CN104892874B - Ordered mesoporous polymer nanosphere, its preparation method and application with flexure type duct - Google Patents
Ordered mesoporous polymer nanosphere, its preparation method and application with flexure type duct Download PDFInfo
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- CN104892874B CN104892874B CN201510268935.2A CN201510268935A CN104892874B CN 104892874 B CN104892874 B CN 104892874B CN 201510268935 A CN201510268935 A CN 201510268935A CN 104892874 B CN104892874 B CN 104892874B
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- nanosphere
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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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 a kind of ordered mesoporous polymer nanosphere with flexure type duct, its particle diameter is 100nm~200nm, and with two-dimentional hexagonal phase meso-hole structure, the two-dimentional hexagonal phase meso-hole structure includes being distributed in nanometer ball surface and through a plurality of circular bender type ducts of nanosphere, and the aperture in the duct is 2nm~3nm.The invention also discloses the preparation method of the nanosphere, including：Phenol and formaldehyde are taken as Material synthesis macromolecule performed polymer; then by macromolecule performed polymer in heating condition system microwave treatment, room temperature is cooled to, and isolate the solids in mixed reactant; thereafter solids is calcined in protective atmosphere, obtains target product.The ordered mesoporous polymer nanosphere that the present invention is provided is a kind of New Type of Mesoporous material, the features such as with unique duct pattern and bigger serface, different phase meso-hole structures, and preparation process is simple is controllable, it is with low cost, efficiency high, environmental protection, is that phenolic resin opens new synthetic technology and application field.
Description
Technical field
It is the present invention relates to a kind of preparation method of mesoporous material more particularly to a kind of with the order mesoporous of flexure type duct
High molecular nanometer sphere, Preparation Method And The Use, such as application in absorbing carbon dioxide.
Background technology
In recent years, ordered mesoporous material because of its bigger serface and pore volume, uniform adjustable aperture and skeleton composition and
Controllable pattern, has broad application prospects in fields such as catalysis, absorption and energy storage, has obtained the extensive attention of people.
Recently, there is researcher successfully to utilize organic solvent volatility process, prepared high-sequential two dimension or three-dimensional structure it is mesoporous
Macromolecule and carbon material.However, this preparation technology workload is big, the production time is long, and can not largely produce.For a long time,
Industry is thirsted for developing a kind of method of simple possible always preparing the orderly and adjustable mesoporous polymer material of structure.
The content of the invention
It is a primary object of the present invention to provide a kind of ordered mesoporous polymer nanosphere with flexure type duct and its
Preparation method, 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 nanosphere with flexure type duct, its particle diameter is 100nm~200nm, and is had
Two-dimentional hexagonal phase meso-hole structure, the two-dimentional hexagonal phase meso-hole structure includes being distributed in the nanometer ball surface and being received through described
A plurality of flexure type ducts of rice ball, the aperture in the duct is 2nm~3nm.
Further, the nanosphere is made up of phenolic resin, i.e. also referred to as bakelite resin nano ball.
Further, the duct is toroidal bend duct.
A kind of preparation method of the ordered mesoporous polymer nanosphere with flexure type duct, it may include：Take phenol with
Excessive formaldehyde synthesizes macromolecule performed polymer, then in the aqueous phase system containing surfactant as raw material with hydro-thermal method
By the macromolecule performed polymer in 120~130 DEG C of 45~60min of microwave treatment, room temperature is cooled to, mixing is isolated afterwards anti-
The solids in thing is answered, and obtained solids is calcined 6~12h in protective atmosphere in 350~380 DEG C, obtained target and produce
Thing.
Among one more preferred embodiment, the preparation method can include：
(1) phenol is mixed with excess formaldehyde, highly basic in aqueous phase system, and 0.5~1h is reacted at 70~75 DEG C, afterwards
Surfactant is added, continues to react 2~3h under conditions of being 66~70 DEG C in temperature, then add water to dilute 20~30 times,
16~20h of reaction is further continued for, macromolecule performed polymer is obtained；
(2) the macromolecule performed polymer is added to the water, and in 120~130 DEG C of 45~more than 60min of microwave treatment；
(3) after step (2) gained mixed reactant being cooled into room temperature, solids therein is isolated, scrubbed successively,
After dried process, khaki solid is obtained；
(4) in protective atmosphere, the khaki solid is calcined 6~12h in 350~380 DEG C, obtains target and produce
Thing.
Further, step (1) can include：Phenol is dissolved in water and forms phenol solution, add excess formaldehyde and strong
Alkali, and 70~75 DEG C react 0.5~1h, surfactant is added afterwards, temperature be 66~70 DEG C, mixing speed be 300
Continue to react 2~more than 3h under conditions of~380rpm, then add water dilution, be further continued for 16~more than 20h of reaction, obtain high
Molecule performed polymer.
