CN104151515A - Graphene modified furan resin and preparation method thereof - Google Patents
Graphene modified furan resin and preparation method thereof Download PDFInfo
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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 resin technical field, relate in particular to a kind of Graphene modified furan resin and preparation method thereof.
Background technology
Furane resin are the polymkeric substance taking furfuryl alcohol as basic raw material, in foundry resin binding agent, have a wide range of applications.The appearance of furane resin, makes molding floor's core manufacturing craft of Single unit job lot production that huge variation occur, and it makes the workshop of Single unit job lot production can form the production of mechanize streamline, has occurred the mechanization moulding line taking " high-speed molding circle " as representative.
At present, it is basic raw material that domestic self-hardening furan resin is produced formalin, urea, the furfuryl alcohol that main employing mass concentration is 36.5%, although the technique of each manufacturer is not quite similar, substantially comprise urea, formaldehyde alkali reaction, add the steps such as furfuryl alcohol acid-reaction.
Application number is the preparation method that 201210377741.2 Chinese patent discloses a kind of furan resin for casting, detailed process for to add furfuryl alcohol 774Kg in reactor, start and stir, be that 15% sodium hydroxide solution adjustment pH is 8.5 by mass concentration, add xylogen 56Kg, be warming up to 70 DEG C of reactions 2 hours, cooling, be that 20% oxalic acid solution adjustment pH is 6.5 by mass concentration, under vacuum state, dewater, dewater to the moisture mass content of resin and stop below 1.0%, obtain lignin modification furfuryl alcohol component 794Kg, stand-by.In reactor, add formaldehyde solution (mass concentration is 37%) 316Kg, start and stir, add urea 72Kg, after urea dissolves, regulating pH value with basic solution is 7.8, is warming up to 85 DEG C of reactions 1 hour; Add lignin modification furfuryl alcohol component 294Kg, then react 1 hour; Adjusting material system pH is 3.7, and 95 DEG C of temperature of reaction, react 1.5 hours; Add urea 18Kg, adjusting material system pH is that 7.5,75 DEG C of reactions are after 1 hour, by material system cooling stopped reaction; The 140Kg that dewaters under vacuum condition, adds residual lignin modification furfuryl alcohol component 500Kg, stirs, and blowing obtains the furane resin of 1060Kg.
Although this furane resin that prior art provides have certain intensity, its cohesive strength and toughness are poor, have limited the application of furane resin.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of Graphene modified furan resin, Graphene modified furan resin provided by the invention has good cohesive strength and toughness.
The invention provides a kind of Graphene modified furan resin, prepared through reaction by formaldehyde, furfuryl alcohol and Graphene.
Preferably, the mass ratio of described formaldehyde, furfuryl alcohol and Graphene is (10～25): (30～60): (0.001～1).
Preferably, prepared by formaldehyde, furfuryl alcohol, Graphene and formaldehyde reducing agent, described formaldehyde reducing agent comprise oxalic dialdehyde, one or more in trimeric cyanamide and polyvinyl alcohol.
The preparation method who the invention provides a kind of Graphene modified furan resin, comprises the following steps:
1), formaldehyde, urea and furfuryl alcohol are carried out to the first reaction, obtain the first reaction product; The pH value of described the first reaction is 8～10, and the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours;
2), described the first reaction product and Graphene are carried out to the second reaction, obtain Graphene modified furan resin, the pH value of described the second reaction is 3～3.5, and the described second time of reacting was 1 hour～3 hours.
Preferably, the raw materials of described Graphene is biomass carbon source.
Preferably, the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), protective gas exist condition under, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), protective gas exist condition under, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), protective gas exist condition under, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), protective gas exist condition under, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
Preferably, the mass ratio of described formaldehyde, urea, 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) the second reaction also comprises after finishing:
The second reaction product obtaining and formaldehyde reducing agent, silane coupling agent are carried out to the 3rd reaction, obtain Graphene modified phenolic resins, described formaldehyde reducing agent comprise oxalic dialdehyde, one or more in trimeric cyanamide and polyvinyl alcohol.
Preferably, the mass ratio of described formaldehyde, urea, 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, prepared through reaction by formaldehyde, furfuryl alcohol and Graphene.The present invention is with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, because Graphene is the atomic crystal of plane polynuclear aromatics, therefore be conducive to increase molecular resin bond energy adding of Graphene, thereby make Graphene modified furan resin provided by the invention there is good cohesive strength; Because the connection between the carbon atom of Graphene inside is very pliable and tough, make the toughness of Graphene modified furan resin provided by the invention better simultaneously.
The invention provides a kind of preparation method of Graphene modified furan resin, comprise the following steps: 1), formaldehyde, urea and furfuryl alcohol are carried out to the first reaction, obtain the first reaction product, the pH value of described the first reaction is 8～10, the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours; 2), described the first reaction product and Graphene are carried out to the second reaction, obtain Graphene modified furan resin, the pH value of described the second reaction is 3～3.5, and the described second time of reacting was 1 hour～3 hours.The Graphene modified furan resin that method provided by the invention prepares has good cohesive strength and toughness.In addition, method provided by the invention has been used solid formaldehyde in the process of preparing Graphene modified furan resin, produces without waste water, has avoided negative pressure of vacuum dehydration simultaneously, makes the consumption of the energy lower, has realized cleaner production, has good environment protecting.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of Graphene modified furan resin, prepared through reaction by paraformaldehyde, furfuryl alcohol and Graphene.
