CN104892874A - Ordered mesoporous macromolecular nanospheres with curved pore passages and preparation method and application thereof - Google Patents
Ordered mesoporous macromolecular nanospheres with curved pore passages and preparation method and application thereof Download PDFInfo
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- CN104892874A CN104892874A CN201510268935.2A CN201510268935A CN104892874A CN 104892874 A CN104892874 A CN 104892874A CN 201510268935 A CN201510268935 A CN 201510268935A CN 104892874 A CN104892874 A CN 104892874A
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention discloses ordered mesoporous macromolecular nanospheres with curved pore passages. Each ordered mesoporous macromolecular nanosphere has the particle diameter of 100nm to 200nm and has a two-dimensional hexagonal-phase mesoporous structure, each two-dimensional hexagonal-phase mesoporous structure comprises a plurality of annular curved pore passages which are distributed in the surface of the corresponding nanosphere and penetrate through the corresponding nanosphere, and the pore size of each pore passage is 2nm to 3nm. The invention also discloses a preparation method for the nanospheres. The preparation method comprises the steps of synthesizing a macromolecular pre-polymer from phenol and formaldehyde, then, carrying out microwave treatment on the macromolecular pre-polymer under the condition of heating, then, cooling the macromolecular pre-polymer to room temperature, separating solids from a reaction mixture, and then, roasting the solids in a protective atmosphere, thereby obtaining the target product. The ordered mesoporous macromolecular nanospheres provided by the invention are of a novel mesoporous material, have the characteristics of unique pore passage morphology, large specific surface area, out-phase mesoporous structure and the like, are simple and controllable in preparation process, low in cost and high in efficiency and are environment-friendly, and novel synthesis techniques and fields of application are opened up for phenol-formaldehyde resin.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous material, particularly relate to a kind of ordered mesoporous polymer nanometer ball, the Preparation Method And The Use with flexure type duct, such as, application in absorbing carbon dioxide.
Background technology
In recent years, ordered mesoporous material draws an analogy surface-area because of it and pore volume, evenly adjustable aperture and skeleton form and controlled pattern, has broad application prospects, obtain the extensive attention of people in fields such as catalysis, absorption and energy storage.Recently, there is investigator successfully to utilize organic solvent volatilization method, prepared the two dimension of high-sequential or the mesoporous polymer of three-dimensional structure and carbon material.But this preparation technology's workload is large, and the production time is long, and can not produce in a large number.For a long time, industry a kind of always thirst for developing simple possible method is to prepare in order and the adjustable mesoporous polymer material of structure.
Summary of the invention
Main purpose of the present invention is to provide a kind of ordered mesoporous polymer nanometer ball with flexure type duct and preparation method thereof, to overcome the deficiencies in the prior art.
For achieving the above object, this invention takes following technical scheme:
A kind of ordered mesoporous polymer nanometer ball with flexure type duct, its particle diameter is 100nm ~ 200nm, and there are two-dimentional six side's phase meso-hole structures, described two-dimentional six side's phase meso-hole structures comprise and are distributed in described nanometer ball surface and run through a plurality of flexure type ducts of described nanometer ball, and the aperture in described duct is 2nm ~ 3nm.
Further, described nanometer ball is made up of resol, namely also can be described as bakelite resin nano ball.
Further, described duct is toroidal bend duct.
A kind of preparation method with the ordered mesoporous polymer nanometer ball in flexure type duct; it can comprise: get phenol and excessive formaldehyde as raw material; with water heat transfer polymer performed polymer in containing the aqueous phase system of tensio-active agent; then by described polymer performed polymer in 120 ~ 130 DEG C of microwave treatment 45 ~ 60min; be cooled to room temperature again; isolate the solids in mixed reactant afterwards; and by obtained solids in protective atmosphere in 350 ~ 380 DEG C of roasting 6 ~ 12h, obtain target product.
