CN111533942A - Fluororesin sponge and preparation method thereof - Google Patents
Fluororesin sponge and preparation method thereof Download PDFInfo
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- CN111533942A CN111533942A CN202010411945.8A CN202010411945A CN111533942A CN 111533942 A CN111533942 A CN 111533942A CN 202010411945 A CN202010411945 A CN 202010411945A CN 111533942 A CN111533942 A CN 111533942A
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- Prior art keywords
- fluororesin
- powder
- sponge
- pore
- particles
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 149
- 239000000843 powder Substances 0.000 claims abstract description 128
- 239000000463 material Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 238000001179 sorption measurement Methods 0.000 claims description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 239000002033 PVDF binder Substances 0.000 claims description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 23
- -1 polychlorotrifluoroethylene Polymers 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 229920001780 ECTFE Polymers 0.000 claims description 9
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 230000017525 heat dissipation Effects 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 8
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 8
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011358 absorbing material Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910003472 fullerene Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 27
- 238000000926 separation method Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- MARCAKLHFUYDJE-UHFFFAOYSA-N 1,2-xylene;hydrate Chemical compound O.CC1=CC=CC=C1C MARCAKLHFUYDJE-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
-
- 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
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C08K3/02—Elements
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- C08K3/041—Carbon nanotubes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The application relates to a fluororesin sponge and a preparation method thereof, comprising the following steps: uniformly mixing fluororesin powder and pore-forming particles according to a proportion; heating the mixture to melt the fluororesin powder; and cooling, putting into an acid solution, and dissolving and removing the pore-forming particles by reaction generated gas to obtain the fluororesin sponge. Another method for preparing a fluororesin sponge, comprising: uniformly mixing fluororesin powder, functional material powder and pore-forming particles according to a proportion; heating the mixture to melt the fluororesin powder; and cooling, putting into an acid solution, and dissolving and removing the pore-forming particles by reaction generated gas to obtain the fluororesin sponge dispersed with the functional material. Through the mode, the preparation method is simple and efficient, and the pore diameter of the sponge can be effectively controlled.
Description
Technical Field
The application relates to the technical field of sponge preparation, in particular to a fluororesin sponge and a preparation method thereof.
Background
The fluororesin is used as a high polymer material with excellent intrinsic hydrophobicity, has reliable thermal stability, mechanical stability, chemical stability and biocompatibility, and has comprehensive performance obviously superior to that of polyurethane, however, the fluororesin is only dissolved in a few high-boiling strong-polarity toxic solvents such as Dimethylformamide (DMF), N-methylpyrrolidone (NMP), Dimethylacetamide (DMAC) and the like, so that the foaming of the fluororesin is difficult, the pore diameter of the sponge is uncontrollable, the preparation process is complex, and the efficiency is low. Therefore, the simple and efficient preparation method suitable for the fluororesin is provided to obtain the sponge material with controllable pore diameter, and the significance is great.
Disclosure of Invention
In order to solve the technical problems, the application provides the fluororesin sponge and the preparation method thereof, which are simple and efficient, and can effectively control the pore diameter of the sponge.
In order to solve the above technical problems, the present application provides a method for preparing a fluororesin sponge, comprising:
a. uniformly mixing fluororesin powder and pore-forming particles according to a proportion;
b. heating the mixture to melt the fluororesin powder;
c. and cooling, putting into an acid solution, and dissolving and removing the pore-forming particles by reaction generated gas to obtain the fluororesin sponge.
Wherein the fluororesin powder includes at least one of polyvinylidene fluoride powder, polychlorotrifluoroethylene powder, polyvinyl fluoride powder, polytetrafluoroethylene powder, ethylene-tetrafluoroethylene copolymer powder, and ethylene-chlorotrifluoroethylene copolymer powder.
The pore-forming particles comprise at least one of calcium carbonate particles, potassium carbonate particles, sodium carbonate particles, magnesium carbonate particles, barium carbonate particles, potassium bicarbonate particles and sodium bicarbonate particles, and the acid solution is an acetic acid water solution with the mass percentage concentration of 5-10%.
Wherein the pore-forming particles have a particle size of 1nm-1 mm.
In step a, the mass ratio of the fluororesin powder to the pore-forming particles is 1: 5-1: 9;
in step b, heating the mixture to 350 ℃ at 180 ℃ and keeping the temperature for 10-60 min;
in step c, the cooled material is placed in a circulating acid solution at 20-80 ℃.