The present invention is with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, because Graphene is the atomic crystal of plane polynuclear aromatics, therefore be conducive to increase molecular resin bond energy adding of Graphene, thereby make Graphene modified furan resin provided by the invention there is good cohesive strength; Because the connection between the carbon atom of Graphene inside is very pliable and tough, make the toughness of Graphene modified furan resin provided by the invention better simultaneously.
In the present invention, the purity of described formaldehyde preferably >=96%.The present invention does not have special restriction to the source of described formaldehyde, can be bought and be obtained by market.
The present invention does not have special restriction to the source of described furfuryl alcohol, can be bought and be obtained by market.
In the present invention, the raw materials 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 catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), protective gas exist condition under, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), protective gas exist condition under, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), protective gas exist condition under, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), protective gas exist condition under, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
The present invention preferably, under the effect of catalyzer, carries out catalytic treatment by biomass carbon source, obtains the first intermediate product, and described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese.In the present invention, described biomass carbon source is preferably one or both in Mierocrystalline cellulose and xylogen, and more preferably Mierocrystalline cellulose, most preferably is porous cellulose.In the present invention, the preparation method of described porous cellulose preferably includes following steps:
A), biomass resource is hydrolyzed in acid, obtain lignocellulose, described biomass resource comprises one or more in plant and agriculture and forestry organic waste material;
B), described lignocellulose is processed, obtain porous cellulose, described processing comprises that acid treatment, salt processes or organic solvent processing.
The present invention is preferably hydrolyzed biomass resource in acid, obtains lignocellulose, and described biomass resource comprises one or more in plant and agriculture and forestry organic waste material.In the present invention, more preferably agriculture and forestry organic waste material of described biomass resource, most preferably is one or more in corn stalk, corn cob, kaoliang stalk, beet pulp, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed, is the most preferably corn cob.
In the present invention, the acid of described hydrolysis is preferably one or more in sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid.In the present invention, the sour consumption of described hydrolysis is preferably the 3wt%～20wt% of biomass 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.
Obtain after lignocellulose, the present invention preferably processes described wood fibre, obtains porous cellulose, and described processing comprises acid treatment, salt processing or organic solvent processing.In the present invention, process the more preferably salt processing of method of described lignocellulose, most preferably be acid sulfite process and process or alkali sulfite process processing.In the present invention, the pH of described acid sulfite process processing is preferably 1～7.In the present invention, when described acid sulfite process is processed, the consumption of acid is preferably the 4wt%～30wt% of lignocellulose.In the present invention, when described acid sulfite process is processed, preferably to make liquid-solid ratio be (2～20) to the concentration expressed in percentage by weight of acid: 1.In the present invention, the temperature of described acid sulfite process processing is preferably 70 DEG C～180 DEG C.In the present invention, the time of described acid sulfite process processing be preferably 1 hour～6 hours.
In the present invention, the pH of described alkali sulfite process processing is preferably 7～14.In the present invention, when described alkali sulfite process is processed, the consumption of alkali is preferably the 4wt%～30wt% of lignocellulose.In the present invention, when described alkali sulfite process is processed, preferably to make liquid-solid ratio be (2～20) to the concentration expressed in percentage by weight of alkali: 1.In the present invention, the temperature of described alkali sulfite process processing is preferably 70 DEG C～180 DEG C.In the present invention, the time of described alkali sulfite process processing be preferably 1 hour～6 hours.
In the present invention, the catalyzer of preparing described Graphene preferably includes the chlorate of prussiate, iron content hydrochlorate, the cobalt of chlorate, the iron of iron, containing the chlorate of cobaltates, nickel with containing one or more in nickelate; More preferably comprise that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close one or more in potassium ferrite, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt and nickelous acetate.
In the present invention, while preparing described Graphene, the mass ratio of catalyzer 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.In the present invention, the time of described catalytic treatment be preferably 2 hours～10 hours.
Obtain after the first intermediate product, under the condition that the present invention preferably exists at protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, this protective gas is designated as to the first protective gas; Described the first temperature is 20 DEG C～40 DEG C, and described the second temperature is 300 DEG C～400 DEG C.In the present invention, the temperature rise rate that described the first intermediate product is warming up to the second temperature from the first temperature is preferably 5 DEG C/min～20 DEG C/min.In the present invention, the soaking time of described the first intermediate product from the first temperature is warming up to the second temperature be preferably 4 hours～8 hours.In the present invention, described the first protective gas is preferably one or more in nitrogen and rare gas element, more preferably nitrogen.
