CN103920432A - Light and flexible super-hydrophobic porous gas gel material and preparation method thereof - Google Patents
Light and 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 75
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 4
- 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
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000006193 liquid solution Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- -1 Carboxylic Acid Ions Chemical class 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 35
- 239000002608 ionic liquid Substances 0.000 claims description 32
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 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
- 238000000034 method Methods 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 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
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012154 double-distilled water Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 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
- 239000002253 acid Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 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
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 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
- 150000002500 ions Chemical class 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
- 238000012545 processing 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a light and flexible super-hydrophobic porous gas gel material. The material is prepared through the following steps of step 1, adding urea, a carboxylic ion liquid solution and a surface active agent into a reactor and mixing; step 2, adding siloxane during the stirring; step 3, transferring to a reaction kettle, and polymerizing and aging in a drying oven for 5h to 8h at the temperature of 70 to 90 DEG C; and step 4, washing by double distilled water and ethanol in sequence, and drying at normal pressure and temperature to obtain the light and flexible super-hydrophobic porous gas gel material. The material has the characteristics that the density is small, the porosity is large, easiness in bending is realized, resilience is available after being compressed, the super-hydrophobility is realized, the material can be applied in the temperature range of 77K to 573K, the pore is stable and can stand the modification of the solution, and the like.
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 rubber material and preparation method thereof specifically.
Background technology
A kind of high dispersive cellular solid of gas gel, its porosu solid structure is made up of colloidal particle or the mutual polymerization of high-polymer molecular, has been full of gaseous state decentralized medium in hole, and porosity is 80%～99.8%, and aperture is conventionally between 1～100 nanometer.Aeroge has lower thermal conductivity, low-density, high porosity, the large controlled advantage of adulterating of specific area, structure makes it be widely used as adsorbent, gaseous storage, catalyst carrier, filter, film and separating medium.Typical silica gas gel, makes by sol-gel process conventionally, has high porosity (>90%) and small-bore (～50 nanometer), and 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, people have done a lot of effort at present.The for example PMSQ gel (K.Kanamori, Y.Kodera, G.Hayase, K.Nakanishi, T.Hanada, J.ColloidInterfaceSci.2011,357,336) of Japanese's invention, density reachable is to 0.22gcm
-3, there is network structure flexibly, improve the performance of gas gel.But some fatal shortcomings are restricted its practical application.For example harsh drying condition: supercritical drying, freeze drying.Normal temperature and pressure is dry to be looked at because method simply is subject to people parent, and still, 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, as acid medium, easily cause environmental pollution with acetic acid.How under normal temperature and pressure drying condition, adopt a kind ofly can maintain the stable solvent of environmental protection again in duct, at present or blank.
Ionic liquid was getting more and more people's extensive concerning in recent years, was due to they low vapour pressures, and good electric conductivity, has the potential that serves as solvent in liquid-liquid extraction.In addition, the combination of different cations and 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 the features such as heat endurance, the normal temperature that fusing point is very low, nonflammable, higher is in a liquid state, low toxicity, this series of advantages that ionic liquid itself has make it as a kind of to the very friendly catalyst of environment and green solvent efficiently, in the current feature that becomes already frontier in chemistry and research aspect chemical.Research and the application of people to it is in recent years more and more extensive, and the designability of ionic liquid structure makes its acidity adjustable, and 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, replace the acetic acid solution of using in other materials as acidic intermedium with green solvent Carboxylic Acid Ions liquid, adopt FOUR EASY STEPS simply, synthetic a kind of super hydrophobic porous gas gel.The method is simple, economy, environmental protection.This material of preparing has little density, and large hole is rate, flexible, after compression, can rebound, and super-hydrophobicity, can be in the temperature range application of 77K-573K, and duct stabilization energy stands the good features such as solution modification.
