CN115340700A - Preparation method of PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) loaded silicon dioxide aerogel flexible composite membrane - Google Patents
Preparation method of PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) loaded silicon dioxide aerogel flexible composite membrane Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000004964 aerogel Substances 0.000 title claims abstract description 76
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 title claims abstract description 58
- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- 238000000352 supercritical drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract description 2
- 229910021641 deionized water Inorganic materials 0.000 abstract description 2
- 229920000131 polyvinylidene Polymers 0.000 abstract description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000009413 insulation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 solar batteries Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WPDWOCRJBPXJFM-UHFFFAOYSA-N 2-bromo-1-phenylpropan-1-one Chemical compound CC(Br)C(=O)C1=CC=CC=C1 WPDWOCRJBPXJFM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C08J5/18—Manufacture of films or sheets
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- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
The invention discloses a preparation method of a PVDF-HFP (polyvinylidene fluoride-HFP) loaded silicon dioxide aerogel flexible composite film, which comprises the following steps: dispersing vinylidene fluoride-hexafluoropropylene powder in n-methyl pyrrolidone, stirring to form a polymer solution, labeled a; grinding hydrophobic silica aerogel into powder, putting the powder into a beaker, adding absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B; adding the obtained B into the obtained A, and uniformly stirring to form a mixed solution C; pouring the obtained C into a mold, adding water to form a composite film, and washing the composite film with water to remove n-methylpyrrolidone to obtain a wet composite film D; and drying the obtained D to obtain the composite membrane. The method adopts n-methyl pyrrolidone as a solvent, is convenient for washing off the n-methyl pyrrolidone by deionized water, and the obtained composite membrane can be directly contacted with the skin; ethanol is used for dispersing in the pores of the aerogel, so that the aerogel completely keeps the three-dimensional nano network skeleton structure.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to a preparation method of an aerogel composite membrane, and particularly relates to a preparation method of a PVDF-HFP (polyvinylidene fluoride-HFP) loaded silicon dioxide aerogel flexible composite membrane.
Technical Field
The aerogel is made into a natural heat-insulating and heat-preserving optimal material due to the uniqueness of ultralow density, ultrahigh porosity, ultrahigh specific surface and the like, is praised as one of ten major technologies in the world in the nineties of the last century, is praised as a first multifunctional environment-friendly material in the twenty-first century, is an environment-friendly and energy-saving material particularly suitable for double-carbon requirements, and has wide application prospects in the fields of aerospace, deep sea and national defense and daily life including power batteries in cold areas and hot areas, automobile glass and building glass, solar batteries, textile clothing including outdoor camping or operation clothing, vegetables and fruits and heat insulation in public places such as supermarkets, schools, hospitals, kindergartens, stations, airports and the like.
Aerogels, however, have the following inherent limitations: the aerogel is low in strength, large in brittleness and poor in flexibility, so that the aerogel is inconvenient to apply independently, rarely applied in a whole block, and mostly applied in a powder form, and further the consumption is large and the cost is high; meanwhile, the intrinsic performance of the aerogel is reduced by orders of magnitude compared with that of a block material due to extremely high porosity; aerogel preparation methods are limited and it is difficult to prepare high quality products quickly, in batches, and inexpensively. These limitations make the excellent thermal insulation and heat protection performance of the aerogel difficult to be fully exerted, thereby significantly limiting the application of the aerogel.
