CN103709346B - A kind of preparation method of phenolic resin aerogel - Google Patents
A kind of preparation method of phenolic resin aerogel Download PDFInfo
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- CN103709346B CN103709346B CN201310617223.8A CN201310617223A CN103709346B CN 103709346 B CN103709346 B CN 103709346B CN 201310617223 A CN201310617223 A CN 201310617223A CN 103709346 B CN103709346 B CN 103709346B
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Abstract
The invention discloses a kind of preparation method of phenolic resin aerogel, it is characterized in that: chitosan, acid, weighting material, phenols are mixed at water or water/dehydrated alcohol mixing solutions with aldehydes, after carrying out hydro-thermal reaction, obtains resol organogel; Resol organogel is soaked and replaces in organic solvent, supercritical CO
2phenolic resin aerogel is obtained after drying.The present invention is simple to operate, reacts safe and reliable, and can regulate and control structure, the mechanical property of gained resol organogel; And dry after the structure of phenolic resin aerogel of gained, the hole of derivative porous carbon materials after density and its carbonization and specific surface area can well be regulated and controled.
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, experienced by the developing history of more than 100 year, has been widely used in the every field such as defence and military and building, traffic, chemical industry and the energy so far.At present, resol is prepared the porous carbon materials of multiple nanostructure as carbon source and is caused the interest of people.Porous carbon materials is paid close attention to widely due to the electric conductivity and obtaining of its higher specific surface area, controlled micro-nano aperture and excellence, in every field, there is potential using value in such as 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 synthesize under the condition of acidity, alkalescence or salt.But the synthesis of current phenolic resin gel is all faced with the great number of issues such as cost is high, reaction difficulty controls and can not regulate and control.Therefore, resol be made to derive porous carbon materials and can obtain large-scale application, adopt the three-dimensional phenolic resin gel of the method for simple economy synthesis then to become problem demanding prompt solution.
At present, phenolic resin gel has prepared and has studied widely, and wherein, Resorcinol and formaldehyde are the most frequently used raw material.U.S.'s " JACS " (Journal of the American Chemical Society, 2011 133 phase 11378 pages) reports and adopts novolak resin gel under Resorcinol, formaldehyde and pluronic F127 alkaline condition; Britain's " materials chemistry magazine " (Journal of Materials Chemistry A, 2013 1 phase 13462 pages) reports and adopts Resorcinol and formaldehyde to be raw material, the phenolic resin aerogel that acidic catalyst synthesis is soft.But aforesaid method all exists following problem, namely Resorcinol is adopted to be raw material, expensive, be not suitable for extensive synthesis, and have higher activity owing to phenyl ring being rich in hydroxyl and not easily storing, and the method reaction times is general longer, poor controllability.
Template is also another important method of novolak resin, such as, Britain's " energy and environment science " (Energy & Environmental Science, 6 phase in 2013 652 pages) report and adopt ionic liquid to be template, Resorcinol and formaldehyde are raw material, and hexanediamine does catalysis and prepared resol porous carbon; Britain's " materials chemistry magazine " (Journal of Materials Chemistry A, 2012 22 phase 21852 pages) reports and adopts ionic liquid to do templated synthesis resorcinol-formaldehyde resin gel.But the method not only exists the problems referred to above, and have employed that synthesis is complicated and ionic liquid cost used is higher, thus significantly limit its application.
Summary of the invention
For solving the weak point existing for above-mentioned prior art, the invention provides the preparation method of the phenolic resin aerogel that a kind of technique is simple, cost is low, to the controlled of phenolic resin gel structure, density, ultimate compression strength and Young's modulus can be realized.
