CN103788279A - Super-hydrophobic aggregate type nano-porous solid alkali material and preparation method thereof - Google Patents
Super-hydrophobic aggregate type nano-porous solid alkali material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a super-hydrophobic aggregate type nano-porous solid alkali material and a preparation method thereof. The preparation method comprises the following steps: stirring for at least three hours by using divinyl benzene as a crosslinking agent monomer, vinyl triazole as an alkaline monomer, an organic solvent as a polymerization solvent and azobisisobutyronitrile as an initiating agent at ordinary temperature and pressure under an airtight condition, copolymerizing the crosslinking agent monomer and the alkaline monomer under a solvothermal condition so as to obtain a nano-porous aggregate type blocky solid, wherein the polymerization temperature is 65-200 DEG C, the polymerization pressure is 0.1-5Mpa, the polymerization time is at least 12 hours, the volume ratio of the volume sum of the organic solvent, the cross-linking agent monomer and the alkaline monomer is 7.5-20, and the volume ratio of the vinyl triazole and the divinyl benzene is 0.2-1.0; carrying out evaporation drying on the obtained solid at room temperature and vacuum evaporation so as to obtain the super-hydrophobic aggregate type nano-porous solid alkali material.
Description
Technical field
The invention belongs to physical chemistry, the technical field of Materials science, relates in particular to a kind of super-hydrophobic aggretion type nanoporous solid alkali material and preparation method thereof.
Background technology
Recent years, along with the development of chemical industry, catalysis industry has obtained increasing extensively attention.Especially in petrochemical complex and field of fine chemical, catalyzer has shown more and more important effect as the most important composition of catalytic field.But the drawbacks limit such as acid catalyst catalytic efficiency is low, and corrodibility is strong its apply on a large scale.Compared with acid catalyst, the advantage that alkaline catalysts shows comprises: the advantages such as catalytic activity is high, and corrodibility is little have important application in organic synthesis and life science.But up to the present, base material kind is few: the common alkalimetal oxide that comprises, oxyhydroxide, hydrotalcites etc., but the regeneration difficulty of material, to airborne water and carbonic acid gas sensitivity, the easy inactivation in active centre, the drawbacks limit such as pore structure scarcity the widespread use of alkaline catalysts.
Existing a kind of strongly basic anion exchange resin, its skeleton is Vinylstyrene and styrol copolymer, active function groups is nitrogenous quaternary amine.As a kind of novel organic backbone solid alkali material, hydrophobic skeleton structure and simple preparation process make this material be widely used in the field such as catalyzed reaction and ion-exchange, now by industrialization.But its low specific surface area, deficient pore structure and the adverse influence of poor stability to catalyzed reaction, hydrophobicity does not reach application requiring yet simultaneously, and still more responsive to water and carbonic acid gas, it applies above-mentioned drawbacks limit widely at Heterogeneous alkali catalytic field.
Summary of the invention
The present invention is in order to overcome conventional solid alkali (alkalimetal oxide, oxyhydroxide, hydrotalcite etc.) to water sensitive, the easily carbonic acid gas in absorbed air and cause active centre inactivation, specific surface area is low, the shortcomings such as, regeneration poor with organic reaction substrate consistency is difficult, provide super-hydrophobic aggretion type nanoporous solid alkali material of a kind of bigger serface, large pore volume, super oleophylic and preparation method thereof.
In order to realize an object of the present invention, the invention provides a kind of preparation method of super-hydrophobic aggretion type nanoporous solid alkali material, comprise the steps: that it is linking agent monomer that a. selects Vinylstyrene, vinyl triazole is alkaline monomer, organic solvent is polymer solvent, azobisisobutyronitrile is initiator, under normal temperature and pressure air tight condition, stir after at least 3 hours, under solvent thermal condition, linking agent monomer and alkaline monomer are carried out to copolymerization, polymerization obtains nanoporous aggretion type blocks of solid, polymerization temperature is 65-200 ℃, polymerization pressure is 0.1-5MPa, polymerization time is 12h at least, the volume ratio of the volume sum of organic solvent and linking agent monomer and alkaline monomer is 7.5-20, the volume ratio of vinyl triazole and Vinylstyrene is 0.2-1.0, b. by the solid obtaining in step a volatile dry, vacuum-evaporation at ambient temperature, obtain super-hydrophobic aggretion type nanoporous solid alkali material.