The inventor discovers in the previous period that when the composite aerogel of lead zirconate titanate (PZT) and vinylidene fluoride (PVDF), the PVDF aerogel is rich in strength and toughness, can be coated and used as a carrier for growth of PZT inorganic aerogel, and thus the PZT/PVDF composite aerogel rich in strength and toughness is formed. In view of the fact that PVDF-Hexafluoropropylene (HFP) material is stronger in hydrophobicity than PVDF and has better chemical stability, thermal stability and acid and alkali corrosion resistance, the PVDF-HFP composite membrane is an ideal membrane material, CN114702712A dissolves PVDF-HFP polymer in an acetone/water composite solvent to form a uniform polymer solution, then silicon oxide aerogel is added to form a PVDF-HFP/silicon oxide aerogel mixed solution, and the super-hydrophobic PVDF-HFP/silicon oxide aerogel composite membrane is obtained by adopting membrane forming treatment and drying. However, acetone is a controlled hazardous chemical due to the limitations of flammability, volatility, toxicity and drug raw materials (bromopropiophenone), and in addition, acetone aqueous solution can enter gaps of the aerogel to damage the network skeleton structure, so that the average pore size of the prepared composite membrane belongs to the micron level, and the heat insulation and refrigeration effects are obviously weakened, thereby being not beneficial to the large-scale production and application of the composite membrane.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a PVDF-HFP loaded silica aerogel flexible composite membrane.
The technical scheme adopted by the invention is as follows: a preparation method of a PVDF-HFP loaded silica aerogel flexible composite membrane is disclosed, a flow chart is shown in figure 1, and the preparation method specifically comprises the following steps:
s1, dispersing vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) polymer powder in n-methyl pyrrolidone, and stirring to form a polymer solution, wherein the polymer solution is marked as A;
s2, grinding the hydrophobic silica aerogel into powder, putting the powder into a beaker, adding absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B;
s3, adding the B obtained in the S2 into the A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the step S3 into a mold, adding water to form a composite film, and washing the composite film with water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, drying the D obtained in the S4 to obtain the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane.
Preferably, the PVDF-HFP polymer described in the step S1 has a weight-average molecular weight of 480000 to 500000.
Preferably, the mass ratio of the PVDF-HFP to the n-methylpyrrolidone in the step S1 is 1-2.
Preferably, the PVDF-HFP powder is sufficiently dissolved in the n-methylpyrrolidone in step S1 at a stirring temperature of 10 to 60 ℃, a stirring time of 10 to 48 hours, and a stirring speed of 100 to 800 rmp.
Preferably, the silica aerogel in step S2 may be one or more of a single silica aerogel, a silica composite aerogel and other hydrophobic aerogels.
Preferably, the mass ratio of the ethanol to the aerogel in the step S2 is 3 to 10.
Preferably, the mass ratio of the silica aerogel to the PVDF-HFP powder in the step S2 is 1 to 25.
Preferably, the stirring time of step S3 is 0.5 to 5 hours, the stirring speed is 100 to 800rmp, and the aerogel is uniformly dispersed.
Preferably, the drying treatment in step S5 is any one of normal pressure drying, freeze drying and supercritical drying;
preferably, the temperature of the atmospheric drying in the step S5 is 100-130 ℃, and the time is 48-72 h.
Preferably, the freeze-drying pre-freezing temperature in the step S5 is-45-0 ℃, the pre-freezing time is 1-12 h, and the freeze-drying time is 12-48 h.
Preferably, the supercritical drying temperature in the step S5 is 35-45 ℃, the pressure is 9-14 MPa, and the time is 12-24 h.
The invention has the beneficial effects that: the preparation method adopts n-methyl pyrrolidone as a solvent, so that the n-methyl pyrrolidone is washed away by deionized water in the subsequent preparation process, and the obtained PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane can be directly contacted with the skin; dispersing the aerogel in pores by using ethanol to ensure that the aerogel completely keeps a three-dimensional nano network skeleton structure in the subsequent preparation process; the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane is prepared by adopting a normal-pressure drying process, and is simple to operate, low in risk and low in energy consumption.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a PVDF-HFP loaded silica aerogel flexible composite membrane of the invention.
Fig. 2 is an SEM photograph showing the PVDF-HFP supported silica aerogel flexible composite film obtained in example 1.
Fig. 3 is a graph showing contact angles of the PVDF-HFP supported silica aerogel flexible composite membrane obtained in example 1 and water.
FIG. 4 is a graph showing N of the PVDF-HFP supported silica aerogel flexible composite film obtained in example 1 2 Gas adsorption desorption curve.
