CN1696180A - Organic pore-borne material generated by self-assembly of organic and organic, and preparation method - Google Patents

Organic pore-borne material generated by self-assembly of organic and organic, and preparation method Download PDF

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CN1696180A
CN1696180A CN 200510025508 CN200510025508A CN1696180A CN 1696180 A CN1696180 A CN 1696180A CN 200510025508 CN200510025508 CN 200510025508 CN 200510025508 A CN200510025508 A CN 200510025508A CN 1696180 A CN1696180 A CN 1696180A
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polymer
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structure directing
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赵东元
孟岩
顾栋
张福强
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Fudan University
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Fudan University
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Abstract

A process for preparing organic meso-porous material by organic-organic self-assembly features that the surfactant or organic high-molecular material is used as the structure guider, and the high-molecular precursor and said structure guider take part in organic-organic self-assembly. Said meso-porous material has ordered mesoporous arteries with different structures, high pore volume and high specific surface area.

Description

Organic mesoporous material that produces by organic-organic self-assembly and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a class by organic-organic mesoporous material of organic self-assembly synthetic (comprising polymer mesoporous material and carbon mesoporous material) and preparation method thereof.
Technical background
The mesoporous material of high-sequential has important application prospects in fields such as catalysis, absorption, separation, mass transfer, chemical sensitisations.In recent years, the research of mesoporous material has obtained fast development, utilizes various tensio-active agents to be template, and people are the mesoporous silicon oxide molecular sieve of synthetic various structures, has proposed various novel synthetic.The synthetic of present silicon oxide mesoporous molecular sieve has been tending towards ripe, and existing multiple mesopore silicon oxide has been realized large-scale industrial production.These meso pore silicon oxide materials have high thermostability and mechanical stability, are used for industrial production as catalyzer or support of the catalyst, sorbent material.Compare with inorganic mesoporous silica material, the development of metal oxide, sulfide mesoporous material relatively slowly many, this mainly is because due to its synthetic difficulty, thermally-stabilised difference.The contriver has proposed " acid base pair " synthetic route recently, has successfully synthesized a series of metal oxide compounds, mixed metal oxide, metal phosphate, hybrid metal phosphoric acid salt, metal borate and hybrid metal borate meso-porous molecular sieve material.Yet, have high stability, dystectic nonmetallic compound (comprising carbon, phosphorus, boron etc.), semi-conductor (comprising carbide, nitride, phosphide and boride etc.), also there is not sophisticated synthetic technology to satisfy its requirement at present, its synthetic report that yet there are no.Utilize the mesopore silicon oxide of high-sequential to be hard template, successfully prepared the anti-phase meso-porous carbon material of high-ratio surface.Yet this carbon material is made up of the armorphous nano carbon-point, the relative broad of accumulation space pore size distribution that produces between rod and the rod, and the cost costliness, its application has been subjected to greatly restriction.
The diversity that organic mesoporous material is formed because of its " softness " skeleton and be easy to characteristics such as finishing has tangible difference with mineral compound, aspect catalysis, gas adsorption, drug delivery, the separation great application prospect is being arranged.But since organic crosslinked self-assembly that is that all right at present is ripe, synthetic difficulty is big, organically forms to have relatively poor thermostability and mechanical stability, has limited the synthetic of organic mesoporous material and uses.For this reason, the researchist is exploring the especially novel method of polymer mesoporous material of synthetic organic mesoporous material with high-sequential duct, high-specific surface area, high pore volume always.
At present, the synthetic method of the relevant nanoporous organic polymer material of having reported mainly contains: control foaming, ion etching method, molecular imprinting and segmented copolymer self-assembly, wherein back two kinds of methods often are used as the organic polymer mesoporous material of synthetic high-sequential.But compare with mesoporous silicon oxide molecular sieve, its synthetic method is comparatively complicated, and the degree of order, specific surface area and the pore volume that obtain material are well below meso pore silicon oxide material.In addition, consequent mesoporous polymer material does not have the covalent structure, only there are weak interactions such as pi-pi bond, hydrogen bond and Van der Waals key between molecule and the molecule,, thereby limited the application of organic mesoporous material widely the less stable of solvent and heat.Up to the present also there are not the aperture of ordered mesoporous polymer material and the report of specific surface area.In order to address the above problem, key is to develop a kind of simple synthetic method, makes gained organic nano hole material have higher order on meso-scale, has higher specific surface area and pore volume simultaneously.
Summary of the invention
The objective of the invention is to propose a kind of simple and easy to do synthetic method with organic mesoporous material in high specific surface area and pore volume, high-sequential duct, and the organic mesoporous material of method synthetic thus.