In one embodiment of the invention, the organic solvent in step a is benzene, ethyl acetate, toluene or tetrahydrofuran (THF).
In one embodiment of the invention, the volume ratio between vinyl triazole and Vinylstyrene is 1:2.
In one embodiment of the invention, the adjusting of polymerization pressure realizes by being filled with nitrogen.
In order to realize another object of the present invention, the present invention also provides a kind of super-hydrophobic aggretion type nanoporous solid alkali material, solid alkali material is polydivinylbenezene-co-1-vinyl triazole, and the specific surface area of described polydivinylbenezene-co-1-vinyl triazole is 300-600m
2/ g, mean pore size is 10-30nm, pore volume is 0.6-1.4ml/g.
In sum, the present invention realizes Vinylstyrene and the copolymerization of vinyl triazole by solvent thermal synthetic technology, and then obtain there is bigger serface, excellence is hydrophobic, the aggretion type nanoporous solid alkali material of the skeleton structure of oleophylic, it is very little that the super-drainage structure of this material makes material be exposed in air the adsorptive capacity to water, greatly overcome the poor stability that conventional solid base material causes due to water suction in air, the shortcomings such as active centre inactivation, have improved the anti-poisoning ability of material and have recycled performance.Meanwhile, large specific surface area overcome traditional base material due to pore structure scarcity cause to its restriction of application aspect widely.We carry out modulation alkali center content by the composition of monomer in modulation polymerization process, and synthetic method is simple, with low cost.Material prepared by the present invention is found by catalysis Knoevenagel condensation and Michael addition reaction test, such novel solid base material has shown very excellent catalytic activity and regenerative power, These characteristics has important potential using value to this material in the application in base catalysis field, for solid alkali and the large-scale industrial application of associated materials thereof provide new approaches.
For above and other objects of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and coordinate accompanying drawing, be described in detail below.
Accompanying drawing explanation
Figure 1A is the nitrogen adsorption isotherm of the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention.
Figure 1B is the pore size distribution curve of the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention.
Fig. 2 is the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention and the infrared spectrum of nanoporous polydivinylbenezene.
Fig. 3 is that super-hydrophobic aggretion type nanoporous solid alkali material prepared by the present invention is tested for the contact angle of various reaction substrates.
Fig. 4 is carbonic acid gas-TPD curve of the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention.
Embodiment
The invention provides a kind of preparation method of super-hydrophobic aggretion type nanoporous solid alkali material, comprise the steps: that it is linking agent monomer that a. selects Vinylstyrene, vinyl triazole is alkaline monomer, organic solvent is polymer solvent, azobisisobutyronitrile is initiator, under normal temperature and pressure air tight condition, stir after at least 3 hours, under solvent thermal condition, linking agent monomer and alkaline monomer are carried out to copolymerization, polymerization obtains nanoporous aggretion type blocks of solid, polymerization temperature is 65-200 ℃, polymerization pressure is 0.1-5MPa, polymerization time is 12h at least, the volume ratio of the volume sum of organic solvent and linking agent monomer and alkaline monomer is 7.5-20, the volume ratio of vinyl triazole and Vinylstyrene is 0.2-1.0, b. by the solid obtaining in step a volatile dry, vacuum-evaporation at ambient temperature, obtain super-hydrophobic aggretion type nanoporous solid alkali material.
