CN103709346A - Preparation method of phenolic resin aerogel - Google Patents
Preparation method of phenolic resin aerogel Download PDFInfo
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- CN103709346A CN103709346A CN201310617223.8A CN201310617223A CN103709346A CN 103709346 A CN103709346 A CN 103709346A CN 201310617223 A CN201310617223 A CN 201310617223A CN 103709346 A CN103709346 A CN 103709346A
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Abstract
The invention discloses a preparation method of phenolic resin aerogel. The preparation method is characterized in that chitosan, one or more acid, one or more filling materials, one or more phenols, one or more aldehydes, and water or a water-anhydrous ethanol mixture are mixed; the mixture undergoes a hydrothermal reaction to produce phenolic resin organogel; the phenolic resin organogel is immersed in an organic solvent for replacement; and the replacement product is subjected to supercritical CO2 drying so that the phenolic resin aerogel is obtained. The preparation method has simple processes and safe and reliable reactions and realizes adjustment of a structure and mechanical properties of the phenolic resin organogel. The structure and density of the phenolic resin aerogel obtained by drying and porosity and a specific surface area of the derivative porous carbon material obtained by carbonization of the phenolic resin aerogel are adjusted and controlled well.
Description
Technical field
The invention belongs to field of material synthesis technology, more particularly, relate to a kind of preparation method of phenolic resin gel.
Background technology
Resol, as one of three large synthetic resins, has experienced the developing history of more than 100 year, has been widely used in so far the every field such as defence and military and building, traffic, chemical industry and the energy.At present, resol is prepared the porous carbon materials of multiple nanostructure and is caused people's interest as carbon source.Porous carbon materials is because it has obtained paying close attention to widely compared with high specific surface area, controlled micro-nano aperture and excellent electric conductivity, in every field, there is potential using value in for example absorption, filtering separation, photonic crystal, support of the catalyst, electrochemical capacitor, lithium ion battery, solar cell, Chu Qing and sensor field.Resol is not only with low cost, and can be synthetic under the condition of acidity, alkalescence or salt.Yet synthesizing of phenolic resin gel is all faced with the great number of issues such as cost is high, reaction difficulty is controlled and can not regulate and control at present.Therefore, make the derivative porous carbon materials of resol can obtain large-scale application, adopt the synthetic three-dimensional phenolic resin gel of method of simple economy to become problem demanding prompt solution.
At present, phenolic resin gel has prepared research widely, and wherein, Resorcinol and formaldehyde are the most frequently used raw material.U.S. < < JACS > > (Journal of the American Chemical Society, 2011 133 phase 11378 pages) has reported novolak resin gel under employing Resorcinol, formaldehyde and pluronic F127 alkaline condition; Britain < < materials chemistry magazine > > (Journal of Materials Chemistry A, 13462 pages of 1 phases in 2013) reported that employing Resorcinol and formaldehyde are raw material, acidic catalyst synthesizes soft resol aerogel.But all there is following problem in aforesaid method, adopt Resorcinol to be raw material, expensive, be not suitable on a large scale synthetic, and have compared with high activity and be difficult for storage owing to being rich in hydroxyl on phenyl ring, and the method reaction times is generally longer, poor controllability.
Template is also another important method of novolak resin, for example, Britain < < energy and environment science > > (Energy & Environmental Science, 652 pages of 6 phases in 2013) reported that employing ionic liquid is template, Resorcinol and formaldehyde are raw material, and hexanediamine is done catalysis and prepared resol porous carbon; Britain < < materials chemistry magazine > > (Journal of Materials Chemistry A, 2012 22 phase 21852 pages) has reported that employing ionic liquid does the synthetic resorcinol-formaldehyde resin gel of template.But not only there are the problems referred to above in the method, and adopted synthetic complexity and ionic liquid cost used higher, thereby limited greatly its application.