The present invention with tensio-active agent or organic polymer as structure directing agent, utilize the organic-organic self-assembly between polymer presoma and the structure directing agent, organic mesoporous material of synthetic high-sequential, comprise polymer mesoporous material and carbon mesoporous material, the gained material has the mesopore orbit of high-sequential, the space structure in its duct can for stratiform (as L α), spiral (as Ia3d), hexagonal (as p6mm, P63/mmc), cube (as Pm3n, Pn3m, Im3m etc.), four directions (as P4/mmm) or quadrature multiple mesoscopic structures such as (as P4mmc); Its aperture is 1.5-20nm, and pore volume is 0.1-2.5cm 2/ g, specific surface area is 400-3000m 2/ g.
The preparation method of organic mesoporous material of the present invention is as follows:
(1) at first structure directing agent is dissolved in and makes settled solution in the solvent;
(2) add the polymer presoma of prepared beforehand again, stir down at 10-80 ℃ and it was fully disperseed in 5-35 minute;
(3) add linking agent or direct heating then, further polymerization macromolecule presoma, temperature is 100-180 ℃, the time is 4-72 hour;
(4) adopt under the inert atmosphere high-temperature roasting or heating method of extraction to remove structure directing agent at last, obtain the organic polymer mesoporous material;
(5) under protection of inert gas, with 1-40 ℃ of min -1Heat-up rate to 700-2100 ℃ of high-temperature roasting 2-10 hour, obtains the carbon mesoporous material;
In the above-mentioned steps, the mass ratio that feeds intake of reaction mass is: structure directing agent: polymer presoma: linking agent: solvent=1: (0.05-10): (0.05-1): (5-100).
Among the present invention, the polymer presoma of synthetic organic mesoporous material is high polymer monomer or performed polymer, can control the molecular weight of presoma by controlling reaction time, temperature of reaction and polymerization starter consumption.It is lower at the initial reaction stage molecular weight, and promptly the molecular weight control of presoma between 000, can well be dissolved in solvent at 100-50, forms the homogeneous system with solvent, structure directing agent.After mesoscopic structure forms, be increased to temperature of reaction 100-180 ℃, prolong reaction times 4-72 hour or add linking agent, further polymerization of precursor.
Among the present invention, the macromolecular scaffold of resulting mesoporous material has stable build (or netted) structure; High glass transition (generally being higher than 100 ℃); Insoluble not molten; Have thermostability and chemical stability preferably with respect to structure directing agent.This family macromolecule can be by polycondensation synthetic resol
Among the present invention, the solvent that can be used for dissolving tensio-active agent, organic polymer structure directing agent and polymer presoma comprises: water, ethanol, methyl alcohol, tetrahydrofuran (THF), methylene dichloride, chloroform, acetone, dimethyl sulfoxide (DMSO), dioxane, second cyanogen, formic acid, acetate or pyridine isopolarity solvent;
The mixture that comprises in nonionogenic tenside, cats product, anion surfactant, the amphoterics one or more among the present invention as the structure directing agent tensio-active agent.Wherein, nonionogenic tenside can be the polyoxyethylene tensio-active agent, as Brij52, and C 16H 33(OCH 2CH 2) 2OH (is abbreviated as C 16EO 2); Brij30, C 12EO 4Brij56, C 16EO 10Brij58, C 16EO 20Brij76, C 18EO 10Brij78, C 16EO 20Brij97, C 18H 35EO 10Brij35, C 12EO 23,