The present application also provides a method for preparing a second fluororesin sponge, comprising:
a. uniformly mixing fluororesin powder, functional material powder and pore-forming particles according to a proportion;
b. heating the mixture to melt the fluororesin powder;
c. and cooling and placing the obtained product into an acid solution to enable the pore-forming particles to react to generate gas to be dissolved and removed, thus obtaining the fluororesin sponge dispersed with the functional material.
In the second method for preparing the fluororesin sponge, the functional material comprises at least one of an adsorption material, a heat dissipation material, a wave-absorbing material, a conductive material, a sound-insulating material and a chemical catalytic material.
In the second method for preparing the fluororesin sponge, the adsorbing material comprises at least one of fullerene, expanded graphite, carbon nanotubes and activated carbon; the heat dissipation material comprises at least one of graphene, carbon black, carbon nano tubes, boron nitride, aluminum nitride, silicon carbide and aluminum oxide; the wave-absorbing material comprises at least one of iron, cobalt, nickel and alloy thereof, and ferrite; the conductive material comprises at least one of metal, graphene, carbon black and carbon nano tubes; the sound-insulation and heat-preservation material is at least one of hollow glass beads, glass fibers and silicon dioxide; the chemical catalytic material comprises at least one of Pt nanoparticles, Au nanoparticles and Ag nanoparticles.
In the second method for producing a fluororesin sponge, the functional material powder is at least one of spherical, spheroidal, polyhedral, rod-like, and tubular; wherein the particle size of the spherical powder, the quasi-spherical powder and the polyhedral powder is 1nm-100 mu m; the length of the rod-shaped powder and the tubular powder is 1 μm-100 μm, and the diameter is 1-100 nm.
In the second method for preparing a fluororesin sponge, the functional material is an adsorbing material, and before step a, the method further comprises:
d. and carrying out surface modification on the adsorption material by adopting a silane coupling agent.
In the second method for preparing the fluororesin sponge, the silane coupling agent includes at least one of vinyltriethoxysilane, gamma-aminopropyltriethoxysilane, and gamma-glycidoxypropyltrimethoxysilane.
In the second method for producing a fluororesin sponge, the fluororesin powder includes at least one of polyvinylidene fluoride powder, polychlorotrifluoroethylene powder, polyvinyl fluoride powder, polytetrafluoroethylene powder, ethylene-tetrafluoroethylene copolymer powder, ethylene-chlorotrifluoroethylene copolymer powder;
the pore-forming particles comprise at least one of calcium carbonate particles, potassium carbonate particles, sodium carbonate particles, magnesium carbonate particles, barium carbonate particles, potassium bicarbonate particles and sodium bicarbonate particles, and the acid solution is an acetic acid water solution with the mass percentage concentration of 5-10%.
In the second method for preparing the fluororesin sponge, the pore-forming particles have a particle size of 1nm to 1 mm.
In the second method for producing a fluororesin sponge, in step a, the mass ratio of the fluororesin powder to the pore-forming particles is 1: 5-1: 9, the mass ratio of the fluororesin powder to the adsorbent powder is 20: 3-20: 1;
in step b, heating the mixture to 350 ℃ at 180 ℃ and keeping the temperature for 10-60 min;
in step c, the cooled material is placed in a circulating acid solution at 20-80 ℃.
The application also provides a fluororesin sponge prepared by the preparation method of the fluororesin sponge.
The fluororesin sponge and the preparation method thereof comprise the following steps: uniformly mixing fluororesin powder and pore-forming particles according to a proportion; heating the mixture to melt the fluororesin powder; and cooling, putting into an acid solution, and dissolving and removing the pore-forming particles by reaction generated gas to obtain the fluororesin sponge. Another method for preparing a fluororesin sponge, comprising: uniformly mixing fluororesin powder, functional material powder and pore-forming particles according to a proportion; heating the mixture to melt the fluororesin powder; and cooling, putting into an acid solution, and dissolving and removing the pore-forming particles by reaction generated gas to obtain the fluororesin sponge dispersed with the functional material. Through the mode, the preparation method is simple and efficient, and the pore diameter of the sponge can be effectively controlled.
Drawings
Fig. 1 is a schematic flow chart of a method for producing a fluororesin sponge shown according to a first embodiment;
FIG. 2 is a schematic flow chart showing a method for producing a fluororesin sponge according to a second embodiment;
FIG. 3 is a graph showing a comparison of the adsorption capacities of sponges produced by the production process 1 for different oil substances in the second example;
FIG. 4 is a comparison graph of reusability of sponges prepared by the preparation process 1 in three different treatment modes in a second example;
FIG. 5 is a graph comparing the water contact angle and the oil-water separation ratio of the sponge prepared by the preparation process 1 in the second embodiment in the harsh environment of strong acid, strong base and high salinity.