Fig. 5 is a graph showing contact angles of the PVDF-HFP supported silica aerogel flexible composite membrane obtained in example 3 and water.
FIG. 6 shows graphs for a thermal infrared imager test of a stainless steel block A (leftmost side) on a flat plate at 120 ℃, a stainless steel block B (middle) using paper of the same thickness as the sample as a spacer and having a thermal conductivity of 0.05W/(m.K), and a stainless steel block C using PVDF-HFP loaded silica aerogel obtained in example 3 as a spacer, respectively.
FIG. 7 shows N of the PVDF-HFP supported silica aerogel flexible composite membrane obtained in example 4 2 Gas adsorption desorption curve.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following examples, but the following examples are only a part of the present invention and not all of the present invention. It should be noted that the following examples are intended to understand the present invention without limiting it, and other examples obtained by a person of ordinary skill in the art without making any inventive step are within the scope of the present invention. The experimental procedures, in which specific conditions are not specified in the examples, were carried out according to the conventional methods and conditions.
Example 1:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, stirring to form a polymer solution, labeled A;
s2, grinding 0.1g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 1ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film with water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, pre-freezing the D obtained in the step S4 at-45 ℃ for 5h, and freeze-drying for 48h to obtain the PVDF-HFP loaded silica aerogel flexible composite membrane which is marked as a sample 1. The aerogel was found to have adhered to the PVDF-HFP substrate by SEM or the like. The BET specific surface area of sample 1 obtained by the BET test was 62.04m 2 (ii)/g, langmuir specific surface area is 205.63m 2 (iv)/g, average pore diameter of 8.9354nm. The nanometer aperture structure of the aerogel in the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane is completely reserved. Sample 1 has a contact angle with water of 96.267 ° and exhibits hydrophobicity.
An SEM photograph of the PVDF-HFP supported silica aerogel flexible composite membrane obtained in example 1 is shown in FIG. 2, a contact angle between the composite membrane and water is shown in FIG. 3, and N of the composite membrane is shown in FIG. 3 2 The gas adsorption desorption curve is shown in fig. 4.
Example 2:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, stirring to form a polymer solution, labeled A;
s2, grinding 0.1g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 1ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film by using water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, drying the D obtained in the step S4 at 120 ℃ for 48h under normal pressure to obtain the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane which is marked as a sample 2. The characterization results of SEM and the like show that the specific surface of the sample 2 is similar to that of the sample 1, and the structural appearance is similar.
Example 3:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, and stirring to form a polymer solution, labeled A;
s2, grinding 0.5g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 3ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film with water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, pre-freezing the D obtained in the step S4 at-45 ℃ for 5h, and freeze-drying for 48h to obtain the PVDF-HFP loaded silica aerogel flexible composite membrane which is marked as a sample 3. The BET test result of sample 3 was 116.1495m as the BET specific surface area 2 (ii)/g, langmuir specific surface area is 414.1644m 2 (iv)/g, average pore diameter of 7.3783nm. The test result of the thermal infrared imager shows that the temperature of the side surface of the iron block A (the leftmost side) is 112 ℃, the temperature of the side surface of the iron block B (the middle) using paper with the thermal conductivity of 0.05W/(m.K) and the same thickness as that of the sample 3 as a gasket is 56 ℃, and the method is used for testing the steel plateThe PVDF-HFP loaded silica aerogel flexible composite obtained in example 3 had an iron block C (rightmost) side temperature of only 18 ℃ as a gasket. The PVDF-HFP load silicon dioxide aerogel flexible composite membrane prepared by the invention has good heat insulation performance. Sample 3 has a contact angle with water of 147.798 ° and exhibits superhydrophobicity.
The contact angle of the PVDF-HFP supported silica aerogel flexible composite film obtained in example 3 and water is shown in fig. 5.