TritonX-100, CH 3C (CH 3) 2CH 2C (CH 3) 2C 6H 4(OCH 2CH 2) 10OH; TritonX-114, CH 3C (CH 3) 2CH 2C (CH 3) 2C 6H 4(OCH 2CH 2) 5OH; Tetronic 908, (EO 113PO 22) 2NCH 2CH 2N (PO 22EO 113) 2Tetronic901, (EO 3PO 18) 2NCH 2CH 2N (PO 18EO 3) 2Tetronic 90R4, (EO 16PO 19) 2NCH 2CH 2N (PO 19EO 16) 2Tween series non-ionic surfactants etc.; Also can be diblock, three block polyox-yethylene-polyoxypropylene block copolymer (EO mBO n, EO xPO yEO x, PO xEO yPO x, EO xBO yEO x), include EO 115BO 103, EO 75BO 54, EO 47BO 62, EO 50BO 70, EO 68BO 65, EO 40BO 79, EO 290BO 33, EO 5PO 70EO 5, EO 13PO 70EO 13EO 17PO 85EO 17, EO 20PO 70EO 20, EO 20PO 30EO 20, EO 26PO 39EO 26, EO 80PO 30EO 80, EO 100PO 39EO 100, EO 106PO 70EO 106, EO 123PO 47EO 123, EO 132PO 50EO 132, PO 19EO 33PO 19, EO 39BO 47EO 39Deng; Also can be organic amine tensio-active agent C nH 2n+1NH 2, H 2NC nH 2nNH 2(n=6～20).Anion surfactant can be long chain alkyl sulfates C nH 2n+1SO 4M 2, chain alkyl sulfonate C nH 2n+1SO 3M, chain alkyl carboxylate salt C nH 2n+1COOM and long-chain alkyl benzene sulfonate C nH 2n+1C 6H 4SO 3M, chain alkyl phosphoric acid salt C nH 2n+1PO 4M 2, n=8～18, M=Na +, K +, NH 4 +Deng; Cats product can be various quaternary ammonium salts such as long-chain trimethylammonium bromide C nH 2n+1N (CH 3) 3Br, (n=10～20), double star seating face promoting agent (Geminisurfactant) C mH 2m+1N (CH 3) 2C nH 2n+1N (CH 3) 3Br 2, (m=10～24, n=2～20), three quaternary surfactant (C nH 2n+1HN (CH 3) 2C sH 2sN (CH 3) C mH 2m+1N (CH 3) 3Br 3, C N-s-m-1), C 14-2-3-1, C 16-2-3-1, C 18-2-3-1And C 22-2-3-1, C 18-3-3-1, C 18-3-4-1Deng; Or rigidity Bolaform type tensio-active agent (CH 3) 3NH 24C 12OC 6H 4C 6H 4OC 12H 24N (CH 3) 3Br 2, (CH 3) 3NC 3H 6(CH 3) 2NH 24C 12OC 6H 4C 6H 4OC 12H 24N (CH 3) 2C 3H 6N (CH 3) 3Br 4Amphoterics can be alkyl betaine-type, dihydroxy ethyl betaine type, alkyl amido betaine type, alkyl hydroxy sulphonic acid betaine type, imidazoline type, carboxylic acid type tetrahydroglyoxaline, sulfonic acid type tetrahydroglyoxaline or amino acid pattern etc.
Among the present invention, have lower thermostability (or second-order transition temperature＜100 ℃) or relatively poor chemical stability, comprise polyethers such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, all kinds of Mierocrystalline celluloses as the organic polymer of structure directing agent; Aliphatic polies such as poly-glycollide, polylactide, polycaprolactone; Polyolefine such as polyethylene, polystyrene; Also can be segmented copolymer, as polystyrene-poly tetrem thiazolinyl pyridine (PS-PVP), polyethylene oxide-poly-ethylethylene or polyethylene oxide-polyethylene propylene alternating copolymer etc.
Among the present invention, there is weak interaction force between polymer presoma and the structure directing agent, comprises that the π-π between organic aromatic nucleus interacts, between the hydroxyl and the intermolecular Van der Waals interaction between hydrogen bond, the charge effect between the zwitterion and the organic group between hydroxyl and ether, the ketone etc.By weak interaction force, polymer presoma and structure directing agent assembling produce orderly mesoscopic structure.
Among the present invention, in the polymerization of polymer presoma, can add linking agent, to increase polymerization velocity and degree of crosslinking.Linking agent is the organic molecule with two or two above functionality, comprises Resorcinol, vulkacit H etc.The add-on of linking agent is: the 0-5 of structure directing agent is (mol ratio) doubly.
Among the present invention, the removal of structure directing agent can be adopted solvent or oxygenant reflux extraction method. and the organic solvent of employing can be: the lower solvents of boiling point such as water, methyl alcohol, ethanol, tetrahydrofuran (THF), acetone; The oxygenant that adopts can be sulfuric acid, aqueous hydrogen peroxide solution.Can adopt also that high-temperature roasting method is with removal of surfactant under the inert atmosphere, maturing temperature is 200-500 ℃, and the treatment time is 5-16 hour.