Summary of the invention
For solving the existing weak point of above-mentioned prior art, the invention provides the preparation method of the resol aerogel that a kind of technique is simple, cost is low, to realizing the controlled of phenolic resin gel structure, density, ultimate compression strength and Young's modulus.
Technical solution problem of the present invention, adopts following technical scheme:
The preparation method of resol aerogel of the present invention, its feature is: comprise the following steps:
A1, chitosan is dispersed in water or water/dehydrated alcohol mixing solutions, then adds acid, stir and obtain chitosan colloidal sol;
Or add weighting material and chitosan in water or water/dehydrated alcohol mixing solutions, and after stirring, add again acid, stir and obtain chitosan colloidal sol;
B1, in described chitosan colloidal sol, add phenols, after stirring, then add aldehydes, acquisition mixed sols again stirs;
C1, described mixed sols is packed in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D1, described resol organogel is immersed in to organic solvent replaces to organic solvent variable color, change organic solvent colourless to the organic solvent soaking after resol organogel, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
Or described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel;
Preferably, the described phenols in step b1 is the several of a kind of or any proportioning in phenol, Resorcinol, Phloroglucinol, cresols, xylenol, mixture cresol, nonyl phenol;
The preparation method of resol aerogel of the present invention also can carry out as follows:
A2, phenols is joined in water/dehydrated alcohol mixing solutions, under 40～100 ℃ of conditions, heated and stirred, to dissolving, obtains mixing solutions;
Or phenols is joined in water/dehydrated alcohol mixing solutions, under 40～100 ℃ of conditions, heated and stirred is extremely dissolved, then adds weighting material, stirs and obtains mixing solutions;
B2, chitosan is dispersed in described mixing solutions, then adds successively acid and aldehyde, stir and obtain mixed sols;
C2, described mixed sols is packed in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D2, described resol organogel is immersed in organic solvent and is replaced to organic solvent variable color, change organic solvent colourless to the organic solvent soaking after resol organogel, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
Or described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel.
Preferably, the described phenols in step b2 is the several of a kind of or any proportioning in Ortho-Aminophenol, 3-amino-phenol, PAP, Resorcinol, Phloroglucinol, cresols, mixture cresol, nonyl phenol, octyl phenol, cardanol, aralkyl phenol, dihydroxyphenyl propane;
Preparation method of the present invention, its feature is also: in described water/dehydrated alcohol mixing solutions, the volume parts of dehydrated alcohol is 1/3-2/3;
Preferably, described aldehydes is the several of a kind of or any proportioning in formaldehyde, paraformaldehyde, furfural, acetaldehyde;
Preferably, described acid is the several of a kind of or any proportioning in formic acid, acetic acid, oxalic acid, tartrate, hydrochloric acid, sulfuric acid, nitric acid;
Preferably, described weighting material is the several of a kind of or any proportioning in clay, polynite, wilkinite, silicon-dioxide, polystyrene; Weighting material is only for strengthening the physical strength of gel and the three-dimensional structure of supplemental support phenolic resin gel, alternative interpolation, and addition can appropriate change, or does not add;
Preferably, described organic solvent is acetone or dehydrated alcohol.
The ratio of the quality of described chitosan, the volume of described acid, the amount of substance of described phenol and the amount of substance of described aldehyde is (0.1g～0.5g): (0.2ml～0.8ml): (0.01mol～0.14mol): (0.02mol～0.04mol).
The temperature of described hydro-thermal reaction is 70 ℃～200 ℃, and the time is 4h～48h.
Preferably, preparation method of the present invention also can carry out as follows:
A, chitosan is dispersed in water, then adds acetic acid, stir and obtain chitosan colloidal sol;
B, in described chitosan colloidal sol, add phenol, after stirring, then add formaldehyde, acquisition mixed sols again stirs;
C, described mixed sols is packed in water heating kettle, be placed in 160 ℃ of baking ovens, reaction 8～10h, obtains resol organogel;
D, described resol organogel is immersed in to organic solvent replaces to organic solvent variable color, change organic solvent colourless to the organic solvent soaking after resol organogel, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
The ratio of the quality of described chitosan, the volume of described acetic acid, the amount of substance of described phenol and the amount of substance of described formaldehyde is (0.1g～0.5g): (0.2ml～0.8ml): (0.02mol～0.14mol): (0.04mol).
