CN103920432B - A kind of lightweight, flexible super hydrophobic porous gas-gel material and preparation method thereof - Google Patents
A kind of lightweight, flexible super hydrophobic porous gas-gel material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 4
- -1 Carboxylic Acid Ions Chemical class 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 239000006193 liquid solution Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 35
- 239000002608 ionic liquid Substances 0.000 claims description 33
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 20
- 229940081066 picolinic acid Drugs 0.000 claims description 10
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 6
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 claims description 5
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical group CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 101100001676 Emericella variicolor andK gene Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention is a kind of lightweight, flexible super hydrophobic porous gas-gel material, this material is obtained by following methods, the first step: urea, Carboxylic Acid Ions liquid solution and surfactant are joined in reactor and mixes, second step: add siloxanes again under stirring, 3rd step: be transferred in reactor, in 70 ~ 90 DEG C of aging 5 ~ 8h of baking oven polymerization.4th step: successively with distilled water and ethanol washing, normal temperature and pressure is dry, obtains lightweight, flexible super hydrophobic porous gas-gel material.Material has little density, large hole system rate, flexible, can rebound after compression, and super-hydrophobicity, can apply in the temperature range of 77K-573K, and duct stabilization energy stands the excellent feature such as solution modification.
Description
Technical field
Technical scheme of the present invention relates to the preparation of porous gas gel, is a kind of lightweight, flexible super hydrophobic porous gas-gel material and preparation method thereof specifically.
Background technology
A kind of high dispersive cellular solid of gas-gel, its porosu solid structure is mutually polymerized by colloidal particle or high-polymer molecular and is formed, and be filled with gaseous state decentralized medium in hole, porosity is 80% ~ 99.8%, and aperture is usually between 1 ~ 100 nanometer.The advantage that aeroge has lower thermal conductivity, low-density, high porosity, large specific area, structure-controllable can adulterate makes it be widely used as adsorbent, gaseous storage, catalyst carrier, filter, film and separating medium.Typical silica gas-gel, usually obtained by sol-gel process, have high porosity (>90%) and small-bore (~ 50 nanometer), loose structure is made up of the aggregation (~ 10nm) of Nano particles of silicon dioxide.But the network structure of silica gas-gel height fragility makes it can not manufactured and large-sized processing.In order to improve the performance of gas-gel, current people have done a lot of effort.The such as PMSQ gel (K.Kanamori, Y.Kodera, G.Hayase, K.Nakanishi, T.Hanada, J.ColloidInterfaceSci.2011,357,336) of Japanese's invention, density can reach 0.22gcm
-3, there is network structure flexibly, improve the performance of gas-gel.But some fatal shortcomings make its practical application be restricted.Such as harsh drying condition: supercritical drying, freeze drying.Normal temperature and pressure is dry to be subject to people parent because method is simple and to look at, but in normal temperature and pressure dry run, duct is stable not, cause density can increase to some extent (A.S.Dorcheh, M.Abbasi, J.Mater.Process.Technol.2008,199,10.).In addition, with acetic acid as acid medium, easily environmental pollution is caused.How under normal temperature and pressure drying condition, a kind of duct that can maintain is adopted to stablize and the solvent of environmental protection, current or blank.
Ionic liquid was getting more and more people's extensive concerning in recent years, and be due to they low vapour pressures, good electric conductivity, has the potential serving as solvent in liquid-liquid extraction.In addition, different cations and the combination of anion can cause ionic liquid to have different character.Carboxylic Acid Ions liquid not only has the high density reaction active site of liquid acids, there is again the fixedness of solid peracid simultaneously, and there is very low, nonflammable, the higher heat endurance of fusing point, the feature such as normal temperature is in a liquid state, low toxicity, this series of advantages that ionic liquid itself has makes it as a kind of catalyst very friendly to environment and efficient green solvent, current chemical in become the feature of frontier in chemistry and research already.People are more and more extensive to its investigation and application in recent years, and the designability of ionic liquid structure makes its acidity adjustable, gentle acidity, makes its application prospect more optimistic.
Summary of the invention
Technical problem to be solved by this invention is: based on the good characteristics of ionic liquid, acetic acid solution in other materials is instead of as acidic intermedium with green solvent Carboxylic Acid Ions liquid, adopt FOUR EASY STEPS simply, synthesize a kind of super hydrophobic porous gas-gel.The method is simple, economy, environmental protection.This material prepared has little density, large hole system rate, flexible, can rebound after compression, and super-hydrophobicity, can apply in the temperature range of 77K-573K, and duct stabilization energy stands the excellent feature such as solution modification.