Among the present invention, institute's synthetic polymer mesoporous material has the mesopore orbit of high-sequential, the space structure in its duct can be stratiform, spiral, hexagonal, cube, multiple mesoscopic structures such as four directions or quadrature.Have adjustable wide aperture (can reach 1.5-20nm), big pore volume (can reach 0.1-2.5cm 3/ g), high specific surface area (can reach 400-3000m 2/ g, especially 1000-3000m 2/ g).Institute's synthetic polymer mesoporous material is through further thermal treatment (being higher than 700 ℃), can be converted into meso-porous carbon material, the gained meso-porous carbon material has the space structure identical with the mesoporous polymer material, and its skeleton can be that agraphitic carbon is formed, and also can be the carbon of greying or semi-graphited.This meso-porous carbon material has higher thermostability, still keeps mesoscopic structure preferably through 1400 ℃ of processing after 5 hours, and its characteristic properties is as follows: (can reach 1.5～20nm), big pore volume (can reach 0.1～2.5cm in adjustable wide aperture 3/ g), high specific surface area (can reach 400～3000m 2/ g).
Description of drawings
Fig. 1 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the feature XRD figure of the polymer mesoporous material of roasting gained spectrum (its duct spatial symmetry is hexagonal structure p6m) under 350 ℃ of nitrogen atmospheres.
Fig. 2 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the feature XRD figure of the polymer mesoporous material of roasting gained spectrum (its duct spatial symmetry is cubic structure Im-3m) under 350 ℃ of nitrogen atmospheres.
Fig. 3 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the feature XRD figure of the polymer mesoporous material of roasting gained spectrum (its duct spatial symmetry is the mixed phase of hexagonal structure p6m and cubic structure Im-3m) under 350 ℃ of nitrogen atmospheres.
Fig. 4 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the ordinary optical photo of the macromolecular material that obtains with mesoscopic structure
Fig. 5 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the feature TEM collection of illustrative plates (A) of the polymer mesoporous material of roasting gained and use 48%H under 350 ℃ of nitrogen atmospheres 2SO 4The feature TEM collection of illustrative plates (B) (its duct spatial symmetry is hexagonal structure p6m) of 95 ℃ of following reflux extractions polymer mesoporous material of gained after 24 hours.
Fig. 6 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the feature TEM collection of illustrative plates (A) of the polymer mesoporous material of roasting gained and use 48%H under 350 ℃ of nitrogen atmospheres 2SO 4The feature TEM collection of illustrative plates (B) (its duct spatial symmetry is cubic structure Im-3m) of 95 ℃ of following reflux extractions polymer mesoporous material of gained after 24 hours.
Fig. 7 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the nitrogen adsorption collection of illustrative plates (A) of the polymer mesoporous material of roasting gained and use 48%H under 350 ℃ of nitrogen atmospheres 2SO 4The feature nitrogen adsorption collection of illustrative plates (B) of the polymer mesoporous material of 95 ℃ of following reflux extractions gained after 24 hours.(its duct spatial symmetry is hexagonal structure p6m)
Fig. 8 is to be precursor with 60 minutes resol performed polymers, EO 106PO 70EO 106As tensio-active agent, the nitrogen adsorption collection of illustrative plates of the polymer mesoporous material of roasting gained under 350 ℃ of nitrogen atmospheres (its duct spatial symmetry is a cube Im-3m).
Fig. 9 is to be precursor with 60 minutes resol performed polymers, EO 20PO 70EO 20As tensio-active agent, the feature XRD figure of the polymer mesoscopic material that newly obtains spectrum (its mesoscopic structure is stratiform L α).
Figure 10 is to be precursor with 60 minutes resol performed polymers, EO 20PO 70EO 20As tensio-active agent, in 48%H 2SO 4The polymer of 95 ℃ of following reflux extractions gained after 24 hours is situated between and sees the feature TEM collection of illustrative plates (its mesoscopic structure is stratiform L α) of material.
Figure 11 is to be parent with the phenolic resin material with six side p6m mesoscopic structures, under nitrogen atmosphere, respectively in the feature XRD spectra (its duct spatial symmetry is hexagonal structure p6m) of the various mesoporous carbon of 900 ℃ and 5 hours gained of 400 ℃ of roastings.
Figure 12 is to be parent to have cube phenolic resin material of Im-3m mesoscopic structure, under nitrogen atmosphere, respectively in the feature XRD spectra (its duct spatial symmetry is cubic structure Im-3m) of the various mesoporous carbon of 900 ℃ and 5 hours gained of 1400 ℃ of roastings.
Figure 13 is to be parent with the phenolic resin material with six side p6m mesoscopic structures, under nitrogen atmosphere, at the feature TEM and the high resolution TEM spectrogram (its duct spatial symmetry is hexagonal structure p6m) of the mesoporous carbon of 5 hours gained of 1400 ℃ of roastings.