Preferably, preparation method of the present invention also can carry out as follows:
A, 3-amino-phenol is joined in water/dehydrated alcohol mixing solutions, heated and stirred, to dissolving, obtains mixing solutions;
B, chitosan is dispersed in described mixing solutions, then adds successively acetic acid and formaldehyde, stir and obtain mixed sols;
C, described mixed sols is packed in water heating kettle, be placed in 100 ℃ of baking ovens, reaction 24h, obtains resol organogel;
D, described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel;
The ratio of the quality of described chitosan, the volume of described acetic acid, the amount of substance of described 3-amino-phenol and the amount of substance of described formaldehyde is (0.1g～0.5g): (0.2ml～0.8ml): (0.01mol～0.14mol): (0.02mol～0.04mol).
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention is simple to operate, reacts safe and reliable, and can regulate and control structure, the mechanical property of gained resol organogel; Hole and the specific surface area of the derivative porous carbon materials after dry after structure, density and its carbonization of the resol aerogel of gained can well be regulated and controled;
2, the present invention adopts the chitosan of low price, environmental protection, wide material sources as template, and the phenol that adopts inexpensive and stable chemical nature is raw material, and raw material is easy to storage, and the reaction times is short, greatly reduces synthetic cost;
3, method of the present invention is a kind of universal method, has both been applicable to stable phenol, is also applicable to unsettled Resorcinol and other phenol, has expanded the range of application of the inventive method.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope picture that the embodiment of the present invention 1 is prepared resol aerogel 1;
Fig. 2 is the transmission electron microscope picture of the resol aerogel 1 of the embodiment of the present invention 1 preparation;
Fig. 3 is the scanning electron microscope picture of the resol carbon aerogels 1 of the embodiment of the present invention 1 preparation;
Fig. 4 is the scanning electron microscope picture of the resol carbon aerogels 1 of the embodiment of the present invention 1 preparation;
Fig. 5 is the intensity, modulus of the resol organogel 1～8 described in the embodiment of the present invention 1～2 and the graph of a relation of the ratio (P/F) of phenol/formaldehyde amount of substance;
Fig. 6 is the compression cycle graphic representation of the resol organogel 1 of the embodiment of the present invention 1 preparation;
Fig. 7 is the compression cycle graphic representation of the resol organogel 7 of the embodiment of the present invention 2 preparations;
Fig. 8 is the compression cycle graphic representation of the resol organogel 8 of the embodiment of the present invention 2 preparations;
Fig. 9 is the scanning electron microscope picture of the resol aerogel 9 described in the embodiment of the present invention 3;
Figure 10 is the scanning electron microscope picture of the resol aerogel 10 described in the embodiment of the present invention 3;
Figure 11 is the photo of the resol organogel 11 described in the embodiment of the present invention 4;
Figure 12 is the scanning electron microscope picture of the resol aerogel 11 described in the embodiment of the present invention 4;
Figure 13 is the density of resol aerogel 1,9,10,11 of the embodiment of the present invention 1,3,4 preparation and the specific surface area of its derived carbon aerogel 1,9,10,11 and the graph of a relation of the add quality of chitosan;
Figure 14 is the scanning electron microscope picture of the resol aerogel 12 described in the embodiment of the present invention 5.