Technical solution problem of the present invention, adopts following technical scheme:
The preparation method of phenolic resin aerogel of the present invention, its feature is: comprise the following steps:
A1, chitosan to be dispersed in water or water/dehydrated alcohol mixing solutions, then to add acid, stir and obtain chitosan colloidal sol;
Or weighting material and chitosan is added in water or water/dehydrated alcohol mixing solutions, add acid again after stirring, stir and obtain chitosan colloidal sol;
B1, in described chitosan colloidal sol, add phenols, after stirring, then add aldehydes, stir acquisition mixed sols again;
C1, described mixed sols to be loaded 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 organic solvent carries out replacing to organic solvent variable color, change organic solvent colourless to the organic solvent soaked after resol organogel, take out described resol organogel and carry out supercritical drying, obtain phenolic resin aerogel;
Or described resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin 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 phenolic resin aerogel of the present invention also can carry out as follows:
A2, join in water/dehydrated alcohol mixing solutions by phenols, under 40 ~ 100 DEG C of conditions, heated and stirred is to dissolving, and obtains mixing solutions;
Or phenols is joined in water/dehydrated alcohol mixing solutions, under 40 ~ 100 DEG C of conditions, heated and stirred is to dissolving, then adds weighting material, stirs and obtains mixing solutions;
B2, chitosan to be dispersed in described mixing solutions, then to add acid and aldehyde successively, stir and obtain mixed sols;
C2, described mixed sols to be loaded in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D2, described resol organogel soaked and carries out in organic solvent replacing to organic solvent variable color, change organic solvent colourless to the organic solvent soaked after resol organogel, take out described resol organogel and carry out supercritical drying, obtain phenolic resin aerogel;
Or described resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin 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 and strengthens the physical strength of gel and the three-dimensional structure of supplemental support phenolic resin gel, alternatively adds, 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 DEG C ~ 200 DEG C, and the time is 4h ~ 48h.
Preferably, preparation method of the present invention also can carry out as follows:
A, chitosan to be dispersed in water, then to add acetic acid, stir and obtain chitosan colloidal sol;
B, in described chitosan colloidal sol, add phenol, after stirring, then add formaldehyde, stir acquisition mixed sols again;
C, loaded in water heating kettle by described mixed sols, be placed in 160 DEG C of baking ovens, reaction 8 ~ 10h, obtains resol organogel;
D, described resol organogel is immersed in organic solvent carries out replacing to organic solvent variable color, change organic solvent colourless to the organic solvent soaked after resol organogel, take out described resol organogel and carry out supercritical drying, obtain phenolic resin 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, join in water/dehydrated alcohol mixing solutions by 3-amino-phenol, heated and stirred, to dissolving, obtains mixing solutions;
B, chitosan to be dispersed in described mixing solutions, then to add acetic acid and formaldehyde successively, stir and obtain mixed sols;
C, loaded in water heating kettle by described mixed sols, be placed in 100 DEG C of baking ovens, reaction 24h, obtains resol organogel;
D, described resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin 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 the structure of the phenolic resin aerogel of gained, density and its carbonization can well be regulated and controled;
2, the present invention adopt low price, environmental protection, wide material sources chitosan as template, adopt inexpensive and the phenol of stable chemical nature is raw material, raw material is easy to store, and the reaction times is short, greatly reduces synthesis cost;
3, method of the present invention is a kind of universal method, has both been applicable to stable phenol, is also applicable to unstable Resorcinol and other phenol, has expanded the range of application of the inventive method.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture that the embodiment of the present invention 1 prepares phenolic resin aerogel 1;
Fig. 2 is the transmission electron microscope picture of phenolic resin aerogel 1 prepared by the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscopic picture of resol carbon aerogels 1 prepared by the embodiment of the present invention 1;
Fig. 4 is the scanning electron microscopic picture of resol carbon aerogels 1 prepared by the embodiment of the present invention 1;