FIG. 6 shows graphs for IR thermography of a stainless steel block A (leftmost side) on a flat plate at 120 ℃, a stainless steel block B (middle) using paper of the same thickness as the sample as a spacer having a thermal conductivity of 0.05W/(m.K), and a stainless steel block C using PVDF-HFP supported silica aerogel flexible composite obtained in example 3 as a spacer, respectively.
Example 4:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, and stirring to form a polymer solution, labeled A;
s2, grinding 1.5g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 10ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film by using water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, pre-freezing the D obtained in the step S4 at-45 ℃ for 5h, and freeze-drying for 48h to obtain the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane which is marked as a sample 4. The BET test result of sample 4 was 211.9524m as the BET specific surface area 2 (ii)/g, langmuir specific surface area is 778.2261m 2 The average adsorption pore diameter is 6.9158nm. The test results show that as the amount of aerogel used in the preparation process increases, the loading of PVDF-HPF on the aerogel increases correspondingly.
PVDF-HFP loaded silica aerogel flexible composite film obtained in example 4N of (2) 2 The gas adsorption and desorption curves are shown in fig. 7.
Example 5:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, stirring to form a polymer solution, labeled A;
s2, grinding 2.5g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 16ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film by using water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, pre-freezing the D obtained in the step S4 at-45 ℃ for 5h, and freeze-drying for 48h to obtain the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane which is marked as a sample 5. The flexibility of the PVDF-HFP loaded silica aerogel flexible composite membrane can be influenced by excessive addition of the aerogel.
Example 6:
s1, dispersing 2g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, and stirring to form a polymer solution, labeled A;
s2, grinding 3g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 20ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film by using water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, carrying out supercritical drying on the D obtained in the S4 at 45 ℃ and 12MPa for 12h to obtain the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane, which is marked as a sample 6.
Comparative example 1:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, and stirring to form a polymer solution, labeled A;
s2, grinding 0g of hydrophobic silica aerogel into powder, putting the powder into a beaker, adding 1ml of absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B;
s3, adding B obtained in the S2 into A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film with water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, pre-freezing the D obtained in the step S4 at-45 ℃ for 5h, and freeze-drying for 48h to obtain the PVDF-HFP flexible film.
Comparative example 2:
s1, dispersing 1g of vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) powder in 19 mln-methyl pyrrolidone, stirring to form a polymer solution, labeled A;
s2, grinding 0.1g of hydrophobic silica aerogel into powder, directly adding the powder into the A obtained in the S1, and uniformly stirring to form a mixed solution B;
and S3, pouring the B obtained in the S2 into a mold, and adding water to form a complete film.
The preparation method of the invention uses the n-methyl pyrrolidone which is difficult to volatilize and easy to purchase to replace the acetone, thereby overcoming the limitation of the acetone; ethanol is mixed with the aerogel powder to disperse the ethanol in pores of the aerogel, so that the nano-pore structure of the aerogel is ensured to be preserved in the subsequent drying process, and the excellent heat insulation performance of the aerogel is further ensured; and then water is used as a film forming agent to replace a special film forming treatment process, so that related equipment and operation processes are obviously simplified, more importantly, the nano-pore structure and the corresponding intrinsic performance of the aerogel are ensured, and the mass production and large-scale application of the aerogel are realized.
The PVDF-HFP load silicon dioxide aerogel flexible composite membrane prepared by the preparation method has the specific surface of 205.63m2/g, the average pore diameter of 8.9354nm, excellent heat insulation performance, environmental protection, hydrophobicity, heat insulation and excellent flexibility, can still keep structural stability after being folded, bent and twisted for many times, can be directly contacted with the skin, has simple preparation process, low energy consumption and low cost, and has wide application prospect in various fields of aerospace vehicles, oil and gas pipelines, power batteries and the like.