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, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The preparation method who the invention discloses a kind of phenolic resin gel, comprising:
A1, chitosan is dispersed in water or water/dehydrated alcohol mixing solutions, then adds acid, stir and obtain chitosan colloidal sol;
Or add weighting material and chitosan in water or water/dehydrated alcohol mixing solutions, and after stirring, add again acid, stir and obtain chitosan colloidal sol;
B1, in chitosan colloidal sol, add phenols, after stirring, then add aldehydes, acquisition mixed sols again stirs;
C1, mixed sols is packed in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D1, resol organogel is immersed in to organic solvent replaces to organic solvent variable color, change organic solvent colourless to the organic solvent soaking after resol organogel, take out resol organogel and carry out supercritical drying, obtain resol aerogel;
Or resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel;
Preferably, the described phenols in step b1 is the several of a kind of or any proportioning in phenol, Resorcinol, Phloroglucinol, cresols, xylenol, mixture cresol, nonyl phenol;
The preparation method of resol aerogel of the present invention also can carry out as follows:
A2, phenols is joined in water/dehydrated alcohol mixing solutions, under 40～100 ℃ of conditions, heated and stirred, to dissolving, obtains mixing solutions;
Or phenols is joined in water/dehydrated alcohol mixing solutions, under 40～100 ℃ of conditions, heated and stirred is extremely dissolved, then adds weighting material, stirs and obtains mixing solutions;
B2, chitosan is dispersed in described mixing solutions, then adds successively acid and aldehyde, stir and obtain mixed sols;
C2, described mixed sols is packed in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D2, described resol organogel is immersed in organic solvent and is replaced to organic solvent variable color, change organic solvent colourless to the organic solvent soaking after resol organogel, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
Or described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel.
Preferably, the phenols in step b2 is the several of a kind of or any proportioning in Ortho-Aminophenol, 3-amino-phenol, PAP, Resorcinol, Phloroglucinol, cresols, mixture cresol, nonyl phenol, octyl phenol, cardanol, aralkyl phenol, dihydroxyphenyl propane;
In the present invention, monomer aldehydes is preferably the several of a kind of or any proportioning in formaldehyde, paraformaldehyde, furfural, acetaldehyde; Acids is catalyzer, is preferably the several of a kind of or any proportioning in formic acid, acetic acid, oxalic acid, tartrate, hydrochloric acid, sulfuric acid, nitric acid; Weighting material is preferably the several of a kind of or any proportioning in clay, polynite, wilkinite, silicon-dioxide, polystyrene.Weighting material is only for strengthening the physical strength of gel and the three-dimensional structure of supplemental support phenolic resin gel, alternative interpolation, and addition can appropriate change, or does not add.
While preparing phenolic resin gel, monomer phenols is preferably the several of a kind of or any proportioning in phenol, Resorcinol, 3-amino-phenol, more preferably phenol; Monomer aldehydes is preferably the several of a kind of or any proportioning in formaldehyde, paraformaldehyde and acetaldehyde, more preferably formaldehyde; Acids is preferably the several of a kind of or any proportioning in formic acid, acetic acid, oxalic acid, tartrate, hydrochloric acid, sulfuric acid, nitric acid, more preferably acetic acid; Weighting material is the several of a kind of or any proportioning in clay, polynite, wilkinite, silicon-dioxide, polystyrene, is preferably polynite.Wherein, while adopting phenol, the condition optimization of hydro-thermal reaction is 140 ℃～160 ℃, 8～10h; While adopting Resorcinol and Phloroglucinol, hydrothermal temperature is preferably 70 ℃-100 ℃, 8～10h; While adopting Ortho-Aminophenol, 3-amino-phenol and PAP, hydrothermal temperature is preferably 100 ℃, 24h.
While preparing resol organogel, the order of addition of each component has a certain impact to the state of mixed sols, for example, step a1 is first uniformly dispersed chitosan in water, add acetic acid and be dissolved into the thick colloidal sol of water white transparency, then add phenol, be stirred into white emulsion, add formaldehyde rapid stirring even, whipping process can not interrupt.Or, step a2 can for first by 3-amino-phenol heating for dissolving in the mixing solutions of water/dehydrated alcohol, then add successively chitosan, acetic acid, mix rear interpolation formaldehyde, rapid stirring becomes thick colloidal sol.Meanwhile, ethanol is the secondary solvent in preparation process, is conducive to the dissolving of each component, and its addition can suitably be adjusted.