The present invention solves this technical problem adopted technical scheme:
A kind of lightweight, flexible super hydrophobic porous gas-gel material, this material is obtained by following methods, comprises the following steps:
The first step: urea, Carboxylic Acid Ions liquid solution and surfactant are joined in reactor and mix, wherein mol ratio is urea: water: Carboxylic Acid Ions liquid: surfactant=(37.9 ~ 45.5): 353.5:(2.5 × 10
-3~ 50 × 10
-3): 1;
Second step: add siloxanes again under stirring, wherein siloxanes is the mixture of trimethoxy silane and dimethoxysilane, and the mol ratio of the two is trimethoxy silane: dimethoxysilane (DMDMS)=3:2, stirs until siloxanes hydrolysis is complete; Wherein in dimethoxysilane and the first step, the mol ratio of surfactant is 6.37:1;
3rd step: be transferred in reactor, in 70 ~ 90 DEG C of aging 5 ~ 8h of baking oven polymerization;
4th step: successively with distilled water and ethanol washing, normal temperature and pressure is dry, obtains lightweight, flexible super hydrophobic porous gas-gel material.
Described Carboxylic Acid Ions liquid is imidazolyl carboxylic acid ionic liquid, picolinic acid ionic liquid or betaine HCL.
The structural formula of described imidazolyl carboxylic acid ionic liquid (I) is as follows:
Wherein, R is linear paraffin base.
Be preferably CH
3, C
4h
7, C
8h
15, C
12h
23or C
16h
31
The structural formula of picolinic acid ionic liquid (II) is as follows:
Described A=Br, CF
3cOO, HSO
4, H
2pO
4or BF
4.
Described surfactant is softex kw (CTAB).
Described trimethoxy silane is MTMS (MTMS), vinyltrimethoxy silane (VTMS) and three is dredged in propyl trimethoxy silicanes (MPTMS) one or both.
Described dimethoxysilane is methyl dimethoxysilane (DMDMS), and structural formula is as follows:
The invention has the beneficial effects as follows:
(1) use Carboxylic Acid Ions liquid as acidic intermedium, environmental protection, and the acidity of Carboxylic Acid Ions liquid gentleness can optimize the structure in hole, can stand the modification of solution, maintain the stable of duct.This invention material size after normal temperature and pressure drying keeps stable.In addition, material the present invention obtained is immersed in water and ethanolic solution after redrying, and remain unchanged with original size, microscopic appearance is similar, and N2 adsorption curve is basically identical.
(2) the gas-gel density of material that the present invention obtains is low to moderate 0.1g/cm
3below, can adsorb organic compound efficiently.Such as, with butyl Carboxylic Acid Ions liquid (ILC4) for acidic intermedium, 0.075g/cm can be reached with the gas-gel density of material that MTMS and methyl dimethoxysilane obtain for presoma
3.Efficient hydrophobicity, can reach 155 ° with the contact angle of water.The adsorbance of n-hexane is reached to 7.2 times of weight own.And gas-gel density of material obtained using acetic acid solution as acidic intermedium under same case is 0.12g/cm
3, adsorbance is 6.2 times (G.Hayase, K.Kanamori, * M.Fukuchi, H.Kaji, andK.Nakanishi.Angew.Chem.Int.Ed.2013,52,1986 – 1989) of weight own.The absorption property that the density that invention material is low is become reconciled makes it more extensive in the application in separation field and analytical chemistry field.
(3) material of the present invention has the softness of height, very easily bending and indeformable after repeatedly bending.Such as with methyl carboxylic acids ionic liquid for acidic intermedium, 0.02MPa is low to moderate with the gas-gel material bending modulus that MTMS and methyl dimethoxysilane obtain for presoma, this material of the very little explanation of bending modulus very easily easily bends, very well flexible.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is described further
Fig. 1: embodiment 1 product gas gel rubber material photo under fluorescent light.
Fig. 2: the scanning electron microscopic picture of embodiment 1 product gas gel rubber material.Wherein 2a is the scanning electron microscopic picture of the gas-gel material of multiplication factor 6000, and 2b is the scanning electron microscopic picture of the gas-gel material of multiplication factor 12000.
Fig. 3: size comparison's digital photograph under fluorescent light before and after embodiment 2 product gas gel rubber material redrying.