Obtain after the second intermediate product, under the condition that the present invention preferably exists at protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product, this protective gas is designated as to the second protective gas; Described the 3rd temperature is 800 DEG C～900 DEG C.In the present invention, the temperature rise rate that described the 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, the soaking time of described the second intermediate product from the second temperature is warming up to the 3rd temperature be preferably 3.5 hours～7 hours.In the present invention, the kind of described the second protective gas is consistent with the kind of the first protective gas described in technique scheme, does not repeat them here.
Obtain after the 3rd intermediate product, under the condition that the present invention preferably exists at protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, this protective gas is designated as to the 3rd protective gas; Described the 4th temperature is 1100 DEG C～1300 DEG C.In the present invention, the temperature rise rate that described the 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, the soaking time of described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature be preferably 6 hours～8 hours.In the present invention, the kind of described the 3rd protective gas is consistent with the kind of the first protective gas described in technique scheme, does not repeat them here.
Obtain after the 4th intermediate product, under the condition that the present invention preferably exists at protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, this protective gas is designated as to the 4th protective gas; Described the 5th temperature is 900 DEG C～1000 DEG C.In the present invention, described the 4th intermediate product is preferably 30 DEG C/min～50 DEG C/min from the rate of temperature fall of the 4th greenhouse cooling to the five temperature.In the present invention, the soaking time of described the 4th intermediate product from the 4th greenhouse cooling to the five temperature be preferably 2 hours～4 hours.In the present invention, the kind of described the 4th protective gas is consistent with the kind of the first protective gas described in technique scheme, does not repeat them here.
In the present invention, described the first protective gas, the second protective gas, the 3rd protective gas and the 4th protective gas can be identical, also can be different; Described the first protective gas, the second protective gas, the 3rd protective gas are preferably identical with the 4th protective gas.
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 is (15～20): (40～50): (0.1～0.6).
In the present invention, described Graphene modified furan resin is preferably prepared by formaldehyde, furfuryl alcohol, Graphene and formaldehyde reducing agent, described formaldehyde reducing agent comprise oxalic dialdehyde, in trimeric cyanamide and polyvinyl alcohol one or more.In the present invention, described formaldehyde reducing agent more preferably oxalic dialdehyde, trimeric cyanamide or polyvinyl alcohol.In the present invention, described formaldehyde reducing agent can react with residual formaldehyde, the content of the Graphene modified furan resin Free Aldehyde that the present invention prepares is reduced, and then improve the moulding environment of Foundry Production Worksite, is conducive to the healthy of 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 have special restriction to the source of described formaldehyde reducing agent, can be bought and be obtained by market.
In the present invention, described Graphene modified furan resin is preferably prepared by formaldehyde, furfuryl alcohol, Graphene and silane coupling agent.In the present invention, described silane coupling agent add the cohesive strength that can further improve Graphene modified furan resin provided by the invention.The present invention does not have special restriction to the kind of described silane coupling agent and source, adopts silane coupling agent well known to those skilled in the art, can be bought and be obtained by market.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 coupling agent 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 is more preferably prepared by formaldehyde, furfuryl alcohol, Graphene, formaldehyde reducing agent and silane coupling agent.In the present invention, the mass ratio of described formaldehyde, furfuryl alcohol, Graphene, formaldehyde reducing 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 preparation method who the invention provides a kind of Graphene modified furan resin, comprises the following steps:
1), formaldehyde, urea and furfuryl alcohol are carried out to the first reaction, obtain the first reaction product; The pH value of described the first reaction is 8～10, and the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours;
2), described the first reaction product and Graphene are carried out to the second reaction, obtain Graphene modified furan resin, the pH value of described the second reaction is 3～3.5, and the described second time of reacting was 1 hour～3 hours.
The Graphene modified furan resin that method provided by the invention prepares has good cohesive strength and toughness.In addition, method provided by the invention has been used formaldehyde in the process of preparing Graphene modified furan resin, therefore produce without waste water, and avoided negative pressure of vacuum dehydration, can make the consumption of the energy lower, realize cleaner production, there is good environment protecting.
In the present invention, the mass ratio of described formaldehyde, urea, furfuryl alcohol and Graphene is 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 is (15～20): (4～10): (40～50): (0.6～0.7): (0.1～0.6).
Formaldehyde, urea and furfuryl alcohol are carried out the first reaction by the present invention, obtains the first reaction product; The pH value of described the first reaction is 8～10, and the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours.In the present invention, the pH value of described the first reaction is preferably 9.In the present invention, the temperature of described the first reaction is preferably 95 DEG C～110 DEG C, more preferably 100 DEG C.In the present invention, the time of described the first reaction is preferably 2 hours.In the present invention, the pressure of described the first reaction is preferably 0.15MPa～0.25MPa, more preferably 0.2MPa.
The present invention does not have special restriction to the source of described urea, can be bought and be obtained by market.In the present invention, the kind of described formaldehyde, Graphene, furfuryl alcohol is consistent with kind and the source of paraformaldehyde, Graphene and furfuryl alcohol described in technique scheme with source, does not repeat them here.
The present invention preferably carries out the first reaction by formaldehyde, urea, furfuryl alcohol and alkali lye, obtains the first reaction product.The present invention does not have special restriction to the kind of alkali in described alkali lye, adopts basic cpd well known to those skilled in the art.Mass concentration and the consumption of the present invention to described alkali lye do not have special restriction, and it is 8～10 that described alkali lye can make the pH value of described the first reaction.
