negative pressure of vacuum dehydration simultaneously, make the consumption of the energy relatively
Low, it is achieved that cleaning produces, and has preferable environment protecting.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that retouched
The embodiment stated is only a part of embodiment of the present invention rather than whole embodiments.Based on the present invention
In embodiment, the institute that those of ordinary skill in the art are obtained under not making creative work premise
There are other embodiments, broadly fall into the scope of protection of the invention.
The invention provides a kind of Graphene modified furan resin, by paraformaldehyde, furfuryl alcohol and Graphene warp
Reaction prepares.
The present invention is with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, due to Graphene
Being the atomic crystal of plane polycyclic aromatic hydrocarbon, therefore there was added of Graphene beneficially increases molecular resin bond energy,
So that the Graphene modified furan resin that the present invention provides has preferable adhesion strength；Simultaneously because stone
Connection between ink carbon atom within alkene is the most pliable and the toughest, makes the Graphene modified furan resin that the present invention provides
Toughness preferable.
In the present invention, the purity of described formaldehyde is preferably >=96%.The source of described formaldehyde is not had by the present invention
Special restriction, can be bought by market and obtain.
The present invention does not has special restriction to the source of described furfuryl alcohol, can be bought by market and obtain.
In the present invention, the raw material of preparing of described Graphene is preferably biomass carbon source.In the present invention,
The preparation method of described Graphene preferably includes following steps:
1), under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtain producing in the middle of first
Thing, described catalyst includes in the chlorate of manganese, iron compound, cobalt compounds and nickel compounds
One or more；
2), under conditions of protective gas exists, described first intermediate product is heated up from the first temperature
Being incubated to the second temperature, obtain the second intermediate product, described first temperature is 20 DEG C～40 DEG C, described the
Two temperature are 300 DEG C～400 DEG C；
3), under conditions of protective gas exists, described second intermediate product is heated up from the second temperature
It is incubated to the 3rd temperature, obtains the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C；
4), under conditions of protective gas exists, described 3rd intermediate product is heated up from the 3rd temperature
Being incubated to the 4th temperature, obtain the 4th intermediate product, described 4th temperature is 1100 DEG C～1300 DEG C；
5), under conditions of protective gas exists, by described 4th intermediate product from the 4th greenhouse cooling
Being incubated to the 5th temperature, obtain Graphene, described 5th temperature is 900 DEG C～1000 DEG C.
Biomass carbon source, preferably under the effect of catalyst, is carried out catalytic treatment, obtains first by the present invention
Intermediate product, described catalyst includes the chlorate of manganese, iron compound, cobalt compounds and nickel class
One or more in compound.In the present invention, described biomass carbon source is preferably cellulose and lignin
In one or both, more preferably cellulose, most preferably porous cellulose.In the present invention, institute
State the preparation method of porous cellulose and preferably include following steps:
A), biomass resource is hydrolyzed in acid, obtains lignocellulose, described biomass resource
Including one or more in plant and agriculture and forestry organic waste material；
B), processing described lignocellulose, obtain porous cellulose, described process includes at acid
Reason, salt treatment or organic solvent process.
Biomass resource is preferably hydrolyzed in acid by the present invention, obtains lignocellulose, described biology
Matter resource includes one or more in plant and agriculture and forestry organic waste material.In the present invention, described biomass money
Source is more preferably agriculture and forestry organic waste material, most preferably corn stalk, corn cob, kaoliang stalk, megasse, Caulis Sacchari sinensis
One or more in slag, furfural dregs, xylose residue, wood flour, cotton stalk and phragmites communis, the most preferably Semen Maydis
Core.
In the present invention, the acid of described hydrolysis be preferably sulphuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid,
One or more in phosphoric acid and acetic acid.In the present invention, the consumption of the acid of described hydrolysis is preferably biology
3wt%～20wt% of matter resource.In the present invention, the temperature of described hydrolysis is preferably 90 DEG C～180 DEG C.
In the present invention, the time of described hydrolysis is preferably 10min～10h.
After obtaining lignocellulose, described wood fibre is preferably processed by the present invention, obtains porous fine
Dimension element, described process includes that acid treatment, salt treatment or organic solvent process.In the present invention, institute is processed
The method stating lignocellulose is more preferably salt treatment, and most preferably acid sulfite process processes or alkalescence
Sulphite process processes.In the present invention, the pH that described acid sulfite process processes is preferably 1～7.
In the present invention, when described acid sulfite process processes, the consumption of acid is preferably lignocellulose
4wt%～30wt%.In the present invention, when described acid sulfite process processes, the concentration expressed in percentage by weight of acid is excellent
It is (2～20) that choosing makes liquid-solid ratio: 1.In the present invention, the temperature that described acid sulfite process processes is preferred
It it is 70 DEG C～180 DEG C.In the present invention, the time that described acid sulfite process processes is preferably 1 hour
～6 hours.
In the present invention, the pH that described alkali sulfite process processes is preferably 7～14.In the present invention,
When described alkali sulfite process processes, the consumption of alkali is preferably 4wt%～30wt% of lignocellulose.?