Detailed Description
The following description of the embodiments of the present application is provided for illustrative purposes, and other advantages and capabilities of the present application will become apparent to those skilled in the art from the present disclosure.
In the following description, reference is made to the accompanying drawings that describe several embodiments of the application. It is to be understood that other embodiments may be utilized and that mechanical, structural, electrical, and operational changes may be made without departing from the spirit and scope of the present application. The following detailed description is not to be taken in a limiting sense, and the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Although the terms first, second, etc. may be used herein to describe various elements in some instances, these elements should not be limited by these terms. These terms are only used to distinguish one element from another.
Also, as used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used in this specification, specify the presence of stated features, steps, operations, elements, components, items, species, and/or groups, but do not preclude the presence, or addition of one or more other features, steps, operations, elements, components, species, and/or groups thereof. The terms "or" and/or "as used herein are to be construed as inclusive or meaning any one or any combination. Thus, "A, B or C" or "A, B and/or C" means "any of the following: a; b; c; a and B; a and C; b and C; A. b and C ". An exception to this definition will occur only when a combination of elements, functions, steps or operations are inherently mutually exclusive in some way.
First embodiment
Fig. 1 is a schematic flow chart of a method for producing a fluororesin sponge shown according to a first embodiment. Referring to fig. 1, the preparation method of the fluororesin sponge of this embodiment includes:
and step 130, cooling, placing into an acid solution, and dissolving and removing the pore-forming particles by reaction to generate gas to obtain the fluororesin sponge.
Wherein the fluororesin powder comprises at least one of polyvinylidene fluoride (PVDF) powder, Polychlorotrifluoroethylene (PCTFE) powder, polyvinyl fluoride (PVF) powder, Polytetrafluoroethylene (PTFE) powder, ethylene-tetrafluoroethylene copolymer (ETFE) powder and ethylene-chlorotrifluoroethylene copolymer (ECTFE) powder.
The pore-forming particles include at least one of calcium carbonate particles, potassium carbonate particles, sodium carbonate particles, magnesium carbonate particles, barium carbonate particles, potassium bicarbonate particles, and sodium bicarbonate particles. The selected pore-forming particles need not to generate decomposition reaction or change physical form when the fluororesin powder is melted, so that the holes at the positions of the particles can be reserved in the preparation process to play a role in pore-forming, therefore, when the raw material is selected, the proper pore-forming particles can be selected according to the melting temperature of the fluororesin powder to be used to be matched for use, so that a better pore-forming effect is achieved. In addition, the selected pore-forming particles also need to react with dilute acid solution with the mass fraction of acetic acid, hydrochloric acid and the like being less than or equal to 10% to generate gas, such as carbon dioxide, so that the gas can be dissolved and removed in the step 130 to leave holes, microscopic positive pressure is formed by utilizing the gas generated in the dissolving process, and partial finer micropores or channels are generated around the holes left by the dissolution of the pore-forming particles, thereby being beneficial to improving various performances of the fluororesin sponge, such as compression resilience, heat insulation, noise reduction and the like. In this embodiment, the acid solution is an acetic acid aqueous solution with a mass percentage concentration of 5-10%, the pore-forming particles are calcium carbonate particles, and the pore-forming particles can be dissolved and removed within 1-60 min, so that the pore-forming efficiency is higher.
In this embodiment, the pore-forming particles have a particle size of 1nm to 1mm and the fluororesin powder has a particle size of 1 to 100 μm, so that the two can be uniformly mixed. When mixing, a non-intrusive material homogenizer is used, the rotation speed is adjustable within the range of 500-2000rpm, for example, when the rotation speed is 1000rpm, the uniform mixing can be carried out for 1-3min, and the uniform mixing can be carried out in the period of negative pressure, so that the mixture obtained by mixing is denser. In this example, the mass ratio of fluororesin powder to pore-forming particles was 1: 5-1: and 9, in the proportion range, pore-forming particles can be uniformly dispersed in the fluororesin powder, and the prepared sponge has proper proportion of the number of pores and less closed pores.