Obtain after the first reaction product, described the first reaction product and Graphene are carried out the second reaction by the present invention, obtains Graphene modified furan resin, and the pH value of described the second reaction is 3～3.5, and the time of described the second reaction is 1 hour～3 hours.In the present invention, the pH value of described the second reaction is preferably 3.2.In the present invention, the time of described the second reaction is preferably 2 hours.In the present invention, the temperature of described the second reaction is preferably 100 DEG C～105 DEG C, more preferably 100 DEG C.
The present invention preferably carries out described the second reaction under the effect of an acidic catalyst.In the present invention, described an acidic catalyst is preferably the aqueous formic acid that Lewis acid or mass concentration are 40%, the aqueous formic acid that more preferably mass concentration is 40%.In the present invention, the consumption of described an acidic catalyst is preferably described the second reaction pH value is provided is 3～3.5 reaction conditions.
Described second reacted after, the present invention preferably carries out the 3rd reaction by the second reaction product obtaining and formaldehyde reducing agent, silane coupling agent, obtains Graphene modified furan resin.In the present invention, kind, source and the consumption of described formaldehyde reducing agent and silane coupling agent is consistent with kind, source and the consumption of formaldehyde reducing agent described in technique scheme and silane coupling agent, does not repeat them here.In the present invention, the temperature of described the 3rd reaction is preferably 50 DEG C～70 DEG C, more preferably 55 DEG C～65 DEG C, most preferably is 60 DEG C.
According to the standard of GB/T265-1988 " petroleum products kinematic viscosity assay method ", the viscosity of testing Graphene modified furan resin provided by the invention, test result is that the viscosity of Graphene modified furan resin provided by the invention is 20 mp
a.s～40 mp
a.s.According to the standard of JB/T7526-2008 " casting self-hardening furan resin ", test cohesive strength and the toughness of Graphene modified furan resin provided by the invention, test result is, 24 hours tensile strength >=2.0MPa of Graphene modified furan resin provided by the invention, 24 hours bending strength >=10 MPa.
The invention provides a kind of Graphene modified furan resin, prepared through reaction by formaldehyde, furfuryl alcohol and Graphene.The present invention is with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, because Graphene is the atomic crystal of plane polynuclear aromatics, therefore be conducive to increase molecular resin bond energy adding of Graphene, thereby make Graphene modified furan resin provided by the invention there is good cohesive strength; Because the connection between the carbon atom of Graphene inside is very pliable and tough, make the toughness of Graphene modified furan resin provided by the invention better simultaneously.
The preparation method who the invention provides a kind of Graphene modified furan resin, comprises the following steps: 1), formaldehyde, urea and furfuryl alcohol are carried out to the first reaction, obtain the first reaction product; The pH value of described the first reaction is 8～10, and the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours; 2), described the first reaction product and Graphene are carried out to the second reaction, obtain Graphene modified furan resin, the pH value of described the second reaction is 3～3.5, and the described second time of reacting was 1 hour～3 hours.The Graphene modified furan resin that method provided by the invention prepares has good cohesive strength and toughness.In addition, method provided by the invention has been used formaldehyde in the process of preparing Graphene modified furan resin, therefore produce without waste water, and avoided negative pressure of vacuum dehydration, can make the consumption of the energy lower, realize cleaner production, there is good environment protecting.
In following examples of the present invention, raw material used is commercial goods.
Embodiment 1
At 90 DEG C, corn cob is carried out in sulfuric acid to the hydrolysis of 10min, obtain lignocellulose, the quality of described sulfuric acid is 3% of described corn cob quality;
At 70 DEG C, described lignocellulose is carried out to the acid sulfite process processing of 1 hour, obtain porous cellulose, pH value in described acid sulfite process treating processes is 1, acid is sulfuric acid, sulphite is magnesium sulfite, and the quality of described sulfuric acid is 4% of described lignocellulose quality, and liquid-solid ratio is 2:1.
The porous cellulose obtaining is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and Manganous chloride tetrahydrate, at 20 DEG C, stir and within 2 hours, carry out catalytic treatment, the mass ratio of described Manganous chloride tetrahydrate and porous cellulose is 0.01:1; Product after the catalytic treatment obtaining is dry at 70 DEG C, obtain first intermediate product of water content lower than 10wt%.
Described the first intermediate product is placed in to charring furnace, gas intake using 200mL/min passes into nitrogen as protection gas in described carbide furnace, described the first intermediate product is warming up to 300 DEG C with the speed of 5 DEG C/min from 25 DEG C, is incubated 4 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 800 DEG C with the speed of 20 DEG C/min from 300 DEG C, is incubated 3.5 hours, obtain the 3rd intermediate product; Described the 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, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 900 DEG C with the speed of 30 DEG C/min from 1100 DEG C, is incubated 2 hours; The 4th intermediate product after described cooling is cooled to 60 DEG C.