Figure 14 is to be parent to have cube phenolic resin material of Im-3m mesoscopic structure, under nitrogen atmosphere, at the feature TEM and the high resolution TEM spectrogram (its duct spatial symmetry is a cube Im-3m) of the mesoporous carbon of 5 hours gained of 1400 ℃ of roastings.
Figure 15 is to be parent to have hexagonal structure m resol mesoporous material, under nitrogen atmosphere, respectively at the feature nitrogen adsorption spectrogram (its duct spatial symmetry is hexagonal structure p6m) of the various mesoporous carbon of 800 ℃ and 5 hours gained of 900 ℃ of roastings.
Figure 16 is to be parent to have cubic structure Im-3m resol mesoporous material, but under the nitrogen atmosphere, respectively at the feature nitrogen adsorption spectrogram (its duct spatial symmetry is cubic structure Im-3m) of the various mesoporous carbon of 900 ℃ and 5 hours gained of 1400 ℃ of roastings.
Embodiment
Embodiment 1, the preparation of polymer presoma:
The mol ratio of reaction mass: phenol (cresols, xylenol): formaldehyde (furfural)=1: (0.8-2.1)
Temperature of reaction: 65-70 ℃; Reaction times: 0.5-2 hour;
PH=1-3 or 7-11
An acidic catalyst: chlorsulfonic acid, hydrochloric acid, perchloric acid, sulfuric acid, oxalic acid
Basic catalyst: NH 3H 2O, NaOH, KOH, Ba (OH) 2
Example approach is as follows:
1.0g phenol in 40-42 ℃ of fusion, is added the 0.21g 20%NaOH aqueous solution and stirred ten minutes under this temperature, add 1.7g 37% formalin, be warming up to 70 ℃ of reactions 1 hour, being cooled to room temperature, is 6-7 with the pH value of 0.6M HCl solution regulator solution, is lower than 50 ℃ of decompression dehydrations.
Embodiment 2, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 20g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer (forming), stirred 5 minutes, make its uniform dispersion, form the homogeneous mixing solutions by 0.61g phenol and 0.39g prepared formaldehyde.Solution is transferred in the watch-glass, and 25 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 24 hours further polymerization macromolecule materials of 100 ℃ of baking oven internal heating fully after 8 hours.The 350 ℃ of roastings under nitrogen atmosphere of material after the polymerization were removed tensio-active agent in 5 hours, and sub-mesoporous material promptly secures satisfactory grades.The aperture of this material is 6.8nm, and pore volume is 0.63cm 3/ g, specific surface area is 652m 2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 3, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 30g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer (forming), stirred 5 minutes, make its uniform dispersion, form the homogeneous mixing solutions by 0.61g phenol and 0.39g prepared formaldehyde.Solution is transferred in the watch-glass, and 15 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 48 hours further polymerization macromolecule materials of 1000 baking oven internal heating fully after 8 hours.With the material 48%H after the polymerization 2SO 4Remove tensio-active agent in 95 ℃ of extractions in 24 hours that reflux, sub-mesoporous material promptly secures satisfactory grades.The pore volume of this material is 071cm 3/ g, specific surface area is 1042m 2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 4, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 15g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer (forming), stirred 10 minutes, make its homodisperse, form uniform solution by 0.92g phenol and 0.58g prepared formaldehyde.Solution is transferred in the watch-glass, and 25 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 72 hours further macromolecular materials that solidify of 100 ℃ of baking oven internal heating fully after 10 hours.The 500 ℃ of roastings under nitrogen atmosphere of material after solidifying were removed tensio-active agent in 5 hours, and sub-mesoporous material promptly secures satisfactory grades.The aperture of this material is 8.1nm, and pore volume is 0.98cm 3/ g, specific surface area is 1032m 2/ g, the duct spatial symmetry of material are the mixed phase of six side p6m structures and cube Im-3m structure.
Embodiment 5, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 25 gram ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer (forming), stirred 10 minutes, make its homodisperse, form uniform solution by 1.2g phenol and 0.78g prepared formaldehyde.Solution is transferred in the watch-glass, and 15 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 24 hours further macromolecular materials that solidify of 100 ℃ of baking oven internal heating fully after 10 hours.The 350 ℃ of roastings under nitrogen atmosphere of material after solidifying were removed tensio-active agent in 5 hours, and sub-mesoporous material promptly secures satisfactory grades.The aperture of this material is 6.8nm, and pore volume is 0.51cm 3/ g, specific surface area is 590m 2/ g, the duct spatial symmetry of material are a cube Im-3m structure.