The present invention adopts cheap chitosan as template, and chitosan can only be scattered in water and insoluble, and adding of acetic acid, impels the dissolving of chitosan, can react with the addition polycondensation of formaldehyde by catalysis of phenol again.Then add phenol, there is interaction of hydrogen bond in amino and the phenol on chitosan molecule surface, form white thick emulsion, add after formaldehyde, formaldehyde can with chitosan reaction, promote the crosslinked of chitosan, can form compared with strong hydrogen bonding with phenol again, thereby further phenol and formaldehyde molecule are adsorbed on around the skeleton of chitosan.In water-heat process, phenol formaldehyde (PF) starts reaction under acetic acid catalysis effect, the polycondensation of dewatering after first addition, and be attached on the skeleton of chitosan molecule, form gradually the three-dimensional framework of phenolic resin gel.Excessive phenol and formaldehyde reaction generate a large amount of linear adjacent position phenolic resin molecule or oligomer molecules, degrade gradually and generate small-molecule substance and be jointly filled in the middle of the three-dimensional framework of phenolic resin gel, thereby make phenolic resin gel have elasticity with chitosan.The phenol adding by regulation and control and the mol ratio of formaldehyde (P/F), can regulate and control the linear adjacent position phenolic resin molecule of filling in skeleton and the amount of oligomer molecules, and then obtain the resol organogel of different mechanical properties, can regulate and control its intensity and Young's modulus.Weighting material is only for strengthening the physical strength of gel and the three-dimensional structure of supplemental support phenolic resin gel, alternative interpolation, and addition can appropriate change, or does not add.Further, by the amount of regulation and control chitosan, in conjunction with supercritical CO
2dry technology, can obtain the resol aerogel of different densities; By the high temperature pyrolysis under shielding gas, can obtain corresponding porous carbon materials, the hole of this carbon material and specific surface area are also different; Chitosan amount is more, and system viscosity is larger, and the skeleton of chitosan is at a distance of nearer, and after hydro-thermal reaction, the organogel of gained is finer and close, and the density of aerogel is just larger, and the specific surface area of corresponding porous carbon materials and porosity are just larger.The ratio of the quality of chitosan, the volume of acetic acid, the amount of substance of phenol and the amount of substance of formaldehyde is preferably (0.1g～0.5g): (0.2ml～0.8ml): (0.02mol～0.14mol): (0.04mol).
The resol organogel of gained can depart from water and exist with the form of bulk, and can be damaged under pressure, and can recover deformation, has certain elasticity.
After prepared resol organogel is dry, get final product to obtain corresponding aerogel, for example, steps d 1, the resol organogel of gained is immersed in organic solvent and is replaced, and solvent for use is preferably acetone or alcohol, more preferably acetone, by the linear small molecules in organogel skeleton or oligomer extraction out, until it is colourless to soak the organic solvent of resol organogel, then take out resol organogel and carry out supercritical drying, obtain resol aerogel.
Resol aerogel prepared by the present invention, structure is uniform porous loose structure, surface hydrophobicity and can bear certain pressure.By changing the consumption of chitosan in synthesis condition, can obtain the resol aerogel of different density degree.Further, by carbonization, can obtain the derivative carbon material of resol of different specific surfaces and porosity.Experiment shows, the resol organogel that the phenol/formaldehyde mol ratio of this experiment preparation is 3.5 can bear 50% compressive set and can recover; After the dry also carbonization of phenolic resin gel of being prepared by 0.45g chitosan, its specific surface area is 743m
2/ g.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The chemical reagent adopting in the embodiment of the present invention is commercial.