In the present invention, when described alkali sulfite process processes, the concentration expressed in percentage by weight of alkali preferably makes the liquid-solid ratio be
(2～20): 1.In the present invention, the temperature that described alkali sulfite process processes is preferably 70 DEG C～180
℃.In the present invention, the time that described alkali sulfite process processes is preferably 1 hour～6 hours.
In the present invention, the catalyst preparing described Graphene preferably includes the cyaniding of the chlorate of ferrum, ferrum
Thing, iron content hydrochlorate, the chlorate of cobalt, containing cobaltatess, the chlorate of nickel and containing the one in nickelate or
Several；More preferably include that iron chloride, ferrous chloride, ferric nitrate, ferrous nitrate, iron sulfate, sulphuric acid are sub-
Ferrum, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid close potassium ferrites, cobaltous chloride, cobalt nitrate, cobaltous sulfate,
One or more in cobalt acetate, Nickel dichloride., nickel nitrate, nickel sulfate and nickel acetate.
In the present invention, when preparing described Graphene, the mass ratio of catalyst and biomass carbon source is preferably
(0.01～2): 1.In the present invention, the temperature of described catalytic treatment is preferably 20 DEG C～180 DEG C.At this
In bright, the time of described catalytic treatment is preferably 2 hours～10 hours.
After obtaining the first intermediate product, the present invention is preferably under conditions of protective gas exists, by described
First intermediate product is incubated after the first temperature is warming up to the second temperature, obtains the second intermediate product, by this
Protective gas is designated as the first protective gas；Described first temperature is 20 DEG C～40 DEG C, described second temperature
It it is 300 DEG C～400 DEG C.In the present invention, described first intermediate product is warming up to the second temperature from the first temperature
Heating rate be preferably 5 DEG C/min～20 DEG C/min.In the present invention, described first intermediate product is from first
Temperature retention time after temperature is warming up to the second temperature is preferably 4 hours～8 hours.In the present invention, described
One protective gas is preferably one or more in nitrogen and noble gas, more preferably nitrogen.
After obtaining the second intermediate product, the present invention is preferably under conditions of protective gas exists, by described
Second intermediate product is incubated after the second temperature is warming up to the 3rd temperature, obtains the 3rd intermediate product, by this
Protective gas is designated as the second protective gas；Described 3rd temperature is 800 DEG C～900 DEG C.In the present invention,
The heating rate that described second intermediate product is warming up to the 3rd temperature from the second temperature is preferably 20 DEG C
/ min～50 DEG C/min.In the present invention, described second intermediate product is warming up to the 3rd temperature from the second temperature
After temperature retention time be preferably 3.5 hours～7 hours.In the present invention, described second protective gas
Kind is consistent with the kind of the first protective gas described in technique scheme, does not repeats them here.
After obtaining the 3rd intermediate product, the present invention is preferably under conditions of protective gas exists, by described
3rd intermediate product is incubated after the 3rd temperature is warming up to the 4th temperature, obtains the 4th intermediate product, by this
Protective gas is designated as the 3rd protective gas；Described 4th temperature is 1100 DEG C～1300 DEG C.In the present invention
In, the heating rate that described 3rd intermediate product is warming up to the 4th temperature from the 3rd temperature is preferably 50 DEG C
/ min～60 DEG C/min.In the present invention, described 3rd intermediate product is warming up to the 4th temperature from the 3rd temperature
After temperature retention time be preferably 6 hours～8 hours.In the present invention, the kind of described 3rd protective gas
Consistent with the kind of the first protective gas described in technique scheme, do not repeat them here.
After obtaining the 4th intermediate product, the present invention is preferably under conditions of protective gas exists, by described
4th intermediate product is incubated after the 4th greenhouse cooling to the 5th temperature, obtains Graphene, by this protectiveness
Gas is designated as the 4th protective gas；Described 5th temperature is 900 DEG C～1000 DEG C.In the present invention, institute
State the 4th intermediate product and be preferably 30 DEG C/min～50 from the rate of temperature fall of the 4th greenhouse cooling to the 5th temperature
℃/min.In the present invention, described 4th intermediate product insulation after the 4th greenhouse cooling to the 5th temperature
Time is preferably 2 hours～4 hours.In the present invention, the kind of described 4th protective gas is with above-mentioned
The kind of the first protective gas described in technical scheme is consistent, does not repeats them here.
In the present invention, described first protective gas, the second protective gas, the 3rd protective gas
Can be identical with the 4th protective gas, it is also possible to different；Described first protective gas, the second protection
Property gas, the 3rd protective gas and the 4th protective gas are the most identical.
In the present invention, the mass ratio of described formaldehyde, furfuryl alcohol and Graphene is preferably (10～25): (30～60):
(0.001～1), more preferably (12～22): (35～55): (0.01～0.8), most preferably (15～20):
(40～50): (0.1～0.6).
In the present invention, described Graphene modified furan resin is preferably by formaldehyde, furfuryl alcohol, Graphene and fall
Aldehyde agent prepares, and described formaldehyde reducing agent includes one or more in Biformyl, tripolycyanamide and polyvinyl alcohol.
In the present invention, described formaldehyde reducing agent is more preferably Biformyl, tripolycyanamide or polyvinyl alcohol.In the present invention
In, described formaldehyde reducing agent can react with the formaldehyde of residual, and the Graphene making the present invention prepare changes
Property furane resins in the content of free aldehyde reduce, and then improve the modeling environment of Foundry Production Worksite, favorably
Healthy in workman.