The graph of a relation of the intensity that Fig. 5 is the resol organogel 1 ~ 8 described in the embodiment of the present invention 1 ~ 2, modulus and the ratio (P/F) of phenol/formaldehyde amount of substance;
Fig. 6 is the compression cycle graphic representation of resol organogel 1 prepared by the embodiment of the present invention 1;
Fig. 7 is the compression cycle graphic representation of resol organogel 7 prepared by the embodiment of the present invention 2;
Fig. 8 is the compression cycle graphic representation of resol organogel 8 prepared by the embodiment of the present invention 2;
Fig. 9 is the scanning electron microscopic picture of the phenolic resin aerogel 9 described in the embodiment of the present invention 3;
Figure 10 is the scanning electron microscopic picture of the phenolic resin 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 microscopic picture of the phenolic resin aerogel 11 described in the embodiment of the present invention 4;
Figure 13 is the density of phenolic resin aerogel 1,9,10,11 and the graph of a relation of the specific surface area of its derived carbon aerogel 1,9,10,11 and the quality of added chitosan of the embodiment of the present invention 1,3,4 preparation;
Figure 14 is the scanning electron microscopic picture of the phenolic resin aerogel 12 described in the embodiment of the present invention 5.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention discloses a kind of preparation method of phenolic resin gel, comprising:
A1, chitosan to be dispersed in water or water/dehydrated alcohol mixing solutions, then to add acid, stir and obtain chitosan colloidal sol;
Or weighting material and chitosan is added in water or water/dehydrated alcohol mixing solutions, add acid again after stirring, stir and obtain chitosan colloidal sol;
B1, in chitosan colloidal sol, add phenols, after stirring, then add aldehydes, stir acquisition mixed sols again;
C1, mixed sols is loaded in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D1, resol organogel is immersed in organic solvent carries out replacing to organic solvent variable color, change organic solvent colourless to the organic solvent soaked after resol organogel, take out resol organogel and carry out supercritical drying, obtain phenolic resin aerogel;
Or resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin 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 phenolic resin aerogel of the present invention also can carry out as follows:
A2, join in water/dehydrated alcohol mixing solutions by phenols, under 40 ~ 100 DEG C of conditions, heated and stirred is to dissolving, and obtains mixing solutions;
Or phenols is joined in water/dehydrated alcohol mixing solutions, under 40 ~ 100 DEG C of conditions, heated and stirred is to dissolving, then adds weighting material, stirs and obtains mixing solutions;
B2, chitosan to be dispersed in described mixing solutions, then to add acid and aldehyde successively, stir and obtain mixed sols;
C2, described mixed sols to be loaded in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D2, described resol organogel soaked and carries out in organic solvent replacing to organic solvent variable color, change organic solvent colourless to the organic solvent soaked after resol organogel, take out described resol organogel and carry out supercritical drying, obtain phenolic resin aerogel;
Or described resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin 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 and strengthens the physical strength of gel and the three-dimensional structure of supplemental support phenolic resin gel, alternatively adds, and addition can appropriate change, or does not add.
When preparing phenolic resin gel, monomer phenols is preferably the several of a kind of or any proportioning in phenol, Resorcinol, 3-amino-phenol, is more preferably phenol; Monomer aldehydes is preferably the several of a kind of or any proportioning in formaldehyde, paraformaldehyde and acetaldehyde, is 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, is 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, when adopting phenol, the condition optimization of hydro-thermal reaction is 140 DEG C ~ 160 DEG C, 8 ~ 10h; When employing Resorcinol and Phloroglucinol, hydrothermal temperature is preferably 70 DEG C-100 DEG C, 8 ~ 10h; When employing Ortho-Aminophenol, 3-amino-phenol and PAP, hydrothermal temperature is preferably 100 DEG C, 24h.
When preparing resol organogel, the state of order of addition to mixed sols of each component has a certain impact, such as, chitosan is first uniformly dispersed by step a1 in water, add acetic acid and become 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 be first by 3-amino-phenol heating for dissolving in the mixing solutions of water/dehydrated alcohol, then add chitosan, acetic acid successively, 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 adjust.