Embodiment 6, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 35g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer and (form by 0.61g phenol and 0.39g prepared formaldehyde, stirred 30 minutes, make its uniform dispersion, form uniform solution.Solution is transferred in the watch-glass, and 20 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 24 hours further macromolecular materials that solidify of 150 ℃ of baking oven internal heating fully after 5 hours.The 900 ℃ of roastings under nitrogen atmosphere of material after solidifying were removed tensio-active agent in 5 hours, and the further charing of macromolecular scaffold promptly gets positive carbon mesoporous material.The aperture of this material is 2.9nm, and pore volume is 0.56cm 3/ g, specific surface area is 968m 2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 7, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 20g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer and (form by 0.61g phenol and 0.39g prepared formaldehyde, stirred 20 minutes, make its uniform dispersion, form uniform solution.Solution is transferred in the watch-glass, and 20 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 10 hours further macromolecular materials that solidify of 180 ℃ of baking oven internal heating fully after 5 hours.With the 2000 ℃ of roastings 3 hours under nitrogen atmosphere of the material after solidifying, the further charing of macromolecular scaffold promptly gets positive carbon mesoporous material.The aperture of this material is 2.2nm, and pore volume is 0.35cm 3/ g, specific surface area is 662m 2/ g, the duct spatial symmetry of material are six side p6m structures.
Embodiment 8, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 10g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer and (form by 1.2g phenol and 0.78g prepared formaldehyde, stirred 5 minutes, make its uniform dispersion, form uniform solution.Solution is transferred in the watch-glass, and 25 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 15 hours further macromolecular materials that solidify of 150 ℃ of baking oven internal heating fully after 5 hours.With the 900 ℃ of roastings 8 hours under nitrogen atmosphere of the material after solidifying, the further charing of macromolecular scaffold promptly gets positive carbon mesoporous material.The aperture of this material is 3.7nm, and pore volume is 0.44cm 3/ g, specific surface area is 778m 2/ g, the duct spatial symmetry of material are a cube Im-3m structure.
Embodiment 9, under the room temperature (25 ℃), with 1.0g EO 106PO 70EO 106Be dissolved in the 10g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer and (form by 1.2g phenol and 0.78g prepared formaldehyde, stirred 5 minutes, make its uniform dispersion, form uniform solution.Solution is transferred in the watch-glass, and 25 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 24 hours further macromolecular materials that solidify of 100 ℃ of baking oven internal heating fully after 5 hours.With the 1400 ℃ of roastings 5 hours under nitrogen atmosphere of the material after solidifying, the further charing of macromolecular scaffold promptly gets positive carbon mesoporous material.The aperture of this material is 4.1nm, and pore volume is 0.86cm 3/ g, specific surface area is 1035m 2/ g, the duct spatial symmetry of material are a cube Im-3m structure.
Embodiment 10, under the room temperature (25 ℃), with 1.0g EO 20PO 70EO 20Be dissolved in the 20g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer (forming), stirred 5 minutes, make its uniform dispersion, form the homogeneous mixing solutions by 1.2g phenol and 0.78g prepared formaldehyde.Solution is transferred in the watch-glass, and 25 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 24 hours further polymerization macromolecule materials of 100 ℃ of baking oven internal heating fully after 8 hours.The 350 ℃ of roastings under nitrogen atmosphere of material after solidifying were removed tensio-active agent in 5 hours, and sub-mesoporous material promptly secures satisfactory grades.The spatial symmetry in this material duct is six side p6m structures.
Embodiment 11, under the room temperature (25 ℃), with 1.0g EO 20PO 70EO 20Be dissolved in the 20g ethanol, stir and make settled solution, in this solution, add resol polymer performed polymer (forming) and 0.5g Resorcinol, stirred 20 minutes, make its uniform dispersion, form the homogeneous mixing solutions by 0.30g phenol and 0.20g prepared formaldehyde.Solution is transferred in the watch-glass, and 25 ℃ leave standstill volatilization ethanol, and the ethanol volatilization is placed on 24 hours further polymerization macromolecule materials of 100 ℃ of baking oven internal heating fully after 8 hours.With the material 48%H after the polymerization 2SO 4Remove tensio-active agent in 95 ℃ of extractions in 24 hours that reflux, sub-mesoporous material promptly secures satisfactory grades.The spatial symmetry in this material duct is a laminate structure.