Fig. 4: the scanning electron microscopic picture of embodiment 2 product gas gel rubber material.Wherein 4a is the scanning electron microscope (SEM) photograph of preliminary obtained gas-gel material; 4b is the scanning electron microscopic picture of redrying after water soaking; 4c is the scanning electron microscope (SEM) photograph of redrying after alcohol immersion.
Fig. 5: N2 adsorption comparison diagram before and after the drying of embodiment 2 material secondary.
Fig. 6: digital photograph under fluorescent light before and after the drying of embodiment 5 product gas gel rubber material.
Fig. 7: 80% 3 stress test buckling curve of embodiment 9 product gas gel rubber material.
Fig. 8: the contact angle of embodiment 1 product gas gel rubber material and the adsorbance resolution chart of n-hexane.Wherein 8a is the contact angle resolution chart of this gas-gel material and water, and 8b is n-hexane recycle 20 absorption figure.
Detailed description of the invention:
In order to clearer explanation the present invention, enumerate following examples, but it is without any restrictions to scope of invention.
The imidazolyl carboxylic acid ionic liquid that the present invention relates to is according to document (H.R.Li, * D.Li, Y.G.Wang, andQ.R.Ru; Chem.AsianJ.2011,6,1443 – 1449) synthesis, as methyl carboxylic acids ionic liquid (I, the R=CH of embodiment use below
3), butyl Carboxylic Acid Ions liquid (I, R=C
4h
7) and cetyl Carboxylic Acid Ions liquid (I, R=C
16h
31);
The picolinic acid ionic liquid related to according to document (Li Xincong, I expires river. Ai Li. chemical reagent, 2008,30 (5), 328 ~ 330; 334) synthesize, as sulfo group picolinic acid ionic liquid (II, the A=HSO used
4)
Betaine HCL (99%) is bought from Aladdin.But Carboxylic Acid Ions liquid required for the present invention is non-is limited to this.
Embodiment 1
The first step: get urea 3.0g (0.05mol), softex kw (0.0011mol) 0.4g, is added to the butyl Carboxylic Acid Ions liquid (I, wherein R=C that 7ml concentration is 4mM
4h
7, be designated as ILC
4) in, mix.
Second step: mixed solution is in a first step churned mechanically adds 0.0105mol MTMS (MTMS) and 0.007mol methyl dimethoxysilane (DMDMS) simultaneously, stirs 30min continuously, complete to hydrolysis.
3rd step: the mixed liquor in second step is transferred in reactor, the aging 7h of gel in the baking oven of 80 DEG C.
4th step: adopt mode use distilled water and the ethanol repeatedly manually soaking-extrude to wash, normal temperature and pressure is dry, obtains porous gas gel rubber material.Be designated as: ILC
4-MTMS-DMDMS.
For the present embodiment product gas gel rubber material digital photograph under fluorescent light as shown in Figure 1.The material wherein obtained is of a size of 25mm × 25mm × 6mm.
The scanning electron microscopic picture of the present embodiment product gas gel rubber material as shown in Figure 2, wherein a is the scanning electron microscopic picture of the gas-gel material of multiplication factor 6000, b is the scanning electron microscopic picture of the gas-gel material of multiplication factor 12000, can be seen the loose pore structure of gas-gel material by scanning electron microscope (SEM) photograph.
As shown in Figure 8, wherein 8a is the contact angle resolution chart of this gas-gel material and water, and 8b is n-hexane recycle 20 absorption figure for the contact angle of the present embodiment product gas gel rubber material and the adsorbance test of n-hexane.By testing the contact angle of this gas-gel material and water is 155 DEG C, the average adsorption amount of n-hexane is 7.2 times of itself weight.
Embodiment 2
Replace the MTMS (MTMS) in embodiment 1 with vinyltrimethoxy silane (VTMS), other steps are with embodiment 1.Gained gas-gel material is designated as: ILC
4after-VTMS-DMDMS. drying, gained gas-gel material is immersed in normal temperature and pressure redrying in water and ethanol respectively.
Before and after the present embodiment product gas gel rubber material redrying, size comparison's digital photograph under fluorescent light as shown in Figure 3.Wherein the size of this material before and after redrying keeps stable, this gas-gel scantling is described not by the impact of solution modification.
The scanning electron microscopic picture of the present embodiment product gas gel rubber material as shown in Figure 4.Wherein 4a is the scanning electron microscope (SEM) photograph of preliminary obtained gas-gel material; 4b is the scanning electron microscopic picture of redrying after water soaking; 4c is the scanning electron microscopic picture of redrying after alcohol immersion.Scanning electron microscopic picture before and after contrast redrying can find out that the microscopic appearance before and after this gas-gel material secondary drying is consistent.