After the powders are mixed evenly, the mixture is poured into a container which can endure the high temperature of 350 ℃ such as a glass, ceramic or common metal container and the like for static heating. When the mixture is heated, the mixture is heated to 350 ℃ of 180 ℃ and kept for 10-60min, so that the fluororesin powder is fully melted and integrated. After the fluororesin powder is fully melted, cooling the melt to room temperature, then putting the cooled resin/salt solid into a circulating acid solution at the temperature of 20-80 ℃, soaking for 1-60 min to enable pore-forming particles to completely react, namely completely dissolving the pore-forming particles, if the pore-forming particles need to be removed more fully, carrying out the cleaning process again, wherein the cleaning time and the cleaning frequency can be adjusted according to the size of the sponge. And after cleaning, squeezing to remove water and performing hot blast drying to obtain the fluororesin sponge. In the drying process, sampling weight loss can be adopted to judge whether the drying is sufficient, for example, a cubic sample is taken, the mass of the two previous times and the mass of the two subsequent times are basically unchanged within a temperature and a time, and the drying is judged to be sufficient.
In the above manner, the pore diameter of the prepared fluororesin sponge is the particle diameter of the pore-forming particles. Therefore, the preparation of the fluororesin sponge with controllable pore diameter can be realized by adding pore-forming particles with different particle diameters. Meanwhile, the pore-forming particles generate gas when dissolved, and partial tiny micropores or channels can be generated around the holes, so that the compression resilience performance, the heat insulation and the noise reduction performance and other performances of the fluororesin sponge are favorably improved. In addition, the preparation process only comprises two steps of heating and weak acid washing, the process is extremely simple and efficient, compared with other methods, the cost is greatly reduced, and the method is suitable for industrial production.
The application also provides a fluororesin sponge prepared by the preparation method of the fluororesin sponge.
The fluororesin sponge of the present invention has functions including:
1. the mechanical buffering is used below the electronic screen, and can weaken the negative effects of pressing on water ripples, structural loss and the like generated on the screen;
2. the common polyurethane sponge is mainly used in medium and low temperature (less than 120 ℃) environment, and the fluororesin sponge can be stably used for a long time at higher temperature, such as ECTFE being 149 ℃, PVDF being 150 ℃, ETFE being 220 ℃ and PTFE being 250 ℃;
3. the sound insulation and heat preservation are realized, and based on a porous inner cavity structure, the sound wave transmission and heat dissipation can be effectively shielded;
4. excellent chemical corrosion resistance and can be stably used in strong acid and strong alkali environments.
Second embodiment
Fig. 2 is a schematic flow chart of a method for producing a fluororesin sponge shown according to a second embodiment. Referring to fig. 2, the preparation method of the fluororesin sponge of the present embodiment includes:
and step 230, cooling, placing into an acid solution, and dissolving and removing the pore-forming particles by reaction to generate gas to obtain the fluororesin sponge dispersed with the functional material.
Wherein the fluororesin powder comprises at least one of polyvinylidene fluoride (PVDF) powder, Polychlorotrifluoroethylene (PCTFE) powder, polyvinyl fluoride (PVF) powder, Polytetrafluoroethylene (PTFE) powder, ethylene-tetrafluoroethylene copolymer (ETFE) powder and ethylene-chlorotrifluoroethylene copolymer (ECTFE) powder.
The pore-forming particles include at least one of calcium carbonate particles, potassium carbonate particles, sodium carbonate particles, magnesium carbonate particles, barium carbonate particles, potassium bicarbonate particles, and sodium bicarbonate particles. The selected pore-forming particles need not to generate decomposition reaction or change physical form when the fluororesin powder is melted, so that the holes at the positions of the particles can be reserved in the preparation process to play a role in pore-forming, therefore, when the raw material is selected, the proper pore-forming particles can be selected according to the melting temperature of the fluororesin powder to be used to be matched for use, so that a better pore-forming effect is achieved. In addition, the selected pore-forming particles also need to react with dilute acid solution with the mass fraction of acetic acid, hydrochloric acid and the like being less than or equal to 10% to generate gas, such as carbon dioxide, so that the gas can be dissolved and removed in the step 130 to leave holes, microscopic positive pressure is formed by utilizing the gas generated in the dissolving process, and partial finer micropores or channels are generated around the holes left by the dissolution of the pore-forming particles, thereby being beneficial to improving various performances of the fluororesin sponge, such as compression resilience, heat insulation, noise reduction and the like. In this embodiment, the acid solution is an acetic acid aqueous solution with a mass percentage concentration of 5-10%, the pore-forming particles are calcium carbonate particles, and the pore-forming particles can be dissolved and removed within 1-60 min, so that the pore-forming efficiency is higher.