Among a comparatively preferred specific embodiments, described preparation method can comprise:
(1) phenol is mixed in aqueous phase system with excess formaldehyde, highly basic, and at 70 ~ 75 DEG C of reaction 0.5 ~ 1h, add tensio-active agent afterwards, be continue reaction 2 ~ 3h under the condition of 66 ~ 70 DEG C in temperature, then add water dilution 20 ~ 30 times, continue reaction 16 ~ 20h again, obtain polymer performed polymer;
(2) described polymer performed polymer is added to the water, and at 120 ~ 130 DEG C of microwave treatment 45 ~ more than 60min;
(3) after step (2) gained mixed reactant being cooled to room temperature, isolate solids wherein, successively after washing, drying treatment, obtain khaki color solid;
(4) in protective atmosphere, by described khaki color solid in 350 ~ 380 DEG C of roasting 6 ~ 12h, target product is obtained.
Further, step (1) can comprise: by water-soluble for phenol formation phenol solution, add excess formaldehyde and highly basic again, and at 70 ~ 75 DEG C of reaction 0.5 ~ 1h, add tensio-active agent afterwards, temperature be 66 ~ 70 DEG C, stirring velocity continues reaction 2 ~ more than 3h under being the condition of 300 ~ 380rpm, then adds water dilution, continue reaction 16 ~ more than 20h again, obtain polymer performed polymer.
As preferably one of embody rule scheme, step (1) can comprise the steps: further
A, phenol to be dissolved in the water under 40 DEG C of conditions, to form phenol solution;
B, to obtain in phenol solution in steps A and add formaldehyde and highly basic, continue to stir 0.5h at 70 DEG C;
C, in step B gained mixing solutions, add tensio-active agent (such as, preferred proportion can be dissolved in 15ml water for 0.96g F127, but is not limited thereto) again, temperature be 70 DEG C, rotating speed stirs more than 2h under being the condition of 350rpm;
D, step C gained mixture added water dilution, continue to stir more than 16h and stop, obtaining polymer resol performed polymer.
Further, step (1) also can comprise: phenol is added formaldehyde solution and is warming up to 70 DEG C, after Keep agitation 0.5 ~ 1h, add highly basic again, continue at 70 ~ 75 DEG C of Keep agitation 0.5 ~ 1h, then add tensio-active agent, temperature be 66 ~ 70 DEG C, stirring velocity continues reaction 2 ~ 3h under being the condition of 300 ~ 380rpm, then add water dilution, then continue reaction 16 ~ 20h, obtain polymer performed polymer.
Comparatively preferred, the mass ratio of described phenol, formaldehyde and highly basic is 10:15:1.
Further, described tensio-active agent can be selected from but be not limited to F127, and described F127 is a kind of triblock polymer (poly-oxygen second alkene – gathers oxygen third alkene – polyoxyethylene), and its molecular formula is PEO-PPO-PEO.
Further, described highly basic can be selected but be not limited to NaOH
Further, described formaldehyde solution can be selected but be not limited to the commercially available formaldehyde solution that concentration is 35 ~ 40wt%.
There is described in present invention also offers the purposes of the ordered mesoporous polymer nanometer ball in flexure type duct.
Such as, provide a kind of carbon dioxide adsorption device, it comprises the described ordered mesoporous polymer nanometer ball with flexure type duct.
Compared with prior art, advantage of the present invention is at least:
(1) synthesized a kind of novel mesoporous material, namely there is the ordered mesoporous polymer nanometer ball in flexure type duct, for resol opens new Application Areas;
(2) generated time of this New Type of Mesoporous material shortens greatly than the generated time of traditional resol, and efficiency is able to effective lifting, thus can save energy, environmental protection.
Accompanying drawing explanation
Fig. 1 is the X-ray scatter diagram of a kind of ordered mesoporous polymer nanometer ball in one embodiment of the invention;
Fig. 2 a-2b is the transmission electron microscope picture of a kind of ordered mesoporous polymer nanometer ball in one embodiment of the invention;
Fig. 3 is the Flied emission surface sweeping Electronic Speculum figure of a kind of ordered mesoporous polymer nanometer ball in one embodiment of the invention;
Fig. 4 is the carbon dioxide adsorption performance test figure of a kind of ordered mesoporous polymer nanometer ball in one embodiment of the invention.