Enumerate embodiment below, illustrate in the present invention, there is bigger serface, the synthetic method of the organic framework structured solid alkali material of large pore volume, stable, super-hydrophobic, oleophylic.The quality of initiator does not affect.The adjusting of polymerization pressure realizes by being filled with nitrogen, and different pressures is for the specific surface area of material, and aperture etc. have larger impact.Change according to the ratio between polymerization process neutral and alkali function monomer and linking agent monomer, the specific surface area of material is at 300-600m
2can modulation between/g, aperture is modulation between 10-30 nanometer.
In embodiment, sample name is divided into two portions: PDVB and represents mesoporous polydivinylbenezene, and VT representative is as the vinyl triazole monomer in alkaline active centre.PDVB-VT-x, x represents the ratio of vinyl triazole monomer and divinyl benzene monomer.The present invention is the skeleton that is incorporated into material by the method Jiang Jian center of copolymerization between linking agent monomer and alkaline monomer.
Embodiment 1: take ethyl acetate as the synthesising mesoporous polydivinylbenezene material of solvent.
By 2 milliliters of divinyl benzene monomers, 0.4 milliliter of vinyl triazole monomer joins in the ethyl acetate solution containing 0.065g Diisopropyl azodicarboxylate and 48 milliliters, under normal temperature and pressure air tight condition, stir after >3 hour, 65 ℃, under 0.1MPa condition, after solvent heat treatment 1-2 days, take out, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enrich the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-0.2) of vinyl triazole copolymerization, the specific surface area of material reaches 600m
2/ g, aperture reaches 30 nanometers, and pore volume reaches 1.4ml/g.
Embodiment 2: take toluene as the synthesising mesoporous polydivinylbenezene material of solvent, modulation alkali center content.
By 2 milliliters of divinyl benzene monomers, 2 milliliters of vinyl triazole monomers join in the toluene solution containing 0.065g Diisopropyl azodicarboxylate and 30 milliliters, under normal temperature and pressure air tight condition, stir after >3 hour, 150 ℃, under 2.5MPa condition, after solvent heat treatment 1-2 days, take out, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enrich the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-1.0) of vinyl triazole copolymerization, the specific surface area of material reaches 300m
2/ g, aperture reaches 10 nanometers, and pore volume reaches 0.6ml/g.
Embodiment 3: take benzene as the synthesising mesoporous polydivinylbenezene material of solvent, modulation synthesis temperature.
By 2 milliliters of divinyl benzene monomers, 2 milliliters of vinyl triazole monomers join in the toluene solution containing 0.075g Diisopropyl azodicarboxylate and 50 milliliters, under normal temperature and pressure air tight condition, stir after >3 hour, 100 ℃, under 5MPa condition, after solvent heat treatment 1-2 days, take out, uncap, the room temperature dry solvent that volatilizees, high-specific surface area be can obtain, the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-1.0) of vinyl triazole copolymerization enriched.
Embodiment 4: take tetrahydrofuran (THF) as the synthesising mesoporous polydivinylbenezene material of solvent.
By 2 milliliters of divinyl benzene monomers, 1.0 milliliters of vinyl triazole monomers join in the toluene solution containing 0.07g Diisopropyl azodicarboxylate and 30 milliliters, under normal temperature and pressure air tight condition, stir after >3 hour, 100 ℃, under 5MPa condition, after solvent heat treatment 1-2 days, take out, uncap, the room temperature dry solvent that volatilizees, high-specific surface area be can obtain, the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-0.5) of vinyl triazole copolymerization enriched.
Embodiment 5: take toluene as the synthesising mesoporous polydivinylbenezene material of solvent.
By 2 milliliters of divinyl benzene monomers, 1.0 milliliters of vinyl triazole monomers join in the toluene solution containing 0.060g Diisopropyl azodicarboxylate and 30 milliliters, under normal temperature and pressure air tight condition, stir after >3 hour, 200 ℃, under 0.5MPa condition, solvent heat treatment is taken out for 1 day afterwards, uncap, vacuum-drying is except desolventizing, high-specific surface area be can obtain, the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-0.5) of vinyl triazole copolymerization enriched.