In the present invention, the mass ratio of described formaldehyde and formaldehyde reducing agent is preferably (10～25): (0.4～1),
More preferably (15～20): (0.5～0.8).The present invention does not has special restriction to the source of described formaldehyde reducing agent,
Can be bought by market and obtain.
In the present invention, described Graphene modified furan resin is preferably by formaldehyde, furfuryl alcohol, Graphene and silicon
Alkane coupling agent prepares.In the present invention, the addition of described silane coupler can improve this further
The adhesion strength of the Graphene modified furan resin that invention provides.The present invention kind to described silane coupler
Class and source do not have special restriction, use silane coupler well known to those skilled in the art, can
Bought by market and obtain.In an embodiment of the present invention, described coupling agent can be KH550 type coupling agent
Or KH560 type coupling agent.
In the present invention, the mass ratio of described formaldehyde and silane coupler is preferably (10～25): (0.2～0.8),
More preferably (15～20): (0.3～0.6).
In the present invention, described Graphene modified furan resin more preferably by formaldehyde, furfuryl alcohol, Graphene,
Formaldehyde reducing agent and silane coupler prepare.In the present invention, described formaldehyde, furfuryl alcohol, Graphene, fall
The mass ratio of aldehyde agent and coupling agent is preferably (10～25): (30～60): (0.001～1): (0.4～1):
(0.2～0.8), more preferably (15～20): (35～55): (0.01～0.8): (0.5～0.8): (0.3～0.6).
The invention provides the preparation method of a kind of Graphene modified furan resin, comprise the following steps:
1), formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction, obtain the first product；Described first
The pH value of reaction is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, described first reaction
Time is 1 hour～3 hours；
2), described first product and Graphene are carried out the second reaction, obtain Graphene modification furan
Resin, the pH value of described second reaction is 3～3.5, and the time of described second reaction is 1 hour～3 hours.
The Graphene modified furan resin that the method that the present invention provides prepares has preferable adhesion strength
And toughness.Additionally, the method that the present invention provides, make during preparing Graphene modified furan resin
With formaldehyde, therefore produce without waste water, and avoid negative pressure of vacuum dehydration, it is possible to make the energy
Consume relatively low, it is achieved that cleaning produces, and has preferable environment protecting.
In the present invention, the mass ratio of described formaldehyde, carbamide, furfuryl alcohol and Graphene preferably (10～25): a:
(30～60): (0.4～1): (0.001～1), 0 ＜ a≤15, more preferably (12～22): (2～12):
(35～55): (0.5～0.8): (0.01～0.8), most preferably (15～20): (4～10): (40～50):
(0.6～0.7): (0.1～0.6).
Formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction by the present invention, obtain the first product；Described
The pH value of one reaction is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, described first reaction
Time be 1 hour～3 hours.In the present invention, the pH value of described first reaction is preferably 9.At this
In invention, the temperature of described first reaction is preferably 95 DEG C～110 DEG C, more preferably 100 DEG C.At this
In bright, the time of described first reaction is preferably 2 hours.In the present invention, the pressure of described first reaction
Power is preferably 0.15MPa～0.25MPa, more preferably 0.2MPa.
The present invention does not has special restriction to the source of described carbamide, can be bought by market and obtain.At this
In bright, described formaldehyde, Graphene, the kind of furfuryl alcohol and source with technique scheme described in paraformaldehyde,
Graphene is consistent with source with the kind of furfuryl alcohol, does not repeats them here.
Formaldehyde, carbamide, furfuryl alcohol and alkali liquor are preferably carried out the first reaction by the present invention, obtain the first reaction and produce
Thing.The present invention does not has special restriction to the kind of alkali in described alkali liquor, uses those skilled in the art ripe
The alkali compounds known.The present invention does not has special restriction to mass concentration and the consumption of described alkali liquor,
Described alkali liquor can make the pH value of described first reaction be 8～10.
After obtaining the first product, it is anti-that described first product and Graphene are carried out second by the present invention
Should, obtaining Graphene modified furan resin, the pH value of described second reaction is 3～3.5, described second anti-
The time answered is 1 hour～3 hours.In the present invention, the pH value of described second reaction is preferably 3.2.
In the present invention, the time of described second reaction is preferably 2 hours.In the present invention, described second anti-
The temperature answered is preferably 100 DEG C～105 DEG C, more preferably 100 DEG C.
The present invention preferably carries out described second reaction under the effect of acidic catalyst.In the present invention, institute
State acidic catalyst preferably lewis acid or mass concentration is the aqueous formic acid of 40%, more preferably matter
Amount concentration is the aqueous formic acid of 40%.In the present invention, the consumption of described acidic catalyst is preferably institute
State the reaction condition that the second reaction provides pH value to be 3～3.5.
After described second has reacted, the present invention is preferably by the second product obtained and formaldehyde reducing agent, silicon
Alkane coupling agent carries out the 3rd reaction, obtains Graphene modified furan resin.In the present invention, described fall aldehyde
Agent and the kind of silane coupler, source and consumption and formaldehyde reducing agent described in technique scheme and silane coupled
The kind of agent, source are consistent with consumption, do not repeat them here.In the present invention, described 3rd reaction
Temperature is preferably 50 DEG C～70 DEG C, more preferably 55 DEG C～65 DEG C, most preferably 60 DEG C.