The present invention adopts cheap chitosan as template, and chitosan can only be scattered in water insoluble, adding of acetic acid, namely impels the dissolving of chitosan, can the addition polycondensation of catalysis of phenol and formaldehyde react again.Then phenol is added, there is interaction of hydrogen bond in amino and the phenol on chitosan molecule surface, form thick white shape emulsion, after adding formaldehyde, formaldehyde can with chitosan reaction, promote the crosslinked of chitosan, comparatively strong hydrogen bonding can be formed with phenol again, thus around the skeleton further phenol and formaldehyde molecule being adsorbed on chitosan.In water-heat process, phenol formaldehyde (PF) starts reaction under acetic acid catalysis effect, dehydrating polycondensation after first addition, and is attached on the skeleton of chitosan molecule, forms the three-dimensional framework of phenolic resin gel gradually.Excessive phenol and formaldehyde reaction generate a large amount of linear adjacent position phenolic resin molecules or oligomer molecules, and degrading gradually with chitosan generates small-molecule substance and be jointly filled in the middle of the three-dimensional framework of phenolic resin gel, thus makes phenolic resin gel have elasticity.The phenol added by regulation and control and the mol ratio (P/F) of formaldehyde, the linear adjacent position phenolic resin molecule of namely filling in controllable skeleton and the amount of oligomer molecules, and then obtain the resol organogel of different mechanical properties, i.e. its intensity of controllable and Young's modulus.Weighting material is only and strengthens the physical strength of gel and the three-dimensional structure of supplemental support phenolic resin gel, alternatively adds, and addition can appropriate change, or does not add.Further, by regulating and controlling the amount of chitosan, in conjunction with supercritical CO
2dry technology, can obtain the phenolic resin aerogel of different densities; Can obtain corresponding porous carbon materials by the high temperature pyrolysis under shielding gas, 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 larger, and the specific surface area and porosity of corresponding porous carbon materials is 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 under stress can not be damaged, and can recover deformation, has certain elasticity.
After prepared resol organogel drying corresponding aerogel, such as, steps d 1, soaked by the resol organogel of gained and replace in organic solvent, solvent for use is preferably acetone or alcohol, is more preferably acetone, by the linear small molecules in organogel skeleton or oligomer extraction out, until the organic solvent soaking resol organogel is colourless, then takes out resol organogel and carry out supercritical drying, obtain phenolic resin aerogel.
Phenolic resin 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, the phenolic resin aerogel of different density degree can be obtained.Further, the carbon material that the resol that can obtain different specific surface and porosity by carbonization derives.Experiment shows, this experiment preparation phenol/formaldehyde mol ratio be 3.5 resol organogel can bear the compressive set of 50% and can recover; After the dry also carbonization of the phenolic resin gel 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 describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The chemical reagent adopted in the embodiment of the present invention is commercial.
Embodiment 1
The present embodiment phenolic resin aerogel is carried out as follows:
A, at volume be 100mL beaker in, 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 the baking oven of 60 DEG C after it melts, taking liquefied carbolic acid 9.411g joins in the water white colloidal sol of above-mentioned chitosan, abundant rapid stirring makes it be mixed into white emulsion, add rapidly 3ml formaldehyde solution again, keep continual stirring to its viscosity fast obviously to increase, obtain mixed sols;
C, described mixed sols to be loaded in 50ml water heating kettle, be placed in the baking oven of 160 DEG C, hydro-thermal reaction 10h, obtain resol organogel, be called organogel 1;
D, the submergence of described resol organogel is soaked three days in acetone, the acetone more renewed every day, colourless to acetone, then take out described resol organogel and carry out supercritical CO
2drying, obtain hydrophobic not having elastic phenolic resin aerogel, 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 the carbon material of porous, be called carbon aerogels 1, the scanning electron microscope (SEM) photograph of its different amplification is respectively as shown in Figure 3 and Figure 4.