At 60 DEG C, in the aqueous sodium hydroxide solution that is 3% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 4 hours, obtain the first washed product; At 70 DEG C, in the aqueous hydrochloric acid that is 4% in mass concentration by described the first washed product, wash 4 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
Embodiment 2
At 180 DEG C, corn cob is carried out in nitric acid to the hydrolysis of 10h, obtain lignocellulose, the quality of described nitric acid is 20% of described corn cob quality;
At 180 DEG C, described lignocellulose is carried out to the acid sulfite process processing of 6 hours, obtain porous cellulose, pH value in described acid sulfite process treating processes is 7, acid is sulfuric acid, sulphite is S-WAT, and the quality of described sulfuric acid is 30% of described lignocellulose quality, and liquid-solid ratio is 20:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and iron nitrate, at 180 DEG C, stir and within 10 hours, carry out catalytic treatment, the mass ratio of described iron nitrate and porous cellulose is 2:1; Product after the catalytic treatment obtaining is dry at 120 DEG C, obtain first intermediate product of water content lower than 5wt%.
Described the first intermediate product is placed in to charring furnace, gas intake using 800mL/min passes into argon gas as protection gas in described carbide furnace, described the first intermediate product is warming up to 400 DEG C with the speed of 20 DEG C/min from 20 DEG C, is incubated 8 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 900 DEG C with the speed of 50 DEG C/min from 400 DEG C, is incubated 7 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1300 DEG C with the speed of 60 DEG C/min from 900 DEG C, is incubated 8 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 1000 DEG C with the speed of 50 DEG C/min from 1300 DEG C, is incubated 4 hours; The 4th intermediate product after described cooling is cooled to 20 DEG C.
At 120 DEG C, in the aqueous sodium hydroxide solution that is 55% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 24 hours, obtain the first washed product; At 150 DEG C, in the aqueous hydrochloric acid that is 10% in mass concentration by described the first washed product, wash 24 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
Embodiment 3
At 130 DEG C, corn cob is carried out in hydrochloric acid to the hydrolysis of 5h, obtain lignocellulose, the quality of described hydrochloric acid is 10% of described corn cob quality;
At 120 DEG C, described lignocellulose is carried out to the acid sulfite process processing of 4 hours, obtain porous cellulose, pH value in described acid sulfite process treating processes is 3, acid is sulfuric acid, sulphite is ammonium sulphite, and the quality of described sulfuric acid is 18% of described lignocellulose quality, and liquid-solid ratio is 10:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and rose vitriol, at 50 DEG C, stir and within 5 hours, carry out catalytic treatment, the mass ratio of described rose vitriol and porous cellulose is 0.1:1; Product after the catalytic treatment obtaining is dry at 90 DEG C, obtain first intermediate product of water content lower than 8wt%.
Described the first intermediate product is placed in to charring furnace, gas intake using 400mL/min passes into nitrogen as protection gas in described carbide furnace, described the first intermediate product is warming up to 320 DEG C with the speed of 10 DEG C/min from 40 DEG C, is incubated 5 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 820 DEG C with the speed of 30 DEG C/min from 320 DEG C, is incubated 5 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1150 DEG C with the speed of 54 DEG C/min from 820 DEG C, is incubated 7 hours, obtain the 4th intermediate product; Described the 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, in the ammoniacal liquor that is 10% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 8 hours, obtain the first washed product; At 90 DEG C, in the aqueous hydrochloric acid that is 6% in mass concentration by described the first washed product, wash 8 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
Embodiment 4
The disclosed method of Chinese patent that is 200810113596.0 according to application number is prepared Graphene, and detailed process is:
Silicon substrate is cleaned to post-drying with deionized water, ethanol, acetone successively, is that the zinc sulphide of 100 nanometers is as catalyzer by gas phase deposition technology in surface of silicon deposition a layer thickness;
The described silicon substrate that deposits zinc sulphide is placed in to clean silica tube middle part, silica tube is put into electric furnace, make the middle part of silica tube be positioned at the central zone of electric furnace, then in silica tube, pass into the hydrogen of 100sccm and the argon gas gas mixture of 100sccm after 60 minutes, start heating;
When the temperature of electric furnace central zone is during up to 850 DEG C, in electric furnace, pass into ethanol as carbon source, reaction starts to carry out;
Reaction is carried out, after 20 minutes, stopping passing into ethanol, closes electric furnace simultaneously, continues to pass into gas mixture to the temperature of the hydrogen of 100sccm and the argon gas of 100sccm and is down to room temperature, obtains depositing the substrate of Graphene;
The hydrochloric acid soln that the described substrate that deposits Graphene is put into 0.1mol/L soaks 60 minutes, removes zinc sulphide, then cleans and dries with deionized water, obtains Graphene.