According to the standard of GB/T265-1988 " oil product kinematic viscosity algoscopy ", test is the present invention carry
The viscosity of the Graphene modified furan resin of confession, test result is, the Graphene modification furan that the present invention provides
The viscosity of furane resins is 20 mpa～40 mp .sa.s.According to JB/T7526-2008, " casting is with from hard furan tree
Fat " standard, the adhesion strength of Graphene modified furan resin that the test present invention provides and toughness, survey
Test result is, 24 hours tensile strength >=2.0MPa of the Graphene modified furan resin that the present invention provides,
24 hours bending strength >=10 MPa.
The invention provides a kind of Graphene modified furan resin, reacted by formaldehyde, furfuryl alcohol and Graphene
Prepare.The present invention with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, due to
Graphene is the atomic crystal of plane polycyclic aromatic hydrocarbon, and therefore the beneficially increase resin that there was added of Graphene divides
Sub-key energy, so that the Graphene modified furan resin that the present invention provides has preferable adhesion strength；With
Time carbon atom within Graphene between connection the most pliable and the toughest, the Graphene making the present invention provide is modified
The toughness of furane resins is preferable.
The invention provides the preparation method of a kind of Graphene modified furan resin, comprise the following steps: 1),
Formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction, obtains the first product；The pH of described first reaction
Value is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, and the time of described first reaction is 1 hour
～3 hours；2), described first product and Graphene are carried out the second reaction, obtain Graphene modified
Furane resins, the pH value of described second reaction is 3～3.5, and the time of described second reaction is 1 hour～3 little
Time.The Graphene modified furan resin that the method that the present invention provides prepares has preferable adhesion strength
And toughness.Additionally, the method that the present invention provides, make during preparing Graphene modified furan resin
With formaldehyde, therefore produce without waste water, and avoid negative pressure of vacuum dehydration, it is possible to make the energy
Consume relatively low, it is achieved that cleaning produces, and has preferable environment protecting.
Raw material used in following example of the present invention is commercial goods.
Embodiment 1
At 90 DEG C, corn cob is carried out in sulphuric acid the hydrolysis of 10min, obtain lignocellulose, described
The quality of sulphuric acid is the 3% of described corn cob quality；
At 70 DEG C, the acid sulfite process carried out described lignocellulose 1 hour processes, and obtains many
Hole cellulose, the pH value in described acid sulfite process processing procedure is 1, and acid is sulphuric acid, sulphite
For magnesium sulfite, the quality of described sulphuric acid is the 4% of described lignocellulose quality, and liquid-solid ratio is 2:1.
The porous cellulose obtained is carried out hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is that described porous is fine
The 5% of dimension quality amount, the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and manganese chloride, at 20 DEG C, stirring carries out catalytic treatment, described chlorine for 2 hours
The mass ratio changing manganese and porous cellulose is 0.01:1；Product after the catalytic treatment that will obtain is at 70 DEG C
It is dried, obtains the water content the first intermediate product less than 10wt%.
Described first intermediate product is placed in retort, with the gas intake of 200mL/min to described carbon
Change in stove and be passed through nitrogen as protection gas, described first intermediate product is risen from 25 DEG C with the speed of 5 DEG C/min
Temperature, to 300 DEG C, is incubated 4 hours, obtains the second intermediate product；By described second intermediate product with 20 DEG C/min
Speed be warming up to 800 DEG C from 300 DEG C, be incubated 3.5 hours, obtain the 3rd intermediate product；By the described 3rd
Intermediate product is warming up to 1100 DEG C with the speed of 50 DEG C/min from 800 DEG C, is incubated 6 hours, obtains in the middle of the 4th
Product；Described 4th intermediate product is cooled to 900 DEG C with the speed of 30 DEG C/min from 1100 DEG C, is incubated 2
Hour；The 4th intermediate product after described cooling is cooled to 60 DEG C.
At 60 DEG C, by the 4th intermediate product after above-mentioned cooling at the sodium hydroxide water that mass concentration is 3%
Solution washs 4 hours, obtains the first washed product；At 70 DEG C, by described first washed product in matter
Measure in the aqueous hydrochloric acid solution that concentration is 4% and wash 4 hours, obtain the second washed product；By described second washing
Product is dried after being washed with distilled water to neutrality, obtains Graphene.
Embodiment 2
At 180 DEG C, corn cob is carried out in nitric acid the hydrolysis of 10h, obtain lignocellulose, described
The quality of nitric acid is the 20% of described corn cob quality；
At 180 DEG C, the acid sulfite process carried out described lignocellulose 6 hours processes, and obtains
Porous cellulose, the pH value in described acid sulfite process processing procedure is 7, and acid is sulphuric acid, sulfurous acid
Salt is sodium sulfite, and the quality of described sulphuric acid is the 30% of described lignocellulose quality, and liquid-solid ratio is 20:1.