Embodiment 1
The present embodiment resol aerogel carries out as follows:
In a, the beaker that is 100mL at volume, 0.45g chitosan (Shanghai traditional Chinese medicines group) is dispersed in 30ml deionized water, then adds the acetic acid of 0.6ml, stir and obtain water white chitosan colloidal sol;
B, phenol is placed in to the baking oven of 60 ℃ after it melts, taking liquefied carbolic acid 9.411g joins in the water white colloidal sol of above-mentioned chitosan, fully rapid stirring makes it be mixed into white emulsion, add rapidly again 3ml formaldehyde solution, keep continual stirring to its viscosity fast obviously to increase, obtain mixed sols;
C, described mixed sols is packed in 50ml water heating kettle, be placed in the baking oven of 160 ℃, hydro-thermal reaction 10h, obtains resol organogel, is called organogel 1;
D, described resol organogel is immersed in acetone and is soaked three days, the acetone more renewing every day, colourless to acetone, then take out described resol organogel and carry out supercritical CO
2dry, obtain the hydrophobic elastic resol aerogel that do not have, be called aerogel 1, its scanning electron microscope (SEM) photograph and transmission electron microscope picture are respectively as depicted in figs. 1 and 2.
Further by carbonization, get final product to obtain the carbon material of porous, be called carbon aerogels 1, the scanning electron microscope (SEM) photograph of its different amplification respectively as shown in Figure 3 and Figure 4.
Utilize the preparation method identical with embodiment 1, adopt 0.45g chitosan, in described step b, the amount of the phenol adding is 1.882g, 3.764g, 5.647g, 6.588g, 7.529g, 11.29g and 13.175g, the formaldehyde adding is 3ml, be that phenol is respectively 0.5,1,1.5,1.75,2,3 and 3.5 with the ratio (P/F) of the amount of substance of formaldehyde, after hydro-thermal reaction, can obtain the resol organogel of different P/F, be numbered respectively organogel 2 to organogel 8; Supercritical CO
2after dry gained aerogel and carbonization, the carbon aerogels of gained is numbered respectively aerogel 2 to aerogel 8, carbon aerogels 2 to carbon aerogels 8.
Because the chitosan amount that reaction adopts is constant, so microcosmic skeleton structure is the same, the different changes of ratio of phenol and formaldehyde be the linear small molecules of filling in the middle of skeleton or the amount of oligopolymer, thereby the mechanical property of the resol organogel changing, i.e. elasticity.Experiment shows, the stagnation point of a phenol/formaldehyde mol ratio of adding of elastic behavior existence of resol organogel, and stagnation point is P/F=2.As Fig. 5.When meeting P/F<2, can access the hard elastic resol organogel that do not have; When meeting P/F >=2, can access elastic resol organogel.For example, when P/F=2.5, the resol organogel of gained can bear 30% compressive set, and can recover 94% deformation after load unloading, as Fig. 6; When P/F=3, the resol organogel of gained can bear 40% compressive set, and can recover 95% deformation after load unloading, as Fig. 7; When P/F=3.5, the resol organogel of gained can bear 50% compressive set, and can recover deformation after load unloading, as Fig. 8; When P/F=7/4, the resol organogel of gained does not have elasticity, compresses irrecoverablely, and the stress under compression that high energy bears 9MPa, as Fig. 5.
Utilize the preparation method identical with embodiment 1, in step a, add respectively the chitosan of 0.3g and 0.2g, obtain respectively resol aerogel 9 and aerogel 10, respectively as shown in Figure 9 and Figure 10, after its carbonization, the carbon material of gained is respectively resol carbon aerogels 9 and carbon aerogels 10 to its scanning electron microscope (SEM) photograph.