The present invention solves this technical problem adopted technical scheme:
A kind of lightweight, flexible super hydrophobic porous gas gel rubber material, this material is made by following methods, comprises the following steps:
The first step: urea, Carboxylic Acid Ions liquid solution and surfactant are joined in reactor and mixed, and 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 under stirring, wherein siloxanes is the mixture of trimethoxy silane and dimethoxy silane again, and the mol ratio of the two is trimethoxy silane: dimethoxy silane (DMDMS)=3:2, stirs until siloxanes hydrolysis is complete; Wherein in dimethoxy silane and the first step, the mol ratio of surfactant is 6.37:1;
The 3rd step: be transferred in reactor, in 70～90 DEG C of aging 5～8h of baking oven polymerization;
The 4th step: successively, with distilled water and ethanol washing, normal temperature and pressure is dry, obtains lightweight, flexible super hydrophobic porous gas gel rubber 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 that MTMS (MTMS), vinyltrimethoxy silane (VTMS) and three are dredged one or both in propyl trimethoxy silicane (MPTMS).
Described dimethoxy silane is methyl dimethoxysilane (DMDMS), and structural formula is as follows:
The invention has the beneficial effects as follows:
(1) with 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, maintains the stable of duct.This invention material size after normal temperature and pressure is dry keeps stable.In addition, the material that the present invention is made is immersed in water and ethanolic solution after redrying, remains unchanged with original size, and microscopic appearance is similar, and nitrogen adsorption curve is basically identical.
(2) the gas gel rubber material density that the present invention makes is low to moderate 0.1g/cm
3below, adsorb organic compound efficiently.For example, taking butyl Carboxylic Acid Ions liquid (ILC4) as acidic intermedium, the gas gel rubber material density reachable 0.075g/cm making as presoma taking MTMS and methyl dimethoxysilane
3.Hydrophobicity, can reach 155 ° with the contact angle of water efficiently.The adsorbance of n-hexane is reached to 7.2 times of own weight.And the gas gel rubber material density making as acidic intermedium taking acetic acid solution under same case is 0.12g/cm
3, 6.2 times (G.Hayase, K.Kanamori, * M.Fukuchi, H.Kaji, and K.Nakanishi.Angew.Chem.Int.Ed.2013,52,1986 – 1989) that adsorbance is weight own.The absorption property that the density that invention material is low is become reconciled makes its application in separation field and analytical chemistry field more extensive.
(3) material of the present invention has the softness of height, very easily bending and indeformable after bending repeatedly.For example, taking methyl carboxylic acids ionic liquid as acidic intermedium, be low to moderate 0.02MPa taking MTMS and methyl dimethoxysilane as the gas gel rubber material bending modulus that presoma makes, this material of the very little explanation of bending modulus is very easily easily bending, flexible fine.
Brief description of the drawings
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.
The ESEM picture of Fig. 2: embodiment 1 product gas gel rubber material.Wherein 2a is the ESEM picture of the gas gel rubber material of multiplication factor 6000, and 2b is the ESEM picture of the gas gel rubber material of multiplication factor 12000.
Fig. 3: embodiment 2 product gas gel rubber material redryings front and back size contrast digital photograph under fluorescent light.
The ESEM picture of Fig. 4: embodiment 2 product gas gel rubber materials.Wherein 4a is the scanning electron microscope (SEM) photograph of the gas gel rubber material that tentatively makes; 4b is the ESEM picture of redrying after water soaking; 4c is the scanning electron microscope (SEM) photograph of redrying after alcohol immersion.
Nitrogen absorption comparison diagram before and after Fig. 5: embodiment 2 material secondaries are dry.
The dry front and back of Fig. 6: embodiment 5 product gas gel rubber materials digital photograph under fluorescent light.
80% 3 stress test buckling curve of Fig. 7: embodiment 9 product gas gel rubber materials.
The contact angle of Fig. 8: 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 rubber material and water, and 8b is 20 absorption figure of n-hexane recycle.
Detailed description of the invention:
For clearer explanation the present invention, enumerate following examples, but it is without any restrictions to scope of invention.