The functional material comprises at least one of an adsorption material, a heat dissipation material, a wave absorbing material, a conductive material, a sound insulation and heat preservation material and a chemical catalysis material, different functional material powders are selected according to the use occasions of the fluororesin sponge, and the fluororesin sponge with corresponding functions can be obtained. Wherein the adsorption material is at least one of fullerene, expanded graphite, carbon nano tube and activated carbon; the heat dissipation material is at least one of graphene, carbon black, carbon nano tubes, boron nitride, aluminum nitride, silicon carbide and aluminum oxide; the wave-absorbing material is at least one of iron, cobalt, nickel and alloy thereof, and ferrite; the conductive material is at least one of metal, graphene, carbon black and carbon nano tubes; the sound insulation and heat preservation material is at least one of hollow glass beads, glass fibers and silicon dioxide; the chemical catalytic material is at least one of Pt nanoparticles, Au nanoparticles and Ag nanoparticles.
The functional material powder is at least one of spherical, sphere-like, polyhedral, rod-like and tubular. Wherein the particle size of the spherical powder, the quasi-spherical powder and the polyhedral powder is 1nm-100 mu m; the length of the rod-shaped powder and the tubular powder is 1 μm-100 μm, and the diameter is 1-100 nm.
In this embodiment, adsorption material is chooseed for use to the functional material, and adsorption material powder is expanded graphite for the sponge of preparation has super hydrophobicity and super lipophilicity simultaneously, can be used to oil-water separation, and very big expansion space has appeared between the graphite layer among the expanded graphite, has greatly improved its adsorption space, and adsorption performance is better.
In this example, the pore-forming particles have a particle size of 1nm to 1mm, the expanded graphite has a particle size of 1 to 5 μm, and the fluororesin powder has a particle size of 1 to 100 μm, so that the three can be uniformly mixed. When mixing, a non-intrusive material homogenizer is used, the rotation speed is adjustable within the range of 500-2000rpm, for example, when the rotation speed is 1000rpm, the uniform mixing can be carried out for 1-3min, and the uniform mixing can be carried out in the period of negative pressure, so that the mixture obtained by mixing is denser. In this example, the mass ratio of fluororesin powder to pore-forming particles was 1: 5-1: 9, the mass ratio of the fluororesin powder to the adsorbent powder is 20: 3-20: 1, in this proportion scope, can make pore-forming granule, adsorption material powder homodisperse in fluororesin powder, the sponge hole proportion that the preparation was obtained is suitable, and the obturator is few to adsorption material dispersion is even, and adsorption performance is good.
In practice, the powdering is performed in step 210Before mixing, the surface of the adsorbing material can be modified by adopting a silane coupling agent, wherein the silane coupling agent comprises at least one of vinyl triethoxysilane, gamma-aminopropyl triethoxysilane and gamma-glycidyl ether propyl trimethoxysilane. Wherein, 90% of alcohol and 10% of H are mixed2Preparing alcohol-water solution from O, adding acetic acid to adjust pH to 4.5-5.5, adding silane coupling agent while stirring to make mass concentration 0.5-1%, and hydrolyzing for 1-5 min. And then, adding the fullerene or the expanded graphite into a silane coupling agent solution, rapidly and mechanically stirring at the rotating speed of 1000r/min for 5-10min, filtering by using a filter screen, and drying at 120 ℃ for 20min to obtain the adsorption material powder with the modified surface. When preparing an alcohol-water solution, the type of the alcohol is generally ethanol or methanol, and the principle of selection is that the silane coupling agent contains methoxyl, and then methanol is selected; if the ethoxy group is contained, ethanol, namely gamma-aminopropyl triethoxysilane, is selected correspondingly; vinyl triethoxysilane, and ethanol; the gamma-glycidyl ether propyl trimethoxy silane is correspondingly selected from methanol, and the gamma-aminopropyl triethoxy silane can be preferably selected from the adsorption material, so that the adsorption of a polar organic solvent is more facilitated. After the surface of the adsorption material is modified by adopting the silane coupling agent, the interface bonding force between the adsorption material and the fluororesin can be increased, the reusability of the sponge is improved, and the adsorption capacity is improved. After the powders are mixed evenly, the mixture is poured into a container which can endure the high temperature of 350 ℃ such as a glass, ceramic or common metal container and the like for static heating. When the mixture is heated, the mixture is heated to 350 ℃ of 180 ℃ and kept for 10-60min, so that the fluororesin powder is fully melted and integrated. After the fluororesin powder is fully melted, cooling the melt to room temperature, then putting the cooled resin/adsorption material/salt solid into a circulating acid solution at the temperature of 20-80 ℃, soaking for 1-60 min to enable pore-forming particles to completely react, namely completely dissolving the pore-forming particles, if the pore-forming particles need to be removed more fully, the cleaning process can be carried out again, and the cleaning time and the cleaning frequency can be adjusted according to the size of the sponge. And after cleaning, squeezing to remove water and performing hot blast drying to obtain the fluororesin sponge. In the drying process, sampling weight loss can be adopted to judge whether the drying is carried outDrying is sufficient, for example, taking a cubic sample, and judging that drying is sufficient when the masses of the two previous and subsequent measurements are not substantially changed within a certain temperature and time.