Claims (9)

1, a kind of organic mesoporous material by organic-organic self-assembly generation, comprise polymer mesoporous material and carbon mesoporous material, it is characterized in that: this material has the mesopore orbit of high-sequential, the space structure in its duct be stratiform, spiral, hexagonal, cube, four directions or orthogonal multiple mesoscopic structure; Its aperture is 1.5-20nm, and pore volume is 0.1-2.5cm 3/ g, specific surface area is 400-3000m 2/ g; As structure directing agent, it is synthetic to carry out organic-organic self-assembly by polymer presoma and structure directing agent with tensio-active agent or organic polymer for it.
2, a kind of preparation methods as claimed in claim 1 is characterized in that:
(1) at first structure directing agent is dissolved in and makes settled solution in the solvent;
(2) add the polymer presoma of prepared beforehand again, stir down at 10-80 ℃ and it was fully disperseed in 5-35 minute;
(3) add linking agent or direct heating then, further polymerization macromolecule presoma, temperature is 100-180 ℃, the time is 4-72 hour;
(4) adopt under the inert atmosphere high-temperature roasting or heating method of extraction to remove structure directing agent at last, obtain the organic polymer mesoporous material;
(5) under protection of inert gas, with 1-40 ℃ of min -1Heat-up rate to 700-2100 ℃ of high-temperature roasting 2-10 hour, obtains the carbon mesoporous material;
In the above-mentioned steps, the mass ratio that feeds intake of reaction mass is: structure directing agent: polymer presoma: linking agent: solvent=1: (0.05-10): (0.05-1): (5-100).
3, preparation method according to claim 2 is characterized in that used polymer presoma is high polymer monomer or performed polymer, and molecular weight control is 100～50, between 000.
4, preparation method according to claim 3 is characterized in that described polymer performed polymer is a polycondensation synthetic resol.
5, preparation method according to claim 2, the solvent that it is characterized in that being used to dissolving structure directing agent and polymer precursor is water, ethanol, methyl alcohol, tetrahydrofuran (THF), methylene dichloride, chloroform, acetone, dimethyl sulfoxide (DMSO), dioxane, second cyanogen, formic acid, acetate or pyridine.
6, according to claim 2 described by the preparation method, it is characterized in that used tensio-active agent comprises among nonionogenic tenside, cats product, anion surfactant, the amphoterics one or more mixture; Wherein, nonionogenic tenside is the polyoxyethylene tensio-active agent, or the tween series non-ionic surfactants, or diblock, three block polyox-yethylene-polyoxypropylene block copolymers, perhaps organic amine tensio-active agent C nH 2n+1NH 2, H 2NC nH 2nNH 2, n=6～20; Anion surfactant is long chain alkyl sulfates C nH 2n+1SO 4M 2, chain alkyl sulfonate C nH 2n+1SO 3M, chain alkyl carboxylate salt C nH 2n+1COOM, long-chain alkyl benzene sulfonate C nH 2n+1C 6H 4SO 3M or chain alkyl phosphoric acid salt C nH 2n+1PO 4M 2, n=8～18, M is Na +, K +, NH 4 +Cats product is following quaternary ammonium salt: long-chain trimethylammonium bromide C nH 2n+1N (CH 3) 3Br, n=10～20, double star seating face promoting agent C mH 2m+1N (CH 3) 2C nH 2n+1N (CH 3) 3Br 2, m=10～24, n=2～20, three a quaternary surfactant (C nH 2n+1HN (CH 3) 2C sH 2sN (CH 3) C mH 2m+1N (CH 3) 3Br 3, C N-s-m-1), C 14-2-3-1, C 16-2-3-1, C 18-2-3-1And C 22-2-3-1, C 18-3-3-1, C 18-3-4-1, perhaps rigidity Bolaform type tensio-active agent (CH 3) 3NH 24C 12OC 6H 4C 6H 4OC 12H 24N (CH 3) 3Br 2, (CH 3) 3NC 3H 6(CH 3) 2NH 24C 12OC 6H 4C 6H 4OC 12H 24N (CH 3) 2C 3H 6N (CH 3) 3Br 4Amphoterics is alkyl betaine-type, dihydroxy ethyl betaine type, alkyl amido betaine type, alkyl hydroxy sulphonic acid betaine type, imidazoline type, carboxylic acid type tetrahydroglyoxaline, sulfonic acid type tetrahydroglyoxaline or amino acid pattern.
7, preparation method according to claim 2 is characterized in that used structure directing agent is
(1) polymer of second-order transition temperature＜100 ℃: polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, Mierocrystalline cellulose, poly-glycollide, polylactide, polycaprolactone, polyethylene, polystyrene; Or
(2) segmented copolymer: polystyrene-poly tetrem thiazolinyl pyridine, polyethylene oxide-poly-ethylethylene or polyethylene oxide-polyethylene propylene alternating copolymer.