Described porous cellulose carries out hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is described porous fibre
The 5% of quality amount, the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and ferric nitrate, at 180 DEG C, stirring carries out catalytic treatment for 10 hours, described
The mass ratio of ferric nitrate and porous cellulose is 2:1；Product after the catalytic treatment that will obtain is at 120 DEG C
It is dried, obtains the water content the first intermediate product less than 5wt%.
Described first intermediate product is placed in retort, with the gas intake of 800mL/min to described carbon
Change in stove and be passed through argon as protection gas, described first intermediate product is risen from 20 DEG C with the speed of 20 DEG C/min
Temperature, to 400 DEG C, is incubated 8 hours, obtains the second intermediate product；By described second intermediate product with 50 DEG C/min
Speed be warming up to 900 DEG C from 400 DEG C, be incubated 7 hours, obtain the 3rd intermediate product；By in the described 3rd
Between product be warming up to 1300 DEG C with the speed of 60 DEG C/min from 900 DEG C, be incubated 8 hours, obtain producing in the middle of the 4th
Thing；From 1300 DEG C, described 4th intermediate product is cooled to 1000 DEG C with the speed of 50 DEG C/min, and insulation 4 is little
Time；The 4th intermediate product after described cooling is cooled to 20 DEG C.
At 120 DEG C, it is the sodium hydroxide of 55% by the 4th intermediate product after above-mentioned cooling in mass concentration
Aqueous wash medium is washed 24 hours, obtains the first washed product；At 150 DEG C, by described first washed product
The aqueous hydrochloric acid solution that mass concentration is 10% washs 24 hours, obtains the second washed product；By described
Two washed product are dried after being washed with distilled water to neutrality, obtain Graphene.
Embodiment 3
At 130 DEG C, corn cob is carried out in hydrochloric acid the hydrolysis of 5h, obtain lignocellulose, described salt
Quality is described corn cob quality the 10% of acid；
At 120 DEG C, the acid sulfite process carried out described lignocellulose 4 hours processes, and obtains
Porous cellulose, the pH value in described acid sulfite process processing procedure is 3, and acid is sulphuric acid, sulfurous acid
Salt is ammonium sulfite, and the quality of described sulphuric acid is the 18% of described lignocellulose quality, and liquid-solid ratio is 10:1.
Described porous cellulose carries out hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is described porous fibre
The 5% of quality amount, the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and cobaltous sulfate, at 50 DEG C, stirring carries out catalytic treatment, described sulfur for 5 hours
The mass ratio of acid cobalt and porous cellulose is 0.1:1；Product after the catalytic treatment that will obtain is dry at 90 DEG C
Dry, obtain the water content the first intermediate product less than 8wt%.
Described first intermediate product is placed in retort, with the gas intake of 400mL/min to described carbon
Change in stove and be passed through nitrogen as protection gas, described first intermediate product is risen from 40 DEG C with the speed of 10 DEG C/min
Temperature, to 320 DEG C, is incubated 5 hours, obtains the second intermediate product；By described second intermediate product with 30 DEG C/min
Speed be warming up to 820 DEG C from 320 DEG C, be incubated 5 hours, obtain the 3rd intermediate product；By in the described 3rd
Between product be warming up to 1150 DEG C with the speed of 54 DEG C/min from 820 DEG C, be incubated 7 hours, obtain producing in the middle of the 4th
Thing；Described 4th intermediate product is cooled to 920 DEG C with the speed of 35 DEG C/min from 1150 DEG C, is incubated 3 hours；
The 4th intermediate product after described cooling is cooled to 30 DEG C.
At 80 DEG C, the 4th intermediate product after above-mentioned cooling is washed in the ammonia that mass concentration is 10%
8 hours, obtain the first washed product；At 90 DEG C, it is 6% by described first washed product in mass concentration
Aqueous hydrochloric acid solution in wash 8 hours, obtain the second washed product；By described second washed product distillation
Water washing is dried to neutrality, obtains Graphene.
Embodiment 4
Graphene, concrete mistake is prepared according to method disclosed in the Chinese patent of Application No. 200810113596.0
Cheng Wei:
Silicon substrate is cleaned post-drying with deionized water, ethanol, acetone successively, passes through gas phase deposition technology
Zinc sulfide that a layer thickness is 100 nanometers is deposited as catalyst in surface of silicon；
Described deposition has the silicon substrate of zinc sulfide be placed in the middle part of the quartz ampoule of cleaning, quartz ampoule is put into electricity
In stove, make the middle part of quartz ampoule be positioned at the central area of electric furnace, in quartz ampoule, be then passed through 100sccm's
The argon gaseous mixture of hydrogen and 100sccm, after 60 minutes, begins to warm up；
When the temperature in center of electric furnace region is up to 850 DEG C, in electric furnace, it is passed through ethanol as carbon source, reaction
Proceed by；
After reaction carries out 20 minutes, stop being passed through ethanol, simultaneously close off electric furnace, continue to be passed through 100sccm's
The gaseous mixture of the argon of hydrogen and 100sccm is down to room temperature to temperature, obtains depositing the substrate of Graphene；
Described deposition has the substrate of Graphene put in the hydrochloric acid solution of 0.1mol/L soak 60 minutes, remove
Devulcanization zinc, is then washed with deionized water clean drying, obtains Graphene.