The imidazolyl carboxylic acid ionic liquid the present invention relates to is according to document (H.R.Li, * D.Li, Y.G.Wang, andQ.R.Ru; Chem.Asian J.2011,6,1443 – 1449) synthetic, as embodiment uses below methyl carboxylic acids ionic liquid (I, R=CH
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 relating to according to document (Li Xincong, I expires river. Ai Li. chemical reagent, 2008,30 (5), 328～330; 334) synthetic, as the sulfo group picolinic acid ionic liquid (II, the A=HSO that use
4)
Betaine HCL (99%) is bought from Aladdin.Be limited to this but Carboxylic Acid Ions liquid required for the present invention is non-.
Embodiment 1
The first step: get urea 3.0g (0.05mol), softex kw (0.0011mol) 0.4g, being added to 7ml concentration is butyl Carboxylic Acid Ions liquid (I, the wherein R=C of 4mM
4h
7, be designated as ILC
4) in, mix.
Second step: churned mechanically 0.0105mol MTMS (MTMS) and the 0.007mol methyl dimethoxysilane (DMDMS) of simultaneously adding of mixed solution in the first step, continuous stirring 30min is complete to hydrolysis.
The 3rd step: the mixed liquor in second step is transferred in reactor to the aging 7h of gel in the baking oven of 80 DEG C.
The 4th step: the mode that employing is manually soaked-extruded use distilled water and ethanol repeatedly washs, and 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 obtaining is of a size of 25mm × 25mm × 6mm.
The ESEM picture of the present embodiment product gas gel rubber material as shown in Figure 2, wherein a is the ESEM picture of the gas gel rubber material of multiplication factor 6000, b is the ESEM picture of the gas gel rubber material of multiplication factor 12000, can be seen the loose pore structure of gas gel rubber material by scanning electron microscope (SEM) photograph.
The contact angle of the present embodiment product gas gel rubber material and the adsorbance of n-hexane are tested as shown in Figure 8, and wherein 8a is the contact angle resolution chart of this gas gel rubber material and water, and 8b is 20 absorption figure of n-hexane recycle.By testing to such an extent that the contact angle of this gas gel rubber material and water is 155 DEG C, the average adsorbance of n-hexane is 7.2 times of itself weight.
Embodiment 2
With the MTMS (MTMS) in vinyltrimethoxy silane (VTMS) replacement embodiment 1, other steps are with embodiment 1.Gained gas gel rubber material is designated as: ILC
4after-VTMS-DMDMS. is dry, gained gas gel rubber material is immersed in respectively normal temperature and pressure redrying in water and ethanol.
The present embodiment product gas gel rubber material redrying front and back size contrast digital photograph under fluorescent light as shown in Figure 3.Wherein the size of this material before and after redrying keeps stable, illustrates that this gas gel rubber material size is not subject to the impact of solution modification.
The ESEM 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 the gas gel rubber material that tentatively makes; 4b is the ESEM picture of redrying after water soaking; 4c is the ESEM picture of redrying after alcohol immersion.ESEM picture before and after contrast redrying can find out that the microscopic appearance before and after this gas gel rubber material redrying is consistent.
Before and after the present embodiment material secondary is dry, nitrogen absorption comparison diagram as shown in Figure 5.The nitrogen absorption figure that contrasts the dry front and back of this material secondary, nitrogen adsorption curve is consistent substantially, further illustrates this material duct stable, is not subject to the impact of solution modification.
Embodiment 3
Dredge propyl trimethoxy silicane (MPTMS) with MTMS (MTMS) and three and replace the MTMS (MTMS) in embodiment 1.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 to dredge propyl trimethoxy silicane (MPTMS, 0.00525mol) by the mol ratio of 1:1 simultaneously, and continuous stirring 30min is complete to hydrolysis.Other steps are with embodiment 1.Gained gas gel rubber material is designated as: ILC
4-MTMS/MPTMS-DMDMS.
Embodiment 4
With the MTMS (MTMS) in vinyltrimethoxy silane (VTMS, 0.00525mol) replacement embodiment 3, other steps are with embodiment 3.Gained gas gel rubber material is designated as: ILC4-VTMS/MPTMS-DMDMS.