Embodiment 6: take toluene as the synthesising mesoporous polydivinylbenezene material of solvent.
By 2 milliliters of divinyl benzene monomers, 0.5 milliliter of vinyl triazole monomer joins in the toluene solution containing 0.065g Diisopropyl azodicarboxylate and 50 milliliters, under normal temperature and pressure air tight condition, stir after >3 hour, 140 ℃, under 3MPa condition, solvent heat treatment is taken out for 1 day afterwards, uncaps, and revolves to steam and removes reaction solvent, high-specific surface area be can obtain, the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-0.25) of vinyl triazole copolymerization enriched.
Embodiment 7: take benzene as the synthesising mesoporous polydivinylbenezene material of solvent.
By 2 milliliters of divinyl benzene monomers, 0.8 milliliter of vinyl triazole monomer joins in the toluene solution containing 0.06g Diisopropyl azodicarboxylate and 21 milliliters, under normal temperature and pressure, under air tight condition, stir after >3 hour, 80 ℃, under 5MPa condition, after solvent heat treatment 12h, take out, uncap, revolve to steam and remove reaction solvent, high-specific surface area be can obtain, the polydivinylbenezene of meso-hole structure and the novel solid base material (PDVB-VT-0.4) of vinyl triazole copolymerization enriched.
Table 1 has provided the catalytic performance contrast of different samples in catalysis Knoevenagel condensation and Michael addition reaction.As can be seen from Table 1, the catalytic performance of the catalyzed by solid base material of preparing in the present invention is obviously excellent in common catalyzed by solid base material, has shown very excellent catalytic activity and regenerability in catalysis Knoevenagel condensation and Michael addition reaction.
A in table, b, c: catalytic activity is to be calculated by the transformation efficiency of methyl aceto acetate, methyl ethyl diketone and methyl aceto acetate respectively;
D: catalyzer has been recycled 5 times;
E: there is the active centre of equal amts with PDVB-VI-0.33.
Wherein, Knoevenagel condensation: 1mmol phenyl aldehyde, 1mmol acetic acid acetyl triethyl is scattered in 2mL alcohol solvent, then adds 20mg solid base catalyst, reacts on 80 ℃ of strong stirring 12h and finishes, and stratographic analysis, take dodecane as interior mark.
Michael addition: 1mmol acetic acid acetyl triethyl, 1mmol acetic acid acetyl triethyl joins 2 milliliters of alcohol solvents, then adds 0.02g catalyzer, and 65 ℃ of reaction 12h finish.
Michael addition: 1mmol methyl ethyl diketone, 4mmol vinyl cyanide adds 4mL toluene solvant, then adds 0.03g catalyzer, and 110 ℃ of strong stirring reaction 12h finish.
Three reaction synthetic routes are as follows:
Figure 1A is the nitrogen adsorption isotherm of the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention.Figure 1B is the pore size distribution curve of the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention.In figure, a is PDVB-VT-0.16, and b is PDVB-VT-0.33.From Figure 1A and Figure 1B, can find out, in the present invention, the solid alkali material of triazole functionalization has typical meso-hole structure, and the pore size distribution of material concentrates on 25 nanometer left and right.
Fig. 2 is the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention and the infrared spectrum of nanoporous polydivinylbenezene.In figure, a is PDVB-VT-0.16, and b is PDVB.As can be seen from Figure 2, compare with pure polydivinylbenezene, emerging INFRARED SPECTRUM peak proves that triazole group is arrived on the skeleton of material by successful grafting.