In the above manner, the pore diameter of the prepared fluororesin sponge is the particle diameter of the pore-forming particles. Therefore, the pore-forming particles with different particle sizes are added, and the preparation of the fluororesin sponge with controllable pore diameter can be realized. Meanwhile, the pore-forming particles generate gas when dissolved, and can generate partial finer micropores or channels around the holes, thereby being beneficial to improving various performances of the fluororesin sponge, such as compression resilience, heat insulation and noise reduction, catalytic efficiency, adsorption capacity (the extra micropores and channels in the sponge cavity can increase the contact area of catalytic reaction and the adsorption volume). In addition, the fluorine resin, the carbon material and the salt crystal which are cheap and easy to obtain are used as raw materials, the preparation process only comprises two steps of heating and weak acid washing, the process is extremely simple and efficient, compared with other methods, the cost is greatly reduced, and the method is suitable for industrial production.
Based on the above preparation method, the functional material-dispersed fluororesin sponge can be prepared by the following 5 preparation processes.
Quickly and uniformly mixing polyvinylidene fluoride powder (with the particle size of 5 mu m), calcium carbonate particles (with the particle size of 0.2mm) and expanded graphite powder (with the diameter of 1 mu m and subjected to gamma-aminopropyltriethoxysilane pretreatment) according to the mass percent of 1:6.8:0.12 to form uniform powder, then pouring the uniform powder into a high-temperature-resistant glass container, and heating to 195 ℃ for 45min to fully melt the polyvinylidene fluoride. And then, cooling to room temperature, taking out, putting into acetic acid solution with the mass fraction concentration of 10% and circulating flow at 60 ℃, soaking for 1h to completely react and remove pore-forming particles, removing water by extrusion, and then carrying out forced air drying at 100 ℃ for 3h to obtain the polyvinylidene fluoride/expanded graphite composite sponge which is used in the fields of oil-water separation, heat dissipation and electric conduction and has the aperture of 0.2 mm.
Quickly and uniformly mixing polyvinylidene fluoride powder (with the particle size of 5 mu m), calcium carbonate particles (with the particle size of 0.1mm) and fullerene powder (with the diameter of 1nm and subjected to gamma-aminopropyltriethoxysilane pretreatment) according to the mass percent of 1:7.5:0.12 to form uniform powder, then pouring the uniform powder into a high-temperature-resistant glass container, and heating to 195 ℃ for 45min to fully melt the polyvinylidene fluoride. And then, cooling to room temperature, taking out, putting into acetic acid solution with the mass fraction concentration of 10% and circulating flow at 60 ℃, soaking for 1h to completely react and remove pore-forming particles, removing water by extrusion, and then drying for 3h by blowing at 100 ℃ to obtain the polyvinylidene fluoride/fullerene composite sponge which is used in the fields of oil-water separation, heat dissipation and electric conduction and has the aperture of 0.1 mm.
According to the mass percentage of 1:6.5:0.12, polytetrafluoroethylene (with the particle size of 5 microns), calcium carbonate particles (with the particle size of 0.2mm) and carbon nano tubes (with the length of 10-20 microns and the tube diameter of 8-15nm, which are pretreated by gamma-aminopropyltriethoxysilane) are quickly and uniformly mixed to form uniform powder, and then the uniform powder is poured into a high-temperature resistant glass container and heated to 350 ℃ for 45min to fully melt the polytetrafluoroethylene. And then cooling to room temperature, taking out, putting into acetic acid solution with the mass fraction concentration of 10% and circulating flow at 60 ℃, soaking for 1h to completely react and remove pore-forming particles, removing water by extrusion, and then drying by blowing air at 100 ℃ for 3h to obtain the polytetrafluoroethylene/carbon nanotube composite sponge which is used in the field of sound insulation and heat preservation and has the aperture of 0.2 mm.