Embodiment 5
The betaine HCL that is 0.4mM by 7ml concentration replaces the butyl Carboxylic Acid Ions liquid (ILC in embodiment 1
4), other steps are with embodiment 1.Gained gas gel rubber material is designated as: BETHCL-MTMS-DMDMS.
The dry front and back of the present embodiment product gas gel rubber material digital photograph under fluorescent light as shown in Figure 6.Contrast is dried the size of front and back can be seen, this gas gel rubber material keeps stablizing in dry front and back size.
Embodiment 6
The betaine HCL that is 0.4mM by 7ml concentration replaces the butyl Carboxylic Acid Ions liquid (ILC in embodiment 2
4), other steps are with embodiment 2.
Embodiment 7
The betaine HCL that is 0.4mM by 7ml concentration replaces the butyl Carboxylic Acid Ions liquid (ILC in embodiment 3
4), other steps are with embodiment 3.
Embodiment 8
The betaine HCL that is 0.4mM by 7ml concentration replaces the butyl Carboxylic Acid Ions liquid (ILC in embodiment 4
4), other steps are with embodiment 4.
Embodiment 9
The methyl carboxylic acids ionic liquid (I, the wherein R=CH that are 4mM by 7ml concentration
3, be designated as ILC
1) replace the butyl Carboxylic Acid Ions liquid (ILC in embodiment 1
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
Methyl carboxylic acids ionic liquid (the ILC that is 4mM by 7ml concentration
1) replace the butyl Carboxylic Acid Ions liquid (ILC in embodiment 2
4), other steps are with embodiment 2.
Embodiment 11
Methyl carboxylic acids ionic liquid (the ILC that is 4mM by 7ml concentration
1) replace the butyl Carboxylic Acid Ions liquid (ILC in embodiment 3
4), other steps are with embodiment 3.
Methyl carboxylic acids ionic liquid (the ILC that embodiment 12 use 7ml concentration are 4mM
1) replace the butyl Carboxylic Acid Ions liquid (ILC in embodiment 4
4), other steps are with embodiment 4.
Cetyl Carboxylic Acid Ions liquid (I, wherein R=C that embodiment 13 use 7ml concentration are 4mM
16h
31, be designated as ILC
16) replace the butyl Carboxylic Acid Ions liquid (ILC in embodiment 1
4), other steps are with embodiment 1.
Embodiment 14
The cetyl Carboxylic Acid Ions liquid (ILC that is 4mM by 7ml concentration
16) replacing the butyl carboxylic acid functional ionic liquid (ILC4) in embodiment 2, other steps are with embodiment 2.
Embodiment 15
The cetyl Carboxylic Acid Ions liquid (ILC that is 4mM by 7ml concentration
16) replacing the butyl Carboxylic Acid Ions liquid (ILC4) in embodiment 3, other steps are with embodiment 3.
The cetyl Carboxylic Acid Ions liquid (ILC that embodiment 16 use 7ml concentration are 4mM
16) replacing the butyl Carboxylic Acid Ions liquid (ILC4) in embodiment 4, other steps are with embodiment 4.
Sulfo group picolinic acid ionic liquid (II, A=HSO that embodiment 17 use 7ml concentration are 1mM
4) replace the butyl Carboxylic Acid Ions liquid (ILC in embodiment 1
4), other steps are with embodiment 1.
Embodiment 18
The sulfo group picolinic acid ionic liquid that is 1mM by 7ml concentration replaces the butyl carboxylic acid functional ionic liquid (ILC4) in embodiment 2, and other steps are with embodiment 2.
Embodiment 19
The sulfo group picolinic acid ionic liquid that is 1mM by 7ml concentration replaces the butyl Carboxylic Acid Ions liquid (ILC4) in embodiment 3, and other steps are with embodiment 3.