Fig. 3 is that super-hydrophobic aggretion type nanoporous solid alkali material prepared by the present invention is tested for the contact angle of various reaction substrates.In figure, a is methyl aceto acetate, and b is methyl acrylate, and c is phenyl aldehyde, and d is vinyl cyanide, and e is water.As can be seen from Figure 3, PDVB-VT-0.16 prepared by the present invention is 0 ° to the contact angle of all kinds of substrates, and illustrative material has excellent wetting property to multiple reaction substrate; And material reaches 150 ° for the contact angle of water, illustrate that the solid alkali material of preparing in the present invention has super-hydrophobic constructional feature.The excellent hydrophobic lipophilicity of material prepared by the present invention derives from its full organic backbone and unique nano-porous structure.
Material prepared by the present invention comprises majority of organic solvent: benzene and homologue thereof, and alkane etc. have extraordinary absorption property (8-12g/g) and swelling behavior, and multiclass organic reaction substrate is had to excellent consistency; To the adsorptive capacity of water very low (50mg/g<), contact angle 120-155 ° adjustable, oily contact angle is approximately less than to 15 °.These characteristics be conducive to that this material overcomes that conventional solid alkali exists to water sensitive, easily absorbing carbon dioxide causes the shortcomings such as active centre inactivation,, regeneration difficulty poor with organic reaction substrate consistency, this material improves the consistency of substrate in catalytic reaction process greatly to the good swelling property of organism and absorption property.
Fig. 4 is carbonic acid gas-TPD curve of the super-hydrophobic aggretion type nanoporous solid alkali material prepared of the present invention.As can be seen from Figure 4 the desorption temperature of the PDVB-VT-0.16 that prepared by the present invention is 225 and 370 ℃, illustrates that such solid alkali has stronger base strength, and strong basicity improves the base catalysis performance of this material greatly.
In sum, the present invention realizes Vinylstyrene and the copolymerization of vinyl triazole by solvent thermal synthetic technology, and then obtain there is bigger serface, excellence is hydrophobic, the aggretion type nanoporous solid alkali material of the skeleton structure of oleophylic, it is very little that the super-drainage structure of this material makes material be exposed in air the adsorptive capacity to water, greatly overcome the poor stability that conventional solid base material causes due to water suction in air, the shortcomings such as active centre inactivation, have improved the anti-poisoning ability of material and have recycled performance.Meanwhile, large specific surface area overcome traditional base material due to pore structure scarcity cause to its restriction of application aspect widely.We carry out modulation alkali center content by the composition of monomer in modulation polymerization process, and synthetic method is simple, with low cost.Material prepared by the present invention is found by catalysis Knoevenagel condensation and Michael addition reaction test, such novel solid base material has shown very excellent catalytic activity and regenerative power, These characteristics has important potential using value to this material in the application in base catalysis field, for solid alkali and the large-scale industrial application of associated materials thereof provide new approaches.
Although the present invention is disclosed as above by preferred embodiment; but not in order to limit the present invention, anyly know this skill person, without departing from the spirit and scope of the present invention; can do a little change and retouching, therefore protection scope of the present invention is when being as the criterion depending on claims scope required for protection.
Claims (5)
1. a preparation method for super-hydrophobic aggretion type nanoporous solid alkali material, is characterized in that, comprises the steps:
A. selecting Vinylstyrene is linking agent monomer, vinyl triazole is alkaline monomer, organic solvent is polymer solvent, azobisisobutyronitrile is initiator, under normal temperature and pressure air tight condition, stir after at least 3 hours, under solvent thermal condition, linking agent monomer and alkaline monomer are carried out to copolymerization, polymerization obtains nanoporous aggretion type blocks of solid, polymerization temperature is 65-200 ℃, polymerization pressure is 0.1-5MPa, polymerization time is 12h at least, the volume ratio of the volume sum of organic solvent and linking agent monomer and alkaline monomer is 7.5-20, the volume ratio of vinyl triazole and Vinylstyrene is 0.2-1.0,
B. by the solid obtaining in step a volatile dry, vacuum-evaporation at ambient temperature, obtain super-hydrophobic aggretion type nanoporous solid alkali material.