Claims (10)
1. A preparation method of a PVDF-HFP loaded silica aerogel flexible composite membrane specifically comprises the following steps:
s1, dispersing vinylidene fluoride (PVDF) -Hexafluoropropylene (HFP) polymer powder in n-methyl pyrrolidone, and stirring to form a polymer solution, wherein the polymer solution is marked as A;
s2, grinding the hydrophobic silica aerogel into powder, putting the powder into a beaker, adding absolute ethyl alcohol, stirring to disperse the ethyl alcohol in pores of the aerogel, and marking the ethyl alcohol-dispersed aerogel as B;
s3, adding the B obtained in the S2 into the A obtained in the S1, and uniformly stirring to form a mixed solution C;
s4, pouring the C obtained in the S3 into a mold, adding water to form a composite film, and washing the composite film with water to remove n-methylpyrrolidone to obtain a wet composite film D;
and S5, drying the D obtained in the S4 to obtain the PVDF-HFP loaded silicon dioxide aerogel flexible composite membrane.
2. The method for preparing the PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the weight-average molecular weight of the PVDF-HFP polymer in the step S1 is 480000-500000.
3. The method for preparing PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the mass ratio of PVDF-HFP to n-methylpyrrolidone in step S1 is 1-2.
4. The method for preparing PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein in step S1, the stirring temperature is 10-60 ℃, the stirring time is 10-48 h, and the stirring speed is 100-800 rmp, so that the PVDF-HFP powder is fully dissolved in n-methylpyrrolidone.
5. The method for preparing a PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the silica aerogel in step S2 is one or more of a single silica aerogel, a silica composite aerogel and other hydrophobic aerogels.
6. The preparation method of PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the mass ratio of ethanol to aerogel in step S2 is 3-10, so that ethanol can be filled in the pores of aerogel.
7. The method for preparing PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the mass ratio of the silica aerogel in step S2 to the PVDF-HFP powder is 1-25.
8. The preparation method of PVDF-HFP loaded silica aerogel flexible composite membrane as claimed in claim 1, wherein the stirring time of step S3 is 0.5-5 h, the stirring speed is 100-800 rmp, and the aerogel is dispersed uniformly.
9. The method for preparing PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the drying treatment in step S5 is any one of atmospheric drying, freeze drying and supercritical drying.
10. The preparation method of the PVDF-HFP loaded silica aerogel flexible composite membrane according to claim 1, wherein the temperature of the atmospheric drying in the step S5 is 100-130 ℃ and the time is 48-72 hours; or/and the freeze-drying pre-freezing temperature in the step S5 is-45-0 ℃, the pre-freezing time is 1-12 h, and the freeze-drying time is 12-48 h;
or/and the supercritical drying temperature in the step S5 is 35-45 ℃, the pressure is 9-14 MPa, and the time is 12-24 h.
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| US20090082479A1 (en) * | 2007-09-20 | 2009-03-26 | Samsung Electronics Co., Ltd. | Fused aerogel-polymer composite, methods of manufacture thereof and articles comprising the same |
| CN112553914A (en) * | 2020-12-01 | 2021-03-26 | 苏州大学 | Preparation method and application of waterproof heat-insulation coating agent |
| CN113277832A (en) * | 2021-05-15 | 2021-08-20 | 苏州热象纳米科技有限公司 | Preparation method of PVDF/silicon dioxide aerogel membrane material |
| CN114702712A (en) * | 2022-04-24 | 2022-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super-hydrophobic PVDF-HFP/silica aerogel composite membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090082479A1 (en) * | 2007-09-20 | 2009-03-26 | Samsung Electronics Co., Ltd. | Fused aerogel-polymer composite, methods of manufacture thereof and articles comprising the same |
| CN112553914A (en) * | 2020-12-01 | 2021-03-26 | 苏州大学 | Preparation method and application of waterproof heat-insulation coating agent |
| CN113277832A (en) * | 2021-05-15 | 2021-08-20 | 苏州热象纳米科技有限公司 | Preparation method of PVDF/silicon dioxide aerogel membrane material |
| CN114702712A (en) * | 2022-04-24 | 2022-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super-hydrophobic PVDF-HFP/silica aerogel composite membrane and preparation method and application thereof |
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