Embodiment 20
The sulfo group picolinic acid ionic liquid that is 1mM by 7ml concentration replaces the butyl Carboxylic Acid Ions liquid (ILC4) in embodiment 4, and other steps are with embodiment 4.
In above embodiment, can prepare lightweight, flexible super-hydrophobicity porous gas gel rubber material by changing siloxanes and Carboxylic Acid Ions liquid, and this material has little density, big hole rate, flexible, after compression, can rebound, can, in the temperature range application of 77K-573K, can stand the good features such as solution modification.This invention material has strong adsorption capacity to organic matter, aspect analytical chemistry and O/W separation, is being widely used.
Table one: (density obtains by general frame quality and volume the porous of each material.Porosity is passed 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 record with instrument ASAP2020V3.04H).
It is known technology that the present invention does not state matters.
Claims (7)
1. lightweight, a flexible super hydrophobic porous gas gel rubber material, is characterized by this material and made by following methods, comprises the following steps:
The first step: urea, Carboxylic Acid Ions liquid solution and surfactant are joined in reactor and mixed, and 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 under stirring, wherein siloxanes is the mixture of trimethoxy silane and dimethoxy silane again, and the mol ratio of the two is trimethoxy silane: dimethoxy silane (DMDMS)=3:2, stirs until siloxanes hydrolysis is complete; Wherein in dimethoxy silane and the first step, the mol ratio of surfactant is 6.37:1;
The 3rd step: be transferred in reactor, in 70～90 DEG C of aging 5～8h of baking oven polymerization;
The 4th step: successively, with distilled water and ethanol washing, normal temperature and pressure is dry, obtains lightweight, flexible super hydrophobic porous gas gel rubber material;
Described Carboxylic Acid Ions liquid is imidazolyl carboxylic acid ionic liquid, picolinic acid ionic liquid or betaine HCL.
2. lightweight as claimed in claim 1, flexible super hydrophobic porous gas gel rubber material, the structural formula that it is characterized by described imidazolyl carboxylic acid ionic liquid (I) is as follows:
Wherein, R is linear paraffin base.
3. lightweight as claimed in claim 2, flexible super hydrophobic porous gas gel rubber material, is characterized by R and be preferably CH
3, C
4h
7, C
8h
15, C
12h
23or C
16h
31.
4. lightweight as claimed in claim 1, flexible super hydrophobic porous gas gel rubber material, the structural formula that it is characterized by picolinic acid ionic liquid (II) is as follows:
Wherein, A=Br, CF
3cOO, HSO
4, H
2pO
4or BF
4.
5. lightweight as claimed in claim 1, flexible super hydrophobic porous gas gel rubber material, it is characterized by described surfactant is softex kw (CTAB).
6. lightweight as claimed in claim 1, flexible super hydrophobic porous gas gel rubber material, it is characterized by described trimethoxy silane is that MTMS (MTMS), vinyltrimethoxy silane (VTMS) and three are dredged one or both in propyl trimethoxy silicane (MPTMS).
7. lightweight as claimed in claim 1, flexible super hydrophobic porous gas gel rubber material, it is characterized by described dimethoxy silane is methyl dimethoxysilane (DMDMS).
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| CN110945064A (en) * | 2017-08-25 | 2020-03-31 | 国立大学法人京都大学 | Low density gel and method of making same |
| CN114558528A (en) * | 2022-02-06 | 2022-05-31 | 河南师范大学 | Preparation method of ionic liquid counterion-mixed surfactant thermal response and UV (ultraviolet) light and heat double response gel |
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| CN110945064A (en) * | 2017-08-25 | 2020-03-31 | 国立大学法人京都大学 | Low density gel and method of making same |
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| CN114558528A (en) * | 2022-02-06 | 2022-05-31 | 河南师范大学 | Preparation method of ionic liquid counterion-mixed surfactant thermal response and UV (ultraviolet) light and heat double response gel |
| CN114558528B (en) * | 2022-02-06 | 2024-04-12 | 河南师范大学 | Preparation method of ionic liquid counter ion-mixed surfactant UV light and heat dual-response gel |
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