Embodiment
Generally, the present invention is based on organic-organic self-assembly strategy, select triblock copolymer F127 (polyethylene oxide-poly(propylene oxide)-polyethylene oxide) as tensio-active agent, with phenol and formaldehyde for high polymer monomer, adopt microwave in conjunction with reduction technique after original position one step, by changing high polymer monomer ratio or concentration and experimental technique condition, realize the pore passage structure of ordered mesoporous phenolic resin material and the Effective Regulation of pattern, obtain the orderly functional mesoporous material with large specific surface sum annular curved duct, it is expected at gaseous storage, heavy metal ion adsorbed, the aspects such as organic catalysis are widely used.
Below in conjunction with accompanying drawing and preferred embodiment, technical scheme of the present invention is further described.
A kind of preparation method with the ordered mesoporous polymer nanometer ball in flexure type duct involved by this embodiment comprises the steps:
Step 1: the synthesis of polymer performed polymer: a certain amount of phenol is added in there-necked flask at 40 DEG C, add 2.1ml 35-40wt% formaldehyde solution again, after being warming up to 70 DEG C, continue to stir 30min, add 0.1M sodium hydroxide solution 15ml, after continuing to stir 30min, add the aqueous solution that 15ml is dissolved with 0.96g F127, adjustment temperature to 66 DEG C, after stirring 2h, adds the dilution of 50ml water under 350rpm rotating speed.Continue to stir 16-18h, until there is red precipitate to occur, stops heating, be cooled to room temperature, after produced resolution of precipitate, prepare polymer performed polymer.
Step 2: above-mentioned obtained 3.5ml polymer performed polymer is loaded 30ml microwave reaction pipe, and add the dilution of 11ml water.After microwave reaction pipe is reacted 1h under 120 degree, microwave, be cooled to room temperature, by centrifugal for the solid of ageing in reaction tubes, after the distilled water wash removal of impurity, after drying treatment, obtain khaki color solid.
Step 3: by above-mentioned obtained khaki color solid under nitrogen protection condition, under 350 DEG C of conditions, roasting 6h, removing tensio-active agent F127, obtains target product, namely has the ordered mesoporous polymer nanometer ball in bending types duct.
Step 4: a series of sign is carried out to above-mentioned target product.
All kinds of intermediate product involved in the present embodiment building-up process and final product (being once referred to as " sample ") carry out structural characterization by following means:
Transmission electron microscope obtains under 200kV at Japanese JEOL JEM2011 type high-resolution-ration transmission electric-lens;
The S 4800 type cold field emission scanning electronic microscope that stereoscan photograph is produced in Japanese HITACHI company obtains under 3.0kV;
N measured by the NOVA 4000 type surface area test instrument produced by Kang Ta company of the U.S.
2adsorption isothermal curve, the specific surface area of sample is obtained by BET Equation for Calculating.
Refer to Fig. 1, preceding aim product has high-sequential two dimension six side's phase pore structures.
Please continue to refer to Fig. 2 a-Fig. 2 b, preceding aim its surface can observe the existence of mesopore orbit, is a kind of special toroidal bend duct.Meanwhile, refer to Fig. 3, preceding aim product is spheroidal particle, and size is relatively more even, and mean diameter is greatly about about 100nm.Further, composition graphs 2a, Fig. 2 b and Fig. 3, also very clearly can see that preceding aim product has high-sequential two dimension six side's phase pore structures.
Refer to Fig. 4, find after tested, preceding aim product shows higher adsorptive power to carbonic acid gas.Ordered mesoporous polymer nanometer ball of the present invention is a kind of New Type of Mesoporous material, and have the feature such as unique duct pattern and bigger serface, not homophase meso-hole structure, and preparation technology is simply controlled, with low cost, efficiency is high, environmental protection.The present invention is that resol opens new synthetic technology and Application Areas.
Should be appreciated that and the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention; for a person skilled in the art; within the spirit and principles in the present invention all, any amendment, improvement etc. done, all should be included within protection scope of the present invention.
Claims (10)
1. one kind has the ordered mesoporous polymer nanometer ball in flexure type duct, it is characterized in that the particle diameter of described nanometer ball is 100nm ~ 200nm, and there are two-dimentional six side's phase meso-hole structures, described two-dimentional six side's phase meso-hole structures comprise and are distributed in described nanometer ball surface and run through a plurality of flexure type ducts of described nanometer ball, and the aperture in described duct is 2nm ~ 3nm.