8, preparation method according to claim 2 is characterized in that adding linking agent in the polymerization of polymer presoma, to increase polymerization velocity or degree of crosslinking; Wherein linking agent is the organic molecule with two or two above functionality, and the add-on of linking agent is the 0-5 mol ratio of structure directing agent.
9, preparation method according to claim 2 is characterized in that the removal of structure directing agent,
(1) adopt solvent or oxygenant reflux extraction method, used solvent is: water, methyl alcohol, ethanol, tetrahydrofuran (THF) or acetone, used oxygenant are sulfuric acid, aqueous hydrogen peroxide solution; Perhaps
(2) adopt high-temperature roasting method under the inert atmosphere, maturing temperature is 200-500 ℃, roasting time 5-16 hour.
CN 200510025508 2005-04-28 2005-04-28 Organic pore-borne material generated by self-assembly of organic and organic, and preparation method Pending CN1696180A (en)

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Cited By (9)

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CN100395310C (en) * 2006-03-06 2008-06-18 复旦大学 Method of preparing multiporous. polymer or multiporous carbon material with large ratio of surface and high sequence in water solution
CN101735473B (en) * 2009-11-30 2012-07-04 上海师范大学 Polymer composite with plasticity, ordered mesoporous polymer of multi-level structure and ordered mesoporous carbon material
CN101993058B (en) * 2009-08-31 2012-09-05 中国石油化工股份有限公司 Method for preparing mesoporous carbon materials
US8559162B2 (en) 2009-12-07 2013-10-15 Delta Electronics, Inc. Mesoporous carbon material, fabrication method thereof and supercapacitor
CN104693472A (en) * 2013-12-10 2015-06-10 中国科学院大连化学物理研究所 Ordered-mesoporous redox resin and synthetic method of ordered-mesoporous redox resin
CN106083165A (en) * 2016-06-06 2016-11-09 南京航空航天大学 A kind of preparation method of order mesoporous strontium titanates
CN111825171A (en) * 2020-06-12 2020-10-27 武汉尚源新能环境有限公司 Preparation method of mesoporous carbon electrode and organic wastewater treatment equipment
CN113086963A (en) * 2019-12-23 2021-07-09 中国科学院青岛生物能源与过程研究所 Monodisperse hollow-structure carbon mesoporous microsphere material and preparation method by taking organic-inorganic hybrid salt as template for induced assembly
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100395310C (en) * 2006-03-06 2008-06-18 复旦大学 Method of preparing multiporous. polymer or multiporous carbon material with large ratio of surface and high sequence in water solution
CN101993058B (en) * 2009-08-31 2012-09-05 中国石油化工股份有限公司 Method for preparing mesoporous carbon materials
CN101735473B (en) * 2009-11-30 2012-07-04 上海师范大学 Polymer composite with plasticity, ordered mesoporous polymer of multi-level structure and ordered mesoporous carbon material
US8559162B2 (en) 2009-12-07 2013-10-15 Delta Electronics, Inc. Mesoporous carbon material, fabrication method thereof and supercapacitor
CN104693472A (en) * 2013-12-10 2015-06-10 中国科学院大连化学物理研究所 Ordered-mesoporous redox resin and synthetic method of ordered-mesoporous redox resin
CN106083165A (en) * 2016-06-06 2016-11-09 南京航空航天大学 A kind of preparation method of order mesoporous strontium titanates
CN106083165B (en) * 2016-06-06 2018-11-23 南京航空航天大学 A kind of preparation method of order mesoporous strontium titanates
CN113086963A (en) * 2019-12-23 2021-07-09 中国科学院青岛生物能源与过程研究所 Monodisperse hollow-structure carbon mesoporous microsphere material and preparation method by taking organic-inorganic hybrid salt as template for induced assembly
CN113086963B (en) * 2019-12-23 2022-10-25 中国科学院青岛生物能源与过程研究所 Monodisperse hollow-structure carbon mesoporous microsphere material and induced assembly preparation method using organic-inorganic hybrid salt as template
CN111825171A (en) * 2020-06-12 2020-10-27 武汉尚源新能环境有限公司 Preparation method of mesoporous carbon electrode and organic wastewater treatment equipment
CN117343467A (en) * 2023-12-05 2024-01-05 内蒙古大学 Micelle-silicon dioxide asymmetric hybrid material and preparation method thereof
CN117343467B (en) * 2023-12-05 2024-03-19 内蒙古大学 Micelle-silicon dioxide asymmetric hybrid material and preparation method thereof

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