Embodiment 2
Utilize the preparation method identical with embodiment 1, adopt 0.45g chitosan, in described step b, the amount of the phenol added is 1.882g, 3.764g, 5.647g, 6.588g, 7.529g, 11.29g and 13.175g, the formaldehyde added is 3ml, namely 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, can obtain the resol organogel of different P/F after hydro-thermal reaction, is numbered organogel 2 respectively to organogel 8; Supercritical CO
2after dry gained aerogel and carbonization, the carbon aerogels of gained is numbered aerogel 2 respectively to aerogel 8, carbon aerogels 2 to carbon aerogels 8.
Because it is constant for reacting the chitosan amount adopted, so microcosmic skeleton structure is the same, phenol change different from the ratio of formaldehyde be the amount of linear small molecules or the oligopolymer of filling in the middle of skeleton, thus the mechanical property of the resol organogel of change, i.e. elasticity.Experiment shows, the elastic behavior of resol organogel exists the stagnation point of the phenol/formaldehyde mol ratio that is added, and stagnation point is P/F=2.As Fig. 5.When meeting P/F<2, can obtain hard there is no elastic resol organogel; When meeting P/F >=2, elastic resol organogel can be obtained.Such as, as P/F=2.5, the resol organogel of gained can bear the compressive set of 30%, and can recover the deformation of 94% after load unloading, as Fig. 6; As P/F=3, the resol organogel of gained can bear the compressive set of 40%, and can recover the deformation of 95% after load unloading, as Fig. 7; As P/F=3.5, the resol organogel of gained can bear the compressive set of 50%, and can recover deformation, as Fig. 8 after load unloading; As P/F=7/4, the resol organogel of gained does not have elasticity, compresses irrecoverable, and most high energy bears the stress under compression of 9MPa, as Fig. 5.
Embodiment 3
Utilize the preparation method identical with embodiment 1, the chitosan of 0.3g and 0.2g is added respectively in step a, obtain phenolic resin aerogel 9 and aerogel 10 respectively, 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.
Skeleton structure due to resol organogel depends on the amount of chitosan, and along with the increase of the amount of chitosan, microcosmic skeleton is tending towards fine and close, and therefore the density of gained aerogel and the specific surface area of corresponding carbon material also can increase, as Figure 13.Phenolic resin aerogel prepared by employing 0.3g chitosan is as Fig. 9; Phenolic resin aerogel prepared by employing 0.2g chitosan is as Figure 10.
Embodiment 4
A, at volume be 100mL beaker in, add the deionized water of 30mL and the polynite of 0.5g, add 0.1g chitosan (Shanghai traditional Chinese medicines group) after being uniformly dispersed, magnetic agitation adds the acetic acid of 0.6ml again after making it be uniformly dispersed, and stirs and obtains chitosan colloidal sol;
B, phenol is placed in the baking oven of 60 DEG C after it melts, taking liquefied carbolic acid 9.411g joins in above-mentioned chitosan colloidal sol, abundant rapid stirring makes it be mixed into emulsion, then adds rapidly 3ml formaldehyde solution, keeps continual stirring to it fast to become wood chip shape mixed sols;
C, mixed sols to be loaded in 50ml water heating kettle, be placed in the baking oven of 160 DEG C, hydro-thermal reaction 10h, obtain resol organogel, be called organogel 11, as Figure 11;
D, the submergence of resol organogel is soaked three days in acetone, the acetone more renewed every day, colourless to acetone, then take out described resol organogel and carry out supercritical CO
2drying, obtains hydrophobic not having elastic phenolic resin aerogel, is called aerogel 11, as Figure 12.
Further by carbonization 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, add the 3-amino-phenol of 1.088g after mixing, 60 DEG C of heated and stirred 2 minutes, take out and leave standstill, if there is insolubles again heat and stir, so repeatedly dissolves completely to 3-amino-phenol and obtain uniform mixing solutions;
B, 0.45g chitosan to be dispersed in above-mentioned mixing solutions, then to add the acetic acid of 0.6ml and the formaldehyde of 1.5ml successively, fully stir and obtain mixed sols;
C, mixed sols to be loaded in 50ml water heating kettle, be placed in 100 DEG C of baking ovens and carry out hydro-thermal reaction 24h, obtain resol organogel, be called organogel 12;
D) described resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin aerogel 12, as Figure 14.