Because the skeleton structure of resol organogel depends on the amount of chitosan, along with the increase of the amount of chitosan, it is fine and close that microcosmic skeleton is tending towards, so the specific surface area of the density of gained aerogel and corresponding carbon material also can increase, as Figure 13.Resol aerogel prepared by employing 0.3g chitosan is as Fig. 9; Resol aerogel prepared by employing 0.2g chitosan is as Figure 10.
In a, the beaker that is 100mL at volume, add the polynite of deionized water and the 0.5g of 30mL, add 0.1g chitosan (Shanghai traditional Chinese medicines group) after being uniformly dispersed, magnetic agitation adds the acetic acid of 0.6ml again after it is uniformly dispersed, stir and obtain chitosan colloidal sol;
B, phenol is placed in to the baking oven of 60 ℃ after it melts, taking liquefied carbolic acid 9.411g joins in above-mentioned chitosan colloidal sol, fully rapid stirring makes it be mixed into emulsion, then adds rapidly 3ml formaldehyde solution, keeps continual stirring fast to become wood chip shape mixed sols to it;
C, mixed sols is packed in 50ml water heating kettle, be placed in the baking oven of 160 ℃, hydro-thermal reaction 10h, obtains resol organogel, is called organogel 11, as Figure 11;
D, resol organogel is immersed in acetone and is soaked three days, the acetone more renewing every day, colourless to acetone, then take out described resol organogel and carry out supercritical CO
2dry, obtain the hydrophobic elastic resol aerogel that do not have, be called aerogel 11, as Figure 12.
Further by carbonization, get final product to obtain the carbon material of porous, be called carbon aerogels 11.
Embodiment 5
A, in the beaker of 50ml, add the water of 20ml and the ethanol of 10ml, the 3-amino-phenol that adds 1.088g after mixing, 60 ℃ of heated and stirred 2 minutes, take out standing, if there is insolubles again heat and stir, so repeatedly to 3-amino-phenol, dissolves obtain uniform mixing solutions completely;
B, 0.45g chitosan is dispersed in above-mentioned mixing solutions, then adds successively the acetic acid of 0.6ml and the formaldehyde of 1.5ml, fully stir and obtain mixed sols;
C, mixed sols is packed in 50ml water heating kettle, be placed in 100 ℃ of baking ovens and carry out hydro-thermal reaction 24h, obtain resol organogel, be called organogel 12;
D) described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel 12, as Figure 14.
Utilize the preparation method identical with embodiment 5, in described step a, add respectively Ortho-Aminophenol and the PAP of 1.088g, obtain resol organogel 13 and aerogel 14.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for resol aerogel, is characterized in that: comprise the following steps:
A, chitosan is dispersed in water or water/dehydrated alcohol mixing solutions, then adds acid, stir and obtain chitosan colloidal sol;
Or add weighting material and chitosan in water or water/dehydrated alcohol mixing solutions, and after stirring, add again acid, stir and obtain chitosan colloidal sol;
B, in described chitosan colloidal sol, add phenols, after stirring, then add aldehydes, acquisition mixed sols again stirs;
C, described mixed sols is packed in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D, described resol organogel is immersed in organic solvent and is replaced to organic solvent variable color, changing organic solvent replaces again to organic solvent variable color, repeatedly change organic solvent to the organic solvent that soaks resol organogel and keep colourless, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
Or described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel.
2. a preparation method for resol aerogel, is characterized in that: comprise the following steps:
A, phenols is joined in water/dehydrated alcohol mixing solutions, heated and stirred, to dissolving, obtains mixing solutions;
Or phenols is joined in water/dehydrated alcohol mixing solutions, heated and stirred is extremely dissolved, then adds weighting material, stirs and obtains mixing solutions;
B, chitosan is dispersed in described mixing solutions, then adds successively acid and aldehyde, stir and obtain mixed sols;
C, described mixed sols is packed in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D, described resol organogel is immersed in organic solvent and is replaced to organic solvent variable color, changing organic solvent replaces again to organic solvent variable color, repeatedly change organic solvent to the organic solvent that soaks resol organogel and keep colourless, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
Or described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel.