Embodiment 5
Close bottom outlet valve, open the charging valve of reactor, under conditions of stirring, to described reaction
Still adds the furfuryl alcohol of 40g, the carbamide of 6.5g and the paraformaldehyde of 15g and mass concentration is the hydrogen of 15%
Aqueous solution of sodium oxide, obtains the mixed liquor that pH value is 9.2；
Open steam valve, maintain steam pressure 0.15MPa, in 30 minutes, described reactor is warming up to
100 DEG C, the mixed liquor in described reactor is carried out first reaction of 100 minutes, obtains the first reaction and produce
Thing；
After described first reaction terminates, open cooling water, described first product be cooled to 50 DEG C,
In described first product, add mass concentration be the aqueous formic acid of 40% and the embodiment 1 of 2g is made
The standby Graphene obtained；, it is described first anti-that described mass concentration is that the consumption of the aqueous formic acid of 40% makes
The pH value answering product and Graphene mixture is 4.5；
Open steam valve, the mixture of described first product and Graphene was warming up in 30 minutes
100 DEG C, carry out second reaction of 120 minutes, obtain the second product；
After described second has reacted, described second product is cooled to 60 DEG C, in the condition of stirring
Under, the Biformyl of the KH550 type coupling agent and 5g that add 0.6g in described second product is carried out
3rd reaction, obtains Graphene modified furan resin.
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 5 prepares
The viscosity of modified furan resin, test result is, the Graphene that the embodiment of the present invention 5 prepares is modified
The viscosity of furane resins is 22mpa.s。
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 5 prepares
The adhesion strength of modified furan resin and toughness, test result is, the embodiment of the present invention 5 prepares
24 hours tensile strength of Graphene modified furan resin is 2.38MPa, and within 24 hours, bending strength is 10.2
MPa, adhesion strength and toughness are preferable.
According to the standard of JB/T7526-2008 " casting is with from hard furan ", the test embodiment of the present invention 5 is made
The content of free aldehyde in the standby Graphene modified furan resin obtained, test result is, the embodiment of the present invention 5
In the Graphene modified furan resin prepared, the mass content of free aldehyde is 0.02%.
Embodiment 6
Close bottom outlet valve, open the charging valve of reactor, under conditions of stirring, to described reaction
Still adds the furfuryl alcohol of 40g, the carbamide of 7g and the paraformaldehyde of 20g and mass concentration is the hydrogen-oxygen of 15%
Change sodium water solution, obtain the mixed liquor that pH value is 9.1；
Open steam valve, maintain steam pressure 0.25MPa, in 30 minutes, described reactor is warming up to
105 DEG C, the mixed liquor in described reactor is carried out first reaction of 100 minutes, obtains the first reaction and produce
Thing；
After described first reaction terminates, open cooling water, described first product be cooled to 50 DEG C,
Aqueous formic acid and the embodiment 2 of 2.5g that mass concentration is 40% is added in described first product
Mass concentration described in the Graphene prepared is that the consumption of the aqueous formic acid of 40% makes described first reaction
The pH value of the mixture of product and Graphene is 4.6；
Open steam valve, the mixture of described first product and Graphene was warming up in 40 minutes
105 DEG C, carry out second reaction of 100 minutes, obtain the second product；
After described second has reacted, described second product is cooled to 60 DEG C, in the condition of stirring
Under, the tripolycyanamide of the KH560 type coupling agent and 2g that add 0.6g in described second product enters
Row the 3rd reacts, and obtains Graphene modified furan resin.
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 6 prepares
The viscosity of modified furan resin, test result is, the Graphene that the embodiment of the present invention 6 prepares is modified
The viscosity of furane resins is 27mpa.s。
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 6 prepares
The adhesion strength of modified furan resin and toughness, test result is, the embodiment of the present invention 6 prepares
24 hours tensile strength of Graphene modified furan resin is 2.25MPa, and within 24 hours, bending strength is 10.2
MPa, adhesion strength and toughness are preferable.
According to the standard of JB/T7526-2008 " casting is with from hard furan ", the test embodiment of the present invention 6 is made
The content of free aldehyde in the standby Graphene modified furan resin obtained, test result is, the embodiment of the present invention 6
In the Graphene modified furan resin prepared, the mass content of free aldehyde is 0.01%.
Embodiment 7
Close bottom outlet valve, open the charging valve of reactor, under conditions of stirring, to described reaction
Still adds the furfuryl alcohol of 45g, the carbamide of 7.5g and the paraformaldehyde of 22g and mass concentration is the hydrogen of 15%
Aqueous solution of sodium oxide, obtains the mixed liquor that pH value is 8.95；
Open steam valve, maintain steam pressure 0.2MPa, in 30 minutes, described reactor is warming up to
103 DEG C, the mixed liquor in described reactor is carried out first reaction of 100 minutes, obtains the first reaction and produce
Thing；
After described first reaction terminates, open cooling water, described first product be cooled to 50 DEG C,
Aqueous formic acid and the embodiment 3 of 2.3g that mass concentration is 40% is added in described first product
The Graphene prepared, it is described first anti-that described mass concentration is that the consumption of the aqueous formic acid of 40% makes
The pH value answering the mixture of product and Graphene is 4.45；
Open steam valve, the mixture of described first product and Graphene was warming up in 45 minutes
103 DEG C, carry out second reaction of 100 minutes, obtain the second product；
After described second has reacted, described second product is cooled to 60 DEG C, in the condition of stirring
Under, in described second product, add coupling agent and the polyvinyl alcohol of 2g of the KH560 type of 0.6g
Carry out the 3rd reaction, obtain Graphene modified furan resin.