Embodiment 6
Utilize the preparation method identical with embodiment 5, in described step a, add Ortho-Aminophenol and the PAP of 1.088g respectively, obtain resol organogel 13 and aerogel 14.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (6)
1. a preparation method for phenolic resin aerogel, is characterized in that: comprise the following steps:
A, chitosan to be dispersed in water or water/dehydrated alcohol mixing solutions, then to add acid, stir and obtain chitosan colloidal sol;
Or weighting material and chitosan is added in water or water/dehydrated alcohol mixing solutions, add acid again after stirring, stir and obtain chitosan colloidal sol;
B, in described chitosan colloidal sol, add phenols, after stirring, then add aldehydes, stir acquisition mixed sols again;
C, described mixed sols to be loaded in water heating kettle, be placed in baking oven and carry out hydro-thermal reaction, obtain resol organogel;
D, described resol organogel soaked and carries out in organic solvent replacing to organic solvent variable color, changing organic solvent replaces to organic solvent variable color again, repeatedly change organic solvent and keep colourless to the organic solvent soaking resol organogel, take out described resol organogel and carry out supercritical drying, obtain phenolic resin aerogel;
Or described resol organogel is placed in liquid nitrogen, freezing being placed in freeze drier carries out drying, obtains phenolic resin aerogel;
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).
2. preparation method according to claim 1, is characterized in that: in step a, and in described water/dehydrated alcohol mixing solutions, the volume parts of dehydrated alcohol is 1/3-2/3.
3. preparation method according to claim 1, is characterized in that: in step b, and described phenols is the several of a kind of or any proportioning in phenol, Resorcinol, Phloroglucinol, cresols, xylenol, mixture cresol, nonyl phenol.
4. preparation method according to claim 1, 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.
5. preparation method according to claim 1, is characterized in that: in step c, and the temperature of described hydro-thermal reaction is 70 DEG C ~ 200 DEG C, and the time is 4h ~ 48h.
6. preparation method according to claim 1, is characterized in that: comprise the following steps:
A, chitosan to be dispersed in water, then to add acetic acid, stir and obtain chitosan colloidal sol;
B, in described chitosan colloidal sol, add phenol, after stirring, then add formaldehyde, stir acquisition mixed sols again;
C, described mixed sols loaded in water heating kettle, be placed in 160 DEG C of baking ovens, reaction 8 ~ 10h, obtains resol organogel;
D, described resol organogel soaked and carries out in organic solvent replacing to organic solvent variable color, changing organic solvent replaces to organic solvent variable color again, repeatedly change organic solvent and keep colourless to the organic solvent soaking resol organogel, take out described resol organogel and carry out supercritical drying, obtain phenolic resin 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.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510456331.0A CN104974318B (en) | 2013-11-27 | 2013-11-27 | Preparation method of phenol-formaldehyde resin aerogel |
| CN201310617223.8A CN103709346B (en) | 2013-11-27 | 2013-11-27 | A kind of preparation method of phenolic resin aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310617223.8A CN103709346B (en) | 2013-11-27 | 2013-11-27 | A kind of preparation method of phenolic resin aerogel |
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| CN104892961B (en) * | 2015-05-28 | 2017-12-08 | 南京林业大学 | A kind of preparation method of fibre strip element gel mesoporous material |
| US9776156B2 (en) * | 2015-08-06 | 2017-10-03 | Lawrence Livermore National Security, Llc | Nitrogen-doped carbon aerogels for electrical energy storage |