Used as preferably one of concrete application scheme, step (1) further may include steps of：
A, phenol is dissolved in the water under the conditions of 40 DEG C, forms phenol solution；
B, addition formaldehyde and the highly basic in step A obtains phenol solution, continuation stir 0.5h at 70 DEG C；
C, again in mixed solution obtained by step B add surfactant (for example, preferred proportion can be 0.96g F127
Be dissolved in 15ml water, but not limited to this), temperature be 70 DEG C, rotating speed be 350rpm under conditions of stir more than 2h；
D, by step C gained mixture add water dilution, continue stir more than 16h stop, obtain macromolecule phenolic resin
Performed polymer.
Further, step (1) can also include：Phenol is added into formalin and 70 DEG C are warming up to, 0.5 is persistently stirred
After~1h, highly basic is added, continue at 70~75 DEG C and persistently stir 0.5~1h, be subsequently adding surfactant, be in temperature
66~70 DEG C, mixing speed be 300~380rpm under conditions of continue react 2~3h, then add water dilution, be further continued for reaction
16~20h, obtains macromolecule performed polymer.
More preferred, the mass ratio of the phenol, formaldehyde and highly basic is 10:15:1.
Further, the surfactant may be selected from but be not limited to F127, and the F127 is a kind of triblock polymer
(PEO-PPOX-PEO), its molecular formula is PEO-PPO-PEO.
Further, the highly basic can select but be not limited to NaOH.
Further, the formalin can select but be not limited to the commercially available formalin that concentration is 35~40wt%.
Present invention also offers the purposes of the ordered mesoporous polymer nanosphere with flexure type duct.
For example, provide a kind of carbon dioxide adsorption device, it includes described with the order mesoporous of flexure type duct
High molecular nanometer sphere.
Compared with prior art, advantages of the present invention at least that：
(1) a kind of new mesoporous material, i.e. the ordered mesoporous polymer nanosphere with flexure type duct have been synthesized, have been
Phenolic resin opens new application field；
(2) generated time of the New Type of Mesoporous material is greatly shortened than the generated time of traditional phenolic resin, and efficiency is obtained
Effectively to be lifted, thus can be with energy saving, environmental protection.
Brief description of the drawings
Fig. 1 is a kind of X-ray scatter diagram of ordered mesoporous polymer nanosphere in one embodiment of the invention；
Fig. 2 a-2b are a kind of transmission electron microscope picture of ordered mesoporous polymer nanosphere in one embodiment of the invention；
Fig. 3 is a kind of Flied emission surface sweeping electron microscope of ordered mesoporous polymer nanosphere in one embodiment of the invention；
Fig. 4 is a kind of carbon dioxide adsorption performance test of ordered mesoporous polymer nanosphere in one embodiment of the invention
Figure.
Specific embodiment
Generally, the present invention is based on organic-organic self assembly strategy, from triblock copolymer F127 (polycyclic oxygen
Ethane-PPOX-PEO) as surfactant, with phenol and formaldehyde as high polymer monomer, using microwave knot
Reduction technique after a step in situ is closed, by changing high polymer monomer ratio or concentration and experimental technique condition, is realized to orderly
The pore passage structure of mesoporous phenolic resin material and the Effective Regulation of pattern, obtain with bigger serface and annular curved duct
Orderly functional mesoporous material, it is expected to obtain widely should at the aspect such as gaseous storage, heavy metal ion adsorbed, organic catalysis
With.
Technical scheme is further described below in conjunction with accompanying drawing and preferred embodiment.
A kind of preparation method bag of the ordered mesoporous polymer nanosphere with flexure type duct involved by the embodiment
Include following steps：
Step 1：The synthesis of macromolecule performed polymer：During a certain amount of phenol is added into there-necked flask at 40 DEG C, add
2.1ml35-40wt% formalins, after being warming up to 70 DEG C, continue to stir 30min, add 0.1M sodium hydroxide solution 15ml, after
After continuous stirring 30min, add 15ml dissolved with the aqueous solution of 0.96g F127, adjustment temperature is stirred to 66 DEG C under 350rpm rotating speeds
After mixing 2h, the dilution of 50ml water is added.Continue to stir 16-18h, until there is red precipitate to occur, stop heating, be cooled to room temperature,
After precipitation dissolving produced by, macromolecule performed polymer is prepared.
Step 2：3.5ml macromolecules performed polymer obtained above is loaded into 30ml microwave reaction pipes, and adds 11ml water dilute
Release.After microwave reaction pipe is reacted into 1h under 120 degree of microwave, room temperature is cooled to, the solid that will be aged in reaction tube is centrifuged, with steaming
After distilled water washing impurity-removing matter, khaki solid is obtained after dried process.
Step 3：By khaki solid obtained above under nitrogen protective condition, under the conditions of 350 DEG C, 6h is calcined, removed
Surfactant F127 is removed, target product, i.e. the ordered mesoporous polymer nanosphere with bending types duct is obtained.
Step 4：A series of signs are carried out to above-mentioned target product.