Embodiment 5
Close bleeder valve at the bottom of still, open the charging valve of reactor, under the condition stirring, in described reactor, add furfuryl alcohol, the urea of 6.5g and the paraformaldehyde of 15g of 40g and the aqueous sodium hydroxide solution that mass concentration is 15%, obtain pH value and be 9.2 mixed solution;
Open steam valve, maintain vapor pressure 0.15MPa, in 30 minutes, described reactor is warming up to 100 DEG C, the mixed solution in described reactor is carried out to first reaction of 100 minutes, obtain the first reaction product;
After described the first reaction finishes, opening water coolant, described the first reaction product is cooled to 50 DEG C, is the Graphene that the embodiment 1 of 40% aqueous formic acid and 2g prepares to adding mass concentration in described the first reaction product; , it is 4.5 that the consumption of the aqueous formic acid that described mass concentration is 40% makes the pH value of described the first reaction product and Graphene mixture;
Open steam valve, the mixture of described the first reaction product and Graphene was warming up to 100 DEG C in 30 minutes, carry out second reaction of 120 minutes, obtain the second reaction product;
Described second reacted after, described the second reaction product is cooled to 60 DEG C, stir condition under, in described the second reaction product, add the KH550 type coupling agent of 0.6g and the oxalic dialdehyde of 5g to carry out the 3rd reaction, obtain Graphene modified furan resin.
According to the method described in technique scheme, the viscosity of the Graphene modified furan resin that the test embodiment of the present invention 5 prepares, test result is that the viscosity of the Graphene modified furan resin that the embodiment of the present invention 5 prepares is 22mp
a.s.
According to the method described in technique scheme, cohesive strength and the toughness of the Graphene modified furan resin that the test embodiment of the present invention 5 prepares, test result is, the 24 hours tensile strength of Graphene modified furan resin that the embodiment of the present invention 5 prepares is 2.38MPa, 24 hours bending strengths are 10.2MPa, and cohesive strength and toughness are better.
According to the standard of JB/T7526-2008 " certainly hard furans for casting ", the content of the Graphene modified furan resin Free Aldehyde that the test embodiment of the present invention 5 prepares, test result is that the mass content of the Graphene modified furan resin Free Aldehyde that the embodiment of the present invention 5 prepares is 0.02%.
Embodiment 6
Close bleeder valve at the bottom of still, open the charging valve of reactor, under the condition stirring, in described reactor, add furfuryl alcohol, the urea of 7g and the paraformaldehyde of 20g of 40g and the aqueous sodium hydroxide solution that mass concentration is 15%, obtain pH value and be 9.1 mixed solution;
Open steam valve, maintain vapor pressure 0.25MPa, in 30 minutes, described reactor is warming up to 105 DEG C, the mixed solution in described reactor is carried out to first reaction of 100 minutes, obtain the first reaction product;
After described the first reaction finishes, open water coolant, described the first reaction product is cooled to 50 DEG C, is that to make the pH value of the mixture of described the first reaction product and Graphene be 4.6 for the consumption of the aqueous formic acid that mass concentration is 40% described in the Graphene for preparing of the embodiment 2 of 40% aqueous formic acid and 2.5g to adding mass concentration in described the first reaction product;
Open steam valve, the mixture of described the first reaction product and Graphene was warming up to 105 DEG C in 40 minutes, carry out second reaction of 100 minutes, obtain the second reaction product;
Described second reacted after, described the second reaction product is cooled to 60 DEG C, stir condition under, in described the second reaction product, add the KH560 type coupling agent of 0.6g and the trimeric cyanamide of 2g to carry out the 3rd reaction, obtain Graphene modified furan resin.
According to the method described in technique scheme, the viscosity of the Graphene modified furan resin that the test embodiment of the present invention 6 prepares, test result is that the viscosity of the Graphene modified furan resin that the embodiment of the present invention 6 prepares is 27mp
a.s.
According to the method described in technique scheme, cohesive strength and the toughness of the Graphene modified furan resin that the test embodiment of the present invention 6 prepares, test result is, the 24 hours tensile strength of Graphene modified furan resin that the embodiment of the present invention 6 prepares is 2.25MPa, 24 hours bending strengths are 10.2MPa, and cohesive strength and toughness are better.
According to the standard of JB/T7526-2008 " certainly hard furans for casting ", the content of the Graphene modified furan resin Free Aldehyde that the test embodiment of the present invention 6 prepares, test result is that the mass content of the Graphene modified furan resin Free Aldehyde that the embodiment of the present invention 6 prepares is 0.01%.
Embodiment 7
Close bleeder valve at the bottom of still, open the charging valve of reactor, under the condition stirring, in described reactor, add furfuryl alcohol, the urea of 7.5g and the paraformaldehyde of 22g of 45g and the aqueous sodium hydroxide solution that mass concentration is 15%, obtain pH value and be 8.95 mixed solution;
Open steam valve, maintain vapor pressure 0.2MPa, in 30 minutes, described reactor is warming up to 103 DEG C, the mixed solution in described reactor is carried out to first reaction of 100 minutes, obtain the first reaction product;
After described the first reaction finishes, open water coolant, described the first reaction product is cooled to 50 DEG C, be the Graphene that the embodiment 3 of 40% aqueous formic acid and 2.3g prepares to adding mass concentration in described the first reaction product, it is 4.45 that the consumption of the aqueous formic acid that described mass concentration is 40% makes the pH value of the mixture of described the first reaction product and Graphene;
Open steam valve, the mixture of described the first reaction product and Graphene was warming up to 103 DEG C in 45 minutes, carry out second reaction of 100 minutes, obtain the second reaction product;
Described second reacted after, described the second reaction product is cooled to 60 DEG C, stir condition under, in described the second reaction product, add the coupling agent of KH560 type of 0.6g and the polyvinyl alcohol of 2g to carry out the 3rd reaction, obtain Graphene modified furan resin.