Quickly and uniformly mixing polyvinylidene fluoride (with the particle size of 5 mu m), calcium carbonate particles (with the particle size of 50 mu m) and ferrite powder (with the particle size of 60nm) according to the mass percentage of 1:7.3:0.15 to form uniform powder, then pouring the uniform powder into a high-temperature-resistant ceramic container, and heating to 195 ℃ for 45min to fully melt the polyvinylidene fluoride. And then, cooling to room temperature, taking out, putting into acetic acid solution with the mass fraction concentration of 10% and circulating flow at 60 ℃, soaking for 1h to completely react and remove the pore-forming particles, removing water by extrusion, and then carrying out forced air drying at 100 ℃ for 3h to obtain the polyvinylidene fluoride/ferrite composite sponge which is used in the field of wave absorption and has the aperture of 50 microns.
Quickly and uniformly mixing polyvinylidene fluoride (with the particle size of 5 mu m), calcium carbonate particles (with the particle size of 80 mu m) and Pt nanoparticles (with the particle size of 5nm) according to the mass percentage of 1:7.2:0.10 to form uniform powder, then pouring the uniform powder into a high-temperature-resistant glass container, heating to 195 ℃, and keeping for 45min to fully melt the polyvinylidene fluoride. And then, cooling to room temperature, taking out, soaking in acetic acid solution with the mass fraction concentration of 10% and circulating flow at 60 ℃ for 1h to completely react and remove pore-forming particles, removing water by extrusion, and then drying by blowing air at 100 ℃ for 3h to obtain the polyvinylidene fluoride/Pt nano particle composite sponge which is used in the field of chemical catalysis and has the aperture of 80 microns.
The fluororesin sponge prepared by the preparation process 1 is taken as a sample to be subjected to performance test, and the specific steps are as follows.
1. Adsorption capacity
Cutting the sponge prepared in the preparation process 1 into cubes with the size of 3cm × 3cm × 3cm, weighing the initial mass and recording the mass as m0Respectively immersing the sponges with the sizes to different solvents at room temperature, taking out after about 15min, weighing the mass after adsorption after no liquid drops, and marking as m1Adsorption capacity/% - (m)1-m0)/m0× 100%, the absorption capacity of the sponge for different organic solvents is shown in figure 3, it can be seen from the figure that, for different common organic solvents, the oil absorption capacity of the sponge can be as high as 290% -1250% of the self weight, the absorption capacity of the sponge is different due to the density and viscosity difference of the organic solvents, wherein the absorption capacity of the peanut oil and the lubricating oil with high viscosity and high density is 295-320%, and the absorption capacity of the dichloromethane and the chloroform with low viscosity and low density can be as high as 900-1250%.
As a comparative experiment, the same amount of water as the organic solvent is taken, the sponge (the initial mass of the sponge is weighed) of the same sample is immersed into the bottom of the water, the sponge is taken out after about 15min, the sponge is weighed, the mass of the sponge after adsorption is basically consistent with the initial mass, and the fact that the sponge taken out after immersion in the water cannot adsorb water and has super-hydrophobicity is proved.
Cutting the sponge which is prepared by the relative preparation process 1 without carrying out surface treatment on the adsorption material into a plurality of cubes with the sizes of 3cm multiplied by 3cm, weighing the initial mass, respectively immersing the sponges with the sizes into different solvents at room temperature, taking out the sponges after about 15min, after no liquid drops, weighing the mass after adsorption, and measuring that the adsorption capacity is reduced by 5-20 percent relative to the sponge prepared by the preparation process 1.