Involved all kinds of intermediate products and final product (being once referred to as " sample ") can in the present embodiment building-up process
Structural characterization is carried out by the following means：
Transmission electron microscope is in Japanese JEOL JEM2011 types high-resolution-ration transmission electric-lens in acquisition under 200kV；
The type cold field emission SEM of S 4800 that stereoscan photograph is produced in Japanese HITACHI companies in
Obtained under 3.0kV；
The type surface area test instrument of NOVA 4000 produced by Kang Ta companies of the U.S. measures N2Adsorption isothermal curve, sample
Specific surface area be calculated by BET equations.
Fig. 1 is referred to, preceding aim product has high-sequential two dimension hexagonal phase pore structure.
Please continue to refer to Fig. 2 a- Fig. 2 b, preceding aim its surface is observed that the presence of mesopore orbit, is a kind of special
Different toroidal bend duct.Meanwhile, Fig. 3 is referred to, preceding aim product is spheric granules, and size is than more uniform, average diameter
About in 100nm or so.Also, with reference to Fig. 2 a, Fig. 2 b and Fig. 3, it is also possible to which preceding aim product has height for very clear seeing
The orderly two dimension hexagonal phase pore structure of degree.
Fig. 4 is referred to, is found after tested, preceding aim product shows adsorption capacity higher to carbon dioxide.This hair
Bright ordered mesoporous polymer nanosphere is a kind of New Type of Mesoporous material, with unique duct pattern and bigger serface, difference
The features such as phase meso-hole structure, and preparation process is simple is controllable, with low cost, efficiency high, environmental protection.The present invention is phenolic resin
Open new synthetic technology and application field.
It should be appreciated that the foregoing is only the preferred embodiments of the present invention, it is not intended to limit the invention, for this area
Technical staff for, all any modification, improvement within the spirit and principles in the present invention, made etc. all should be included in this
Within the protection domain of invention.
Claims (8)
1. a kind of ordered mesoporous polymer nanosphere with flexure type duct, it is characterised in that：The nanosphere is by phenolic aldehyde tree
Fat is constituted, and the particle diameter of the nanosphere is 100nm~200nm, and the nanosphere has two-dimentional hexagonal phase meso-hole structure, described
Two-dimentional hexagonal phase meso-hole structure includes being distributed in the nanometer ball surface and through a plurality of toroidal bend holes of the nanosphere
Road, the aperture in the toroidal bend duct is 2nm~3nm.
2. there is the preparation method of the ordered mesoporous polymer nanosphere in flexure type duct described in claim 1, it is characterised in that including：
(1) phenol is mixed with excess formaldehyde, highly basic in aqueous phase system, and 0.5~1h is reacted at 70~75 DEG C, added afterwards
Surfactant, continues to react 2~3h under conditions of being 66~70 DEG C in temperature, then adds water to dilute 20~30 times, followed by
16~20h of continuous reaction, obtains macromolecule performed polymer；
(2) the macromolecule performed polymer is added to the water, and in 120~130 DEG C of 45~60min of microwave treatment；
(3) after step (2) gained mixed reactant being cooled into room temperature, solids therein is isolated, it is scrubbed successively, dry
After treatment, khaki solid is obtained；
(4) in protective atmosphere, the khaki solid is calcined 6~12h in 350~380 DEG C, obtains target product.
3. preparation method according to claim 2, it is characterised in that step (1) includes：
Phenol is dissolved in water and forms phenol solution, add excess formaldehyde and highly basic, and 0.5~1h is reacted at 70~75 DEG C, it
After add surfactant, temperature be 66~70 DEG C, mixing speed be 300~380rpm under conditions of continue react 2~3h,
Water dilution is then added, 16~20h of reaction is further continued for, macromolecule performed polymer is obtained；
Or, phenol is added into formalin and 70 DEG C are warming up to, persistently stir after 0.5~1h, highly basic is added, continue at
70~75 DEG C persistently stir 0.5~1h, be subsequently adding surfactant, temperature be 66~70 DEG C, mixing speed be 300~
Continue to react 2~3h under conditions of 380rpm, then add water dilution, be further continued for 16~20h of reaction, obtain macromolecule pre-polymerization
Body.
4. the preparation method according to any one of claim 2-3, it is characterised in that the mass ratio of the phenol, formaldehyde and highly basic
It is 10:15:1.
5. the preparation method according to any one of claim 2-3, it is characterised in that the surfactant includes F127.
6. the preparation method according to any one of claim 2-3, it is characterised in that the highly basic includes NaOH.
7. preparation method according to claim 3, it is characterised in that the formalin includes that concentration is 35wt%~45wt%
Commercially available formalin.
8. a kind of carbon dioxide adsorption device, it is characterised in that comprising described in claim 1 with the orderly of flexure type duct
Mesoporous polymer nanosphere.
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| CN108584908B (en) * | 2018-06-21 | 2020-04-10 | 夏辉 | Monodisperse porous carbon spheres and preparation method thereof |
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