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 7 prepares
The viscosity of modified furan resin, test result is, the Graphene that the embodiment of the present invention 7 prepares is modified
The viscosity of furane resins is 26mpa.s。
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 7 prepares
The adhesion strength of modified furan resin and toughness, test result is, the embodiment of the present invention 7 prepares
24 hours tensile strength of Graphene modified furan resin is 2.31MPa, and within 24 hours, bending strength is 10.26
MPa, adhesion strength and toughness are preferable.
According to the standard of JB/T7526-2008 " casting is with from hard furan ", the test embodiment of the present invention 7 is made
The content of free aldehyde in the standby Graphene modified furan resin obtained, test result is, the embodiment of the present invention 7
In the Graphene modified furan resin prepared, the mass content of free aldehyde is 0.
Embodiment 8
Close bottom outlet valve, open the charging valve of reactor, under conditions of stirring, to described reaction
Still adds the furfuryl alcohol of 40g, the carbamide of 6.5g and the paraformaldehyde of 15g and mass concentration is the hydrogen of 15%
Aqueous solution of sodium oxide, obtains the mixed liquor that pH value is 9.2；
Open steam valve, maintain steam pressure 0.15MPa, in 30 minutes, described reactor is warming up to
100 DEG C, the mixed liquor in described reactor is carried out first reaction of 100 minutes, obtains the first reaction and produce
Thing；
After described first has reacted, open cooling water, described first product be cooled to 50 DEG C,
In described first product, add mass concentration be the aqueous formic acid of 40% and the embodiment 4 of 2g is made
The standby Graphene obtained, described mass concentration is that the consumption of the aqueous formic acid of 40% makes described first reaction
The pH value of product and Graphene mixture is 4.5；
Open steam valve, the mixture of described first product and Graphene was warming up in 30 minutes
100 DEG C, carry out second reaction of 120 minutes, obtain the second product；
After described second has reacted, described second product is cooled to 60 DEG C, in the condition of stirring
Under, the Biformyl of the KH550 type coupling agent and 2.5g that add 0.6g in described second product enters
Row the 3rd reacts, and obtains Graphene modified furan resin.
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 8 prepares
The viscosity of modified furan resin, test result is, the Graphene that the embodiment of the present invention 8 prepares is modified
The viscosity of furane resins is 40mpa.s。
According to the method described in technique scheme, the Graphene that the test embodiment of the present invention 8 prepares
The adhesion strength of modified furan resin and toughness, test result is, the embodiment of the present invention 8 prepares
24 hours tensile strength of Graphene modified furan resin is 2MPa, and 24 hours bending strengths are 10MPa,
Adhesion strength and toughness are preferable.
According to the standard of JB/T7526-2008 " casting is with from hard furan ", the test embodiment of the present invention 8 is made
The content of free aldehyde in the standby Graphene modified furan resin obtained, test result is, the embodiment of the present invention 8
In the Graphene modified furan resin prepared, the mass content of free aldehyde is 0.05%.
Comparative example 1
Furan tree is prepared according to the method disclosed in the Chinese patent of Application No. 201210377741.2
Fat, detailed process is:
In reactor, add furfuryl alcohol 774Kg, start stirring, be the sodium hydroxide of 15% by mass concentration
It is 8.5 that solution adjusts pH, adds lignin 56Kg, is warming up to 70 DEG C and reacts 2 hours, and cooling is used
Mass concentration be 20% oxalic acid solution adjust pH be 6.5, be dehydrated under vacuum conditions, dehydration extremely
The mass concentration of resin aqueous is less than 1.0% stopping, obtaining lignin modification furfuryl alcohol component 794Kg, stand-by.
In reactor, add formalin (mass concentration is 37%) 316Kg, start stirring, add urine
Element 72Kg, after carbamide dissolves, is 7.8 with alkaline solution regulation pH value, is warming up to 85 DEG C of reactions 1 little
Time；Add lignin modification furfuryl alcohol component 294Kg, then react 1 hour；Adjust material system pH
It is 3.7, at reaction temperature 95 DEG C, reacts 1.5 hours；Add carbamide 18Kg, adjust material system
PH value is 7.5, after reacting 1 hour at 75 DEG C, and stopped reaction that material system is lowered the temperature；At vacuum bar
Add dehydrant 140Kg under part, add residual lignin modification furfuryl alcohol component 500Kg, stir,
Obtain furane resins.
According to the method described in technique scheme, test the Graphene that comparative example 1 of the present invention prepares
The adhesion strength of modified furan resin and toughness, test result is, comparative example 1 of the present invention prepares
The Graphene modified furan resin tensile strength of 24 hours is 1.84MPa, and the bending strength of 24 hours is
7.4MPa。
According to the standard of JB/T7526-2008 " casting is with from hard furan ", test comparative example 1 of the present invention and make
The content of free aldehyde in the standby Graphene modified furan resin obtained, test result is, comparative example 1 of the present invention
In the Graphene modified furan resin prepared, the mass content of free aldehyde is 0.3%.