According to the method described in technique scheme, the viscosity of the Graphene modified furan resin that the test embodiment of the present invention 7 prepares, test result is that the viscosity of the Graphene modified furan resin that the embodiment of the present invention 7 prepares is 26mp
a.s.
According to the method described in technique scheme, cohesive strength and the toughness of the Graphene modified furan resin that the test embodiment of the present invention 7 prepares, test result is, the 24 hours tensile strength of Graphene modified furan resin that the embodiment of the present invention 7 prepares is 2.31MPa, 24 hours bending strengths are 10.26MPa, and cohesive strength and toughness are better.
According to the standard of JB/T7526-2008 " certainly hard furans for casting ", the content of the Graphene modified furan resin Free Aldehyde that the test embodiment of the present invention 7 prepares, test result is that the mass content of the Graphene modified furan resin Free Aldehyde that the embodiment of the present invention 7 prepares is 0.
Embodiment 8
Close bleeder valve at the bottom of still, open the charging valve of reactor, under the condition stirring, in described reactor, add furfuryl alcohol, the urea of 6.5g and the paraformaldehyde of 15g of 40g and the aqueous sodium hydroxide solution that mass concentration is 15%, obtain pH value and be 9.2 mixed solution;
Open steam valve, maintain vapor pressure 0.15MPa, in 30 minutes, described reactor is warming up to 100 DEG C, the mixed solution in described reactor is carried out to first reaction of 100 minutes, obtain the first reaction product;
Described first reacted after, open water coolant, described the first reaction product is cooled to 50 DEG C, be the Graphene that the embodiment 4 of 40% aqueous formic acid and 2g prepares to adding mass concentration in described the first reaction product, it is 4.5 that the consumption of the aqueous formic acid that described mass concentration is 40% makes the pH value of described the first reaction product and Graphene mixture;
Open steam valve, the mixture of described the first reaction product and Graphene was warming up to 100 DEG C in 30 minutes, carry out second reaction of 120 minutes, obtain the second reaction product;
Described second reacted after, described the second reaction product is cooled to 60 DEG C, stir condition under, in described the second reaction product, add the KH550 type coupling agent of 0.6g and the oxalic dialdehyde of 2.5g to carry out the 3rd reaction, obtain Graphene modified furan resin.
According to the method described in technique scheme, the viscosity of the Graphene modified furan resin that the test embodiment of the present invention 8 prepares, test result is that the viscosity of the Graphene modified furan resin that the embodiment of the present invention 8 prepares is 40mp
a.s.
According to the method described in technique scheme, cohesive strength and the toughness of the Graphene modified furan resin that the test embodiment of the present invention 8 prepares, test result is, the 24 hours tensile strength of Graphene modified furan resin that the embodiment of the present invention 8 prepares is 2MPa, 24 hours bending strengths are 10MPa, and cohesive strength and toughness are better.
According to the standard of JB/T7526-2008 " certainly hard furans for casting ", the content of the Graphene modified furan resin Free Aldehyde that the test embodiment of the present invention 8 prepares, test result is that the mass content of the Graphene modified furan resin Free Aldehyde that the embodiment of the present invention 8 prepares is 0.05%.
Comparative example 1
The disclosed method of Chinese patent that is 201210377741.2 according to application number prepares furane resin, and detailed process is:
In reactor, add furfuryl alcohol 774Kg, start and stir, it is 8.5 that the sodium hydroxide solution that is 15% by mass concentration is adjusted pH, adds xylogen 56Kg, is warming up to 70 DEG C of reactions 2 hours, cooling, the oxalic acid solution that is 20% by mass concentration adjust pH be 6.5, under vacuum state, dewater, dewater to the moisture mass concentration of resin be to stop below 1.0%, obtain lignin modification furfuryl alcohol component 794Kg, stand-by.
In reactor, add formaldehyde solution (mass concentration is 37%) 316Kg, start and stir, add urea 72Kg, after urea dissolves, regulating pH value with basic solution is 7.8, is warming up to 85 DEG C of reactions 1 hour; Add lignin modification furfuryl alcohol component 294Kg, then react 1 hour; Adjusting material system pH is 3.7, at 95 DEG C of temperature of reaction, reacts 1.5 hours; Add urea 18Kg, adjusting material system pH is 7.5, reacts after 1 hour, by material system cooling stopped reaction at 75 DEG C; Under vacuum condition, add dewatering agent 140Kg, add residual lignin modification furfuryl alcohol component 500Kg, stir, obtain furane resin.
According to the method described in technique scheme, test cohesive strength and the toughness of the Graphene modified furan resin that comparative example 1 of the present invention prepares, test result is, the Graphene modified furan resin tensile strength of 24 hours that comparative example 1 of the present invention prepares is 1.84MPa, and the bending strength of 24 hours is 7.4MPa.