| CN105601854B (en) * | 2015-09-24 | 2018-02-09 | 北京卫星制造厂 | A kind of preparation method of rigid structure enhancing phenolic aldehyde aeroge heatshield material |
| CN105582895B (en) * | 2015-12-28 | 2018-05-08 | 浙江同信园林建设股份有限公司 | A kind of high adsorption composite material for sewage disposal and preparation method thereof |
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| CN106189066B (en) * | 2016-07-04 | 2020-08-25 | 中国科学技术大学 | Phenolic resin/silicon dioxide composite aerogel material and preparation method thereof |
| US11124414B2 (en) | 2016-10-20 | 2021-09-21 | Osaka University | Method for producing hydrogen peroxide, kit for hydrogen peroxide production, organic polymer photocatalyst used in said method and kit, and method for producing said organic polymer photocatalyst |
| CN108421534B (en) * | 2018-02-08 | 2020-10-20 | 中山大学 | Chitosan gel material, preparation method thereof, wastewater treatment method and application |
| CN109158058B (en) * | 2018-09-11 | 2020-05-22 | 淮阴工学院 | Attapulgite-chitosan composite gel and preparation method thereof |
| CN109289509B (en) * | 2018-10-30 | 2021-03-05 | 广东恒利新包装材料有限公司 | Indoor VOCs purification material for high-humidity environment and preparation method |
| CN109575510B (en) * | 2018-12-12 | 2021-04-20 | 河北工业大学 | Preparation method of nanofiber mineral reinforced phenolic resin three-dimensional aerogel material |
| CN109911880B (en) * | 2019-04-30 | 2021-02-19 | 浙江工业大学 | Method for preparing nitrogen-containing carbon aerogel through normal-pressure drying in super-salt environment |
| CN110160321A (en) * | 2019-05-24 | 2019-08-23 | 浙江农林大学 | A kind of drying means of timber aeroge |
| CN110467742A (en) * | 2019-08-30 | 2019-11-19 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of phenolic aldehyde aeroge |
| CN111099574A (en) * | 2019-12-27 | 2020-05-05 | 浙江大学 | Preparation method of hierarchical porous carbon aerogel for lithium ion battery cathode |
| CN113104833B (en) * | 2021-04-14 | 2022-07-15 | 中国科学技术大学 | Biochar-based hard foam carbon, preparation method thereof and application thereof in electrocatalysis |
| CN113426385B (en) * | 2021-06-11 | 2022-06-03 | 武汉大学 | Carbon aerogel pellet, preparation method thereof and application of carbon aerogel pellet as heavy metal adsorption material |
| CN114452951B (en) * | 2021-12-15 | 2023-12-01 | 淮阴工学院 | Phenol formaldehyde aerogel rubidium/cesium specific adsorbent and preparation method and application thereof |
| CN117617556A (en) * | 2022-08-18 | 2024-03-01 | 深圳市合元科技有限公司 | Atomizer, electronic atomizing device, atomizing assembly and preparation method |
| CN116675896B (en) * | 2023-04-26 | 2024-04-30 | 江南大学 | Phenolic resin sponge material with asymmetric structure and preparation method thereof |
| CN116462885B (en) * | 2023-05-29 | 2024-01-23 | 常熟东南塑料有限公司 | Preparation method of high oil absorption rate phenolic resin aerogel material |
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| CN101186512A (en) * | 2007-10-30 | 2008-05-28 | 哈尔滨工业大学 | Method for preparing heat insulation composite material by microwave |
| CN103285789A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Preparation method of three-dimensional fiber-based aerogel material and product thereof |
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| CN1136964C (en) * | 2001-08-24 | 2004-02-04 | 中国科学院山西煤炭化学研究所 | Process for preparing barrow size distribution charcoal aerogel |
| CN1136963C (en) * | 2001-08-24 | 2004-02-04 | 中国科学院山西煤炭化学研究所 | Method for synthesis of furfural-phenolic aldehyde based charcoal aerogel |
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| CN101186512A (en) * | 2007-10-30 | 2008-05-28 | 哈尔滨工业大学 | Method for preparing heat insulation composite material by microwave |
| CN103285789A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Preparation method of three-dimensional fiber-based aerogel material and product thereof |
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