As seen from the above embodiment, the invention provides a kind of Graphene modified furan resin, by poly first
Aldehyde, furfuryl alcohol and Graphene are reacted to be prepared.The present invention synthesizes stone with formaldehyde and furfuryl alcohol and Graphene
Ink alkene modified furan resin, owing to Graphene is the atomic crystal of plane polycyclic aromatic hydrocarbon, therefore Graphene
There was added beneficially increase molecular resin bond energy so that the present invention provide Graphene modified furan resin
There is preferable adhesion strength；Simultaneously because the connection between carbon atom within Graphene is the most pliable and the toughest, make
The toughness of the Graphene modified furan resin that the present invention provides is preferable.
The preparation method that the invention provides a kind of Graphene modified furan resin comprises the following steps: 1),
Formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction, obtains the first product；The pH of described first reaction
Value is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, and the time of described first reaction is 1 hour
～3 hours；2), described first product and Graphene are carried out the second reaction, obtain Graphene modified
Furane resins, the pH value of described second reaction is 3～3.5, and the time of described second reaction is 1 hour～3 little
Time.The Graphene modified furan resin that the method that the present invention provides prepares has preferable adhesion strength
And toughness.Additionally, the method that the present invention provides, make during preparing Graphene modified furan resin
With formaldehyde, therefore produce without waste water, and avoid negative pressure of vacuum dehydration, it is possible to make the energy
Consume relatively low, it is achieved that cleaning produces, and has preferable environment protecting.
Claims (12)
1. a Graphene modified furan resin, by the reacted system of the raw material including formaldehyde, furfuryl alcohol and Graphene
For obtaining.
Graphene modified furan resin the most according to claim 1, it is characterised in that described formaldehyde,
The mass ratio of furfuryl alcohol and Graphene is (10～25): (30～60): (0.001～1).
Graphene modified furan resin the most according to claim 1, it is characterised in that by formaldehyde, bran
Alcohol, Graphene and formaldehyde reducing agent prepare, and described formaldehyde reducing agent includes Biformyl, tripolycyanamide and polyvinyl alcohol
In one or more.
4. a preparation method for Graphene modified furan resin, comprises the following steps:
1), formaldehyde, carbamide and furfuryl alcohol are carried out the first reaction, obtain the first product；Described first anti-
The pH value answered is 8～10, and the temperature of described first reaction is 90 DEG C～120 DEG C, the time of described first reaction
It it is 1 hour～3 hours；
2), described first product and Graphene are carried out the second reaction, obtain Graphene modification furan tree
Fat, the pH value of described second reaction is 3～3.5, and the time of described second reaction is 1 hour～3 hours.
Method the most according to claim 4, it is characterised in that the raw material of preparing of described Graphene is made a living
Material carbon source.
Method the most according to claim 5, it is characterised in that the preparation method of described Graphene includes
Following steps:
1), under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtains the first intermediate product,
Described catalyst includes the one in the chlorate of manganese, iron compound, cobalt compounds and nickel compounds
Or it is several；
2), under conditions of protective gas exists, described first intermediate product is warming up to from the first temperature
Being incubated after second temperature, obtain the second intermediate product, described first temperature is 20 DEG C～40 DEG C, described second temperature
Degree is 300 DEG C～400 DEG C；
3), under conditions of protective gas exists, described second intermediate product is warming up to from the second temperature
It is incubated after 3rd temperature, obtains the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C；
4), under conditions of protective gas exists, described 3rd intermediate product is warming up to from the 3rd temperature
Being incubated after 4th temperature, obtain the 4th intermediate product, described 4th temperature is 1100 DEG C～1300 DEG C；
5), protective gas exist under conditions of, by described 4th intermediate product from the 4th greenhouse cooling to
Being incubated after 5th temperature, obtain Graphene, described 5th temperature is 900 DEG C～1000 DEG C.
Method the most according to claim 4, it is characterised in that described formaldehyde, carbamide, furfuryl alcohol and stone
The mass ratio of ink alkene is (10～25): a:(30～60): (0.001～1), 0 ＜ a≤15.
Method the most according to claim 4, it is characterised in that described step 1) in the first reaction pressure
Power is 0.15MPa～0.25MPa.
Method the most according to claim 4, it is characterised in that step 1) in first reaction temperature
It it is 95 DEG C～110 DEG C；
Described step 2) in second reaction temperature be 95 DEG C～110 DEG C.
Method the most according to claim 4, it is characterised in that described step 2) in second reaction
PH value is 3.2.
11. methods according to claim 4, it is characterised in that described step 2) second reaction terminate
After also include:
The second product obtained and formaldehyde reducing agent, silane coupler are carried out the 3rd reaction, obtains Graphene
Modified furan resin, described formaldehyde reducing agent includes one or more in Biformyl, tripolycyanamide and polyvinyl alcohol.
12. methods according to claim 11, it is characterised in that described formaldehyde, carbamide, furfuryl alcohol,
The mass ratio of Graphene and formaldehyde reducing agent is (10～25): b:(30～60): (0.001～1): (0.4～1), 0 ＜ b
≤15。
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