According to the standard of JB/T7526-2008 " certainly hard furans for casting ", test the content of the Graphene modified furan resin Free Aldehyde that comparative example 1 of the present invention prepares, test result is that the mass content of the Graphene modified furan resin Free Aldehyde that comparative example 1 of the present invention prepares is 0.3%.
As seen from the above embodiment, the invention provides a kind of Graphene modified furan resin, prepared through reaction by paraformaldehyde, furfuryl alcohol and Graphene.The present invention is with formaldehyde and furfuryl alcohol and Graphene synthesizing graphite alkene modified furan resin, because Graphene is the atomic crystal of plane polynuclear aromatics, therefore be conducive to increase molecular resin bond energy adding of Graphene, thereby make Graphene modified furan resin provided by the invention there is good cohesive strength; Because the connection between the carbon atom of Graphene inside is very pliable and tough, make the toughness of Graphene modified furan resin provided by the invention better simultaneously.
The preparation method who the invention provides a kind of Graphene modified furan resin comprises the following steps: 1), formaldehyde, urea and furfuryl alcohol are carried out to the first reaction, obtain the first reaction product; The pH value of described the first reaction is 8～10, and the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours; 2), described the first reaction product and Graphene are carried out to the second reaction, obtain Graphene modified furan resin, the pH value of described the second reaction is 3～3.5, and the described second time of reacting was 1 hour～3 hours.The Graphene modified furan resin that method provided by the invention prepares has good cohesive strength and toughness.In addition, method provided by the invention has been used formaldehyde in the process of preparing Graphene modified furan resin, therefore produce without waste water, and avoided negative pressure of vacuum dehydration, can make the consumption of the energy lower, realize cleaner production, there is good environment protecting.
Claims (12)
1. a Graphene modified furan resin, is prepared through reaction by formaldehyde, furfuryl alcohol and Graphene.
2. Graphene modified furan resin according to claim 1, is characterized in that, the mass ratio of described formaldehyde, furfuryl alcohol and Graphene is (10～25): (30～60): (0.001～1).
3. Graphene modified furan resin according to claim 1, is characterized in that, prepared by formaldehyde, furfuryl alcohol, Graphene and formaldehyde reducing agent, described formaldehyde reducing agent comprise oxalic dialdehyde, one or more in trimeric cyanamide and polyvinyl alcohol.
4. a preparation method for Graphene modified furan resin, comprises the following steps:
1), formaldehyde, urea and furfuryl alcohol are carried out to the first reaction, obtain the first reaction product; The pH value of described the first reaction is 8～10, and the temperature of described the first reaction is 90 DEG C～120 DEG C, and the time of described the first reaction is 1 hour～3 hours;
2), described the first reaction product and Graphene are carried out to the second reaction, obtain Graphene modified furan resin, the pH value of described the second reaction is 3～3.5, and the described second time of reacting was 1 hour～3 hours.
5. Graphene modified furan resin according to claim 4, is characterized in that, the raw materials of described Graphene is biomass carbon source.
6. Graphene modified furan resin according to claim 5, is characterized in that, the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyzer, biomass carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyzer comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), protective gas exist condition under, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), protective gas exist condition under, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), protective gas exist condition under, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), protective gas exist condition under, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
7. method according to claim 4, is characterized in that, the mass ratio of described formaldehyde, urea, furfuryl alcohol and Graphene is (10～25): a:(30～60): (0.001～1), 0 < a≤15.
8. method according to claim 4, is characterized in that, described step 1) in the first reaction pressure be 0.15MPa～0.25MPa.
9. method according to claim 4, is characterized in that 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.
10. method according to claim 4, is characterized in that, described step 2) in second reaction pH value be 3.2.
11. methods according to claim 4, is characterized in that, described step 2) the second reaction also comprises after finishing:
The second reaction product obtaining and formaldehyde reducing agent, silane coupling agent are carried out to the 3rd reaction, obtain Graphene modified furan resin, described formaldehyde reducing agent comprise oxalic dialdehyde, one or more in trimeric cyanamide and polyvinyl alcohol.
12. methods according to claim 11, it is characterized in that, the mass ratio of described formaldehyde, urea, furfuryl alcohol, Graphene and formaldehyde reducing agent is (10～25): b:(30～60): (0.001～1): (0.4～1), 0 < b≤15.
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| CN114307971A (en) * | 2021-12-20 | 2022-04-12 | 辽宁工业大学 | Preparation method of functionalized graphene oxide for adsorbing lead ions |
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| EP3192902A4 (en) * | 2014-11-20 | 2017-08-09 | Jinan Shengquan Group Share Holding Co., Ltd. | Graphene-containing viscose fibre and preparation method therefor |
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| CN112222351A (en) * | 2020-09-28 | 2021-01-15 | 宁夏共享化工有限公司 | Furan resin and production method thereof |
| CN112222351B (en) * | 2020-09-28 | 2022-08-05 | 宁夏共享化工有限公司 | Furan resin and production method thereof |
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