2. the ordered mesoporous polymer nanometer ball with flexure type duct according to claim 1, is characterized in that described nanometer ball is made up of resol, and described duct is toroidal bend duct.
3. there is according to any one of claim 1-2 the method for making of the ordered mesoporous polymer nanometer ball in flexure type duct; it is characterized in that comprising: get phenol and excessive formaldehyde as raw material; with water heat transfer polymer performed polymer in containing the aqueous phase system of tensio-active agent; then by described polymer performed polymer in 120 ~ 130 DEG C of microwave treatment 45 ~ 60min; be cooled to room temperature again; isolate the solids in mixed reactant afterwards; and by obtained solids in protective atmosphere in 350 ~ 380 DEG C of roasting 6 ~ 12h, obtain target product.
4. method for making according to claim 3, is characterized in that comprising:
(1) phenol is mixed in aqueous phase system with excess formaldehyde, highly basic, and at 70 ~ 75 DEG C of reaction 0.5 ~ 1h, add tensio-active agent afterwards, be continue reaction 2 ~ 3h under the condition of 66 ~ 70 DEG C in temperature, then add water dilution 20 ~ 30 times, continue reaction 16 ~ 20h again, obtain polymer performed polymer;
(2) described polymer performed polymer is added to the water, and at 120 ~ 130 DEG C of microwave treatment 45 ~ 60min;
(3) after step (2) gained mixed reactant being cooled to room temperature, isolate solids wherein, successively after washing, drying treatment, obtain khaki color solid;
(4) in protective atmosphere, by described khaki color solid in 350 ~ 380 DEG C of roasting 6 ~ 12h, target product is obtained.
5. method for making according to claim 4, is characterized in that step (1) comprising:
By water-soluble for phenol formation phenol solution, add excess formaldehyde and highly basic again, and at 70 ~ 75 DEG C of reaction 0.5 ~ 1h, add tensio-active agent afterwards, temperature be 66 ~ 70 DEG C, stirring velocity continues reaction 2 ~ 3h under being the condition of 300 ~ 380rpm, then add water dilution, then continue reaction 16 ~ 20h, obtain polymer performed polymer;
Or, phenol is added formaldehyde solution and is warming up to 70 DEG C, after Keep agitation 0.5 ~ 1h, add highly basic again, continue at 70 ~ 75 DEG C of Keep agitation 0.5 ~ 1h, then add tensio-active agent, temperature be 66 ~ 70 DEG C, stirring velocity continues reaction 2 ~ 3h under being the condition of 300 ~ 380rpm, then add water dilution, then continue reaction 16 ~ 20h, obtain polymer performed polymer.
6. the method for making according to any one of claim 4-5, is characterized in that the mass ratio of described phenol, formaldehyde and highly basic is 10:15:1.
7. the method for making according to any one of claim 4-5, is characterized in that described tensio-active agent comprises F127.
8. the method for making according to any one of claim 4-5, is characterized in that described highly basic comprises NaOH.
9. method for making according to claim 5, is characterized in that described formaldehyde solution comprises the commercially available formaldehyde solution that concentration is 35wt% ~ 45wt%.
10. a carbon dioxide adsorption device, is characterized in that the ordered mesoporous polymer nanometer ball with flexure type duct comprised according to any one of claim 1-2.
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| CN105566589A (en) * | 2015-12-08 | 2016-05-11 | 上海师范大学 | Amino-functionalization ordered mesopore phenolic resin material and preparing method thereof |
| CN108584908A (en) * | 2018-06-21 | 2018-09-28 | 夏辉 | A kind of monodisperse porous carbon ball and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105566589A (en) * | 2015-12-08 | 2016-05-11 | 上海师范大学 | Amino-functionalization ordered mesopore phenolic resin material and preparing method thereof |
| CN105566589B (en) * | 2015-12-08 | 2017-11-07 | 上海师范大学 | Amino functional ordered mesoporous phenolic resin material and preparation method thereof |
| CN108584908A (en) * | 2018-06-21 | 2018-09-28 | 夏辉 | A kind of monodisperse porous carbon ball and preparation method thereof |
| CN108584908B (en) * | 2018-06-21 | 2020-04-10 | 夏辉 | Monodisperse porous carbon spheres and preparation method thereof |
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