2. the preparation method of super-hydrophobic aggretion type nanoporous solid alkali material according to claim 1, is characterized in that, the organic solvent in step a is benzene, ethyl acetate, toluene or tetrahydrofuran (THF).
3. the preparation method of super-hydrophobic aggretion type nanoporous solid alkali material according to claim 1, is characterized in that, the volume ratio between vinyl triazole and Vinylstyrene is 1:2.
4. the preparation method of super-hydrophobic aggretion type nanoporous solid alkali material according to claim 1, is characterized in that, the adjusting of polymerization pressure realizes by being filled with nitrogen.
5. a super-hydrophobic aggretion type nanoporous solid alkali material prepared by preparation method according to claim 1, it is characterized in that, solid alkali material is polydivinylbenezene-co-1-vinyl triazole, and the specific surface area of described polydivinylbenezene-co-1-vinyl triazole is 300-600m
2/ g, mean pore size is 10-30nm, pore volume is 0.6-1.4ml/g.
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| CN104258906A (en) * | 2014-08-27 | 2015-01-07 | 绍兴文理学院 | Nano porous fixed acid catalyst with organic frame and synthesis method thereof |
| CN105884944A (en) * | 2014-11-14 | 2016-08-24 | 中国科学院理化技术研究所 | Preparation method of porous polymer microspheres and application of prepared porous polymer microspheres |
| CN106008809A (en) * | 2016-07-29 | 2016-10-12 | 浙江大学 | Porous cross-linked polymer containing triazole salt functional group as well as preparation method and application thereof |
| CN108129691A (en) * | 2017-12-22 | 2018-06-08 | 江南大学 | A kind of super-hydrophobic preparation method with micro-nano twin-stage polymer composite microsphere |
| CN114471486A (en) * | 2022-01-29 | 2022-05-13 | 蚌埠学院 | Super-hydrophobic silicon dioxide/polydivinylbenzene nano composite material and preparation method thereof |
| CN114700113A (en) * | 2022-05-10 | 2022-07-05 | 福州大学 | High-stability alkaline solid catalytic material and preparation method and application thereof |
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| CN104258906A (en) * | 2014-08-27 | 2015-01-07 | 绍兴文理学院 | Nano porous fixed acid catalyst with organic frame and synthesis method thereof |
| CN105884944A (en) * | 2014-11-14 | 2016-08-24 | 中国科学院理化技术研究所 | Preparation method of porous polymer microspheres and application of prepared porous polymer microspheres |
| CN105884944B (en) * | 2014-11-14 | 2018-07-17 | 中国科学院理化技术研究所 | A kind of preparation method of porous polymer microsphere and its purposes of made porous polymer microsphere |
| CN106008809A (en) * | 2016-07-29 | 2016-10-12 | 浙江大学 | Porous cross-linked polymer containing triazole salt functional group as well as preparation method and application thereof |
| CN106008809B (en) * | 2016-07-29 | 2018-03-16 | 浙江大学 | Porous crosslinked polymeric of the functional group of salt containing triazole and its preparation method and application |
| CN108129691A (en) * | 2017-12-22 | 2018-06-08 | 江南大学 | A kind of super-hydrophobic preparation method with micro-nano twin-stage polymer composite microsphere |
| CN108129691B (en) * | 2017-12-22 | 2019-12-10 | 江南大学 | preparation method of micro-nano two-stage polymer composite microspheres for super-hydrophobicity |
| CN114471486A (en) * | 2022-01-29 | 2022-05-13 | 蚌埠学院 | Super-hydrophobic silicon dioxide/polydivinylbenzene nano composite material and preparation method thereof |
| CN114700113A (en) * | 2022-05-10 | 2022-07-05 | 福州大学 | High-stability alkaline solid catalytic material and preparation method and application thereof |
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Application publication date: 20140514 |