3. preparation method according to claim 1 and 2, is characterized in that: in step a, in described water/dehydrated alcohol mixing solutions, the volume parts of dehydrated alcohol is 1/3-2/3.
4. preparation method according to claim 1, is characterized in that: in step b, described phenols is the several of a kind of or any proportioning in phenol, Resorcinol, Phloroglucinol, cresols, xylenol, mixture cresol, nonyl phenol.
5. preparation method according to claim 2, it is characterized in that: in step b, described phenols is the several of a kind of or any proportioning in Ortho-Aminophenol, 3-amino-phenol, PAP, Resorcinol, Phloroglucinol, cresols, mixture cresol, nonyl phenol, octyl phenol, cardanol, aralkyl phenol, dihydroxyphenyl propane.
6. preparation method according to claim 1 and 2, is characterized in that: described aldehydes is the several of a kind of or any proportioning in formaldehyde, paraformaldehyde, furfural, acetaldehyde;
Described acid is the several of a kind of or any proportioning in formic acid, acetic acid, oxalic acid, tartrate, hydrochloric acid, sulfuric acid, nitric acid;
Described weighting material is the several of a kind of or any proportioning in clay, polynite, wilkinite, silicon-dioxide, polystyrene;
Described organic solvent is acetone or dehydrated alcohol.
7. preparation method according to claim 1 and 2, is characterized in that: the ratio of the quality of described chitosan, the volume of described acid, the amount of substance of described phenol and the amount of substance of described aldehyde is (0.1g～0.5g): (0.2ml～0.8ml): (0.01mol～0.14mol): (0.02mol～0.04mol).
8. preparation method according to claim 1 and 2, is characterized in that: in step c, the temperature of described hydro-thermal reaction is 70 ℃～200 ℃, and the time is 4h～48h.
9. preparation method according to claim 1, is characterized in that: comprise the following steps:
A, chitosan is dispersed in water, then adds acetic acid, stir and obtain chitosan colloidal sol;
B, in described chitosan colloidal sol, add phenol, after stirring, then add formaldehyde, acquisition mixed sols again stirs;
C, described mixed sols is packed in water heating kettle, be placed in 160 ℃ of baking ovens, reaction 8～10h, obtains resol organogel;
D, described resol organogel is immersed in organic solvent and is replaced to organic solvent variable color, changing organic solvent replaces again to organic solvent variable color, repeatedly change organic solvent to the organic solvent that soaks resol organogel and keep colourless, take out described resol organogel and carry out supercritical drying, obtain resol aerogel;
The ratio of the quality of described chitosan, the volume of described acetic acid, the amount of substance of described phenol and the amount of substance of described formaldehyde is (0.1g～0.5g): (0.2ml～0.8ml): (0.02mol～0.14mol): 0.04mol.
10. preparation method according to claim 2, is characterized in that: carry out as follows:
A, 3-amino-phenol is joined in water/dehydrated alcohol mixing solutions, heated and stirred, to dissolving, obtains mixing solutions;
B, chitosan is dispersed in described mixing solutions, then adds successively acetic acid and formaldehyde, stir and obtain mixed sols;
C, described mixed sols is packed in water heating kettle, be placed in 100 ℃ of baking ovens, reaction 24h, obtains resol organogel;
D, described resol organogel is placed in to liquid nitrogen, freezing being placed in freeze drier is dried, and obtains resol aerogel;
The ratio of the quality of described chitosan, the volume of described acetic acid, the amount of substance of described 3-amino-phenol and the amount of substance of described formaldehyde is (0.1g～0.5g): (0.2ml～0.8ml): (0.01mol～0.14mol): (0.02mol～0.04mol).
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| CN104974318A (en) | 2015-10-14 |
| CN104974318B (en) | 2017-02-01 |
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