Before and after the drying of the present embodiment material secondary, N2 adsorption comparison diagram as shown in Figure 5.Contrast the N2 adsorption figure before and after this material secondary drying, N2 adsorption curve is consistent substantially, further illustrates this material duct and stablizes, not by the impact of solution modification.
Embodiment 3
The MTMS (MTMS) in embodiment 1 is replaced with MTMS (MTMS) and three thin propyl trimethoxy silicanes (MPTMS).Concrete steps are as follows:
1. get urea 3.0 (0.05mol) g, softex kw (CTAB) 0.4g (0.0011mol), being added to 7ml concentration is 4mML
-1butyl Carboxylic Acid Ions liquid (ILC
4) in, mix.
2. the mixed solution in 1 is churned mechanically adds MTMS (MTMS) and three thin propyl trimethoxy silicanes (MPTMS, 0.00525mol) by the mol ratio of 1:1 simultaneously, stirs 30min continuously, complete to hydrolysis.Other steps are with embodiment 1.Gained gas-gel material is designated as: ILC
4-MTMS/MPTMS-DMDMS.
Embodiment 4
Replace the MTMS (MTMS) in embodiment 3 with vinyltrimethoxy silane (VTMS, 0.00525mol), other steps are with embodiment 3.Gained gas-gel material is designated as: ILC4-VTMS/MPTMS-DMDMS.
Embodiment 5
The butyl Carboxylic Acid Ions liquid (ILC in embodiment 1 is replaced with the betaine HCL that 7ml concentration is 0.4mM
4), other steps are with embodiment 1.Gained gas-gel material is designated as: BETHCL-MTMS-DMDMS.
Before and after the drying of the present embodiment product gas gel rubber material, digital photograph under fluorescent light as shown in Figure 6.Size before and after contrast is dry can be seen, this gas-gel material before it is dried rear size keeps stable.
Embodiment 6
The butyl Carboxylic Acid Ions liquid (ILC in embodiment 2 is replaced with the betaine HCL that 7ml concentration is 0.4mM
4), other steps are with embodiment 2.
Embodiment 7
The butyl Carboxylic Acid Ions liquid (ILC in embodiment 3 is replaced with the betaine HCL that 7ml concentration is 0.4mM
4), other steps are with embodiment 3.
Embodiment 8
The butyl Carboxylic Acid Ions liquid (ILC in embodiment 4 is replaced with the betaine HCL that 7ml concentration is 0.4mM
4), other steps are with embodiment 4.
Embodiment 9
With the methyl carboxylic acids ionic liquid (I, wherein R=CH that 7ml concentration is 4mM
3, be designated as ILC
1) replace in embodiment 1 butyl Carboxylic Acid Ions liquid (ILC
4), other steps are with embodiment 1.
80% 3 stress test buckling curve of the present embodiment product gas gel rubber material as shown in Figure 7.After 20 bend cycles, stress curve is still consistent, and bending modulus is 0.02MPa, illustrates that this material is very easily bending and flexible fabulous.
Embodiment 10
With the methyl carboxylic acids ionic liquid (ILC that 7ml concentration is 4mM
1) replace in embodiment 2 butyl Carboxylic Acid Ions liquid (ILC
4), other steps are with embodiment 2.
Embodiment 11
With the methyl carboxylic acids ionic liquid (ILC that 7ml concentration is 4mM
1) replace in embodiment 3 butyl Carboxylic Acid Ions liquid (ILC
4), other steps are with embodiment 3.
Embodiment 12 is the methyl carboxylic acids ionic liquid (ILC of 4mM by 7ml concentration
1) replace in embodiment 4 butyl Carboxylic Acid Ions liquid (ILC
4), other steps are with embodiment 4.
Embodiment 13 is the cetyl Carboxylic Acid Ions liquid (I, wherein R=C of 4mM by 7ml concentration
16h
31, be designated as ILC
16) replace in embodiment 1 butyl Carboxylic Acid Ions liquid (ILC
4), other steps are with embodiment 1.
Embodiment 14
With the cetyl Carboxylic Acid Ions liquid (ILC that 7ml concentration is 4mM
16) replacing in embodiment 2 butyl carboxylic acid functional ionic liquid (ILC4), other steps are with embodiment 2.
Embodiment 15
With the cetyl Carboxylic Acid Ions liquid (ILC that 7ml concentration is 4mM
16) replacing in embodiment 3 butyl Carboxylic Acid Ions liquid (ILC4), other steps are with embodiment 3.
Embodiment 16 is the cetyl Carboxylic Acid Ions liquid (ILC of 4mM by 7ml concentration
16) replacing in embodiment 4 butyl Carboxylic Acid Ions liquid (ILC4), other steps are with embodiment 4.
Embodiment 17 is sulfo group picolinic acid ionic liquid (II, the A=HSO of 1mM by 7ml concentration
4) replace in embodiment 1 butyl Carboxylic Acid Ions liquid (ILC
4), other steps are with embodiment 1.
Embodiment 18
Replace the butyl carboxylic acid functional ionic liquid (ILC4) in embodiment 2 with the sulfo group picolinic acid ionic liquid that 7ml concentration is 1mM, other steps are with embodiment 2.
Embodiment 19
Replace the butyl Carboxylic Acid Ions liquid (ILC4) in embodiment 3 with the sulfo group picolinic acid ionic liquid that 7ml concentration is 1mM, other steps are with embodiment 3.
Embodiment 20
Replace the butyl Carboxylic Acid Ions liquid (ILC4) in embodiment 4 with the sulfo group picolinic acid ionic liquid that 7ml concentration is 1mM, other steps are with embodiment 4.
Lightweight, flexible super-hydrophobicity porous gas gel rubber material can be prepared by change siloxanes and Carboxylic Acid Ions liquid in above embodiment, and this material has little density, big hole rate, flexible, can rebound after compression, can apply in the temperature range of 77K-573K, the feature that solution modification etc. is excellent can be stood.This invention material has strong adsorption capacity to organic matter, is widely used in analytical chemistry and O/W separation.
Table one: (density is obtained by general frame quality and volume the porous of each material.Porosity passes through formula: porosity ε=(1-V
b/ V
s) × 100%, wherein V
brepresent entity density, V
srepresent general frame density.Specific area, aperture, pore volume instrument ASAP2020V3.04H record).
It is known technology that the present invention does not state matters.
Claims (4)
1. lightweight, a flexible super hydrophobic porous gas-gel material, is characterized by this material and is obtained by following methods, comprise the following steps:
The first step: urea, Carboxylic Acid Ions liquid solution and surfactant are joined in reactor and mix, wherein mol ratio is urea: water: Carboxylic Acid Ions liquid: surfactant=(37.9 ~ 45.5): 353.5:(2.5 × 10
-3~ 50 × 10
-3): 1;
Second step: add siloxanes again under stirring, wherein siloxanes is the mixture of trimethoxy silane and dimethoxysilane, and the mol ratio of the two is trimethoxy silane: dimethoxysilane (DMDMS)=3:2, stirs until siloxanes hydrolysis is complete; Wherein in dimethoxysilane and the first step, the mol ratio of surfactant is 6.37:1;
3rd step: be transferred in reactor, in 70 ~ 90 DEG C of aging 5 ~ 8h of baking oven polymerization;
4th step: successively with distilled water and ethanol washing, normal temperature and pressure is dry, obtains lightweight, flexible super hydrophobic porous gas-gel material;
Described Carboxylic Acid Ions liquid is imidazolyl carboxylic acid ionic liquid, picolinic acid ionic liquid or betaine HCL;
Described surfactant is softex kw (CTAB);
Described trimethoxy silane is MTMS (MTMS), vinyltrimethoxy silane (VTMS) and three is dredged in propyl trimethoxy silicanes (MPTMS) one or both;
Described dimethoxysilane is methyl dimethoxysilane (DMDMS).
2. lightweight, flexible super hydrophobic porous gas-gel material as claimed in claim 1, the structural formula that it is characterized by described imidazolyl carboxylic acid ionic liquid (I) is as follows:
（Ⅰ）
Wherein, R is linear paraffin base.
3. lightweight, flexible super hydrophobic porous gas-gel material as claimed in claim 2, is characterized by R and be preferably CH
3, C
4h
7, C
8h
15, C
12h
23or C
16h
31.
4. lightweight, flexible super hydrophobic porous gas-gel material as claimed in claim 1, the structural formula that it is characterized by picolinic acid ionic liquid (II) is as follows:
（Ⅱ）
Wherein, A=Br, CF
3cOO, HSO
4, H
2pO
4or BF
4.
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