2. Repeated use property
Cutting the sponge prepared by the preparation process 1 into a plurality of cubes with the mass of 1g, weighing the initial mass, taking out the organic solvent which takes chloroform as an experimental object after immersing in the solvent for about 5min each time, weighing the adsorption mass, respectively processing by three methods of heating, extruding and releasing, recording as a period, and sequentially and circularly performing for 10 periods. Wherein, the heating method: taking out the sponge adsorbing the solvent each time, and drying in a fume hood at 70 ℃ for 15 min; extrusion method: after the sponge absorbing the solvent is taken out each time, the solvent is forcibly extruded and removed, and in addition, a flat plate device capable of extruding up and down can also be used for extrusion; a release method comprises the following steps: after each removal of the solvent-adsorbed sponge, it was immediately immersed in 50mL of an analytically pure ethanol solvent for about 20min and then dried at 80 ℃ for 15 min. A comparison of the oil absorption capacity of the sponge prepared in example 1 when treated in three different ways is shown in fig. 4, which shows that the reusability of the sponge treated in the three different ways is high, and the oil absorption capacity of the sponge remains substantially stable over 10 cycles.
3. Water contact angle
The sponge prepared by the preparation process 11 is cut into a cube with the size of 3cm multiplied by 3cm, 5 mu L of deionized water is dripped on the surface of the sponge under the room temperature condition, and the measured static water contact angle is 154 degrees, so that the sponge has excellent hydrophobic property.
4. Resistance to harsh environment
Cutting the sponge prepared in the preparation process 1 into cubes with the size of 3cm × 3cm × 3cm, weighing the initial mass and recording the mass as m0And respectively immersing the materials in 3mol/L HCl, 3mol/L NaOH and 3mol/L NaCl solution for 24h, taking out and fully drying the materials, and representing the chemical stability of the materials through water contact angles. Placing the dried sponge treated in harsh environment in xylene-water mixed solution (1:1) with stirring rate of 500r/min for 5min, wherein the oil-water separation efficiency is (m)1-m0) M × 100% where m1For the mass of the sponge after adsorption, m is the initial xylene in the mixtureAnd (4) quality. Fig. 5 shows that after the sponge is subjected to strong acid, strong base and high salinity environments, the static water contact angle of the sponge is larger than 150 degrees, the excellent hydrophobic property is still maintained, and the oil-water separation efficiency is still maintained above 99%, which indicates that the sponge can still maintain extremely excellent chemical stability even under extremely severe environments.
As a comparative experiment, the static water contact angle of the sponge which is not treated by strong acid, alkali and salt environment is measured, and the xylene-water mixed liquor (1:1) which is not treated by strong acid, alkali and salt environment and is placed under the stirring speed of 500r/min is kept for 5min, and the measured static water contact angle, the oil-water separation efficiency and the sponge which is treated by strong acid, alkali and salt environment are basically kept consistent.
5. Ultraviolet ray resistance
Cutting the sponge prepared in the preparation process 1 into cubes with the size of 3cm × 3cm × 3cm, weighing the initial mass and recording the mass as m0Placing under 3 × 5W 365nm ultraviolet lamp, irradiating for 36h, characterizing chemical stability of the material by water contact angle, measuring water contact angle to be 152 deg. in addition, placing the dried sponge after ultraviolet treatment in xylene-water mixed liquid (1:1) at stirring speed of 500r/min for 5min, and obtaining oil-water separation efficiency/% (m1-m0) M × 100% where m1The oil-water separation efficiency is measured to be 99.3% for the mass of the sponge after adsorption and m is the initial mass of dimethylbenzene in the mixed solution, which shows that the chemical stability of the sponge is basically unchanged under the long-time radiation of high-intensity ultraviolet rays.
As a comparative test, the water contact angle of the sponge without ultraviolet treatment was measured, and the sponge without ultraviolet treatment was placed in a xylene-water mixture (1:1) at a stirring rate of 500r/min for 5min, and the measured water contact angle and oil-water separation efficiency were substantially the same as those of the sponge subjected to ultraviolet treatment.
Each of the above tests was performed on 10 sample points, and the mean was used as the final result.
Experiments show that the polyvinylidene fluoride/expanded graphite composite sponge prepared by the method has excellent hydrophobicity and lipophilicity, and can selectively and rapidly adsorb oil substances (or other organic solvents) so as to realize high-efficiency separation of an oil-water mixture (the separation efficiency is more than 99%); the volume compression ratio is more than 50 percent, and the original shape can still be basically recovered after multiple cycles of binding and releasing; the oil absorption capacity can reach 290-1250 percent of the self weight.
In addition, the polyvinylidene fluoride/expanded graphite composite sponge prepared by the method can be repeatedly used through processes of extrusion, heating or release in other solvents and the like, and can still keep the stability of oil absorption capacity through repeated circulation; in strong acid, strong base, high salinity and high ultraviolet radiation environment, the oil-water separation efficiency and the super-hydrophobicity are still kept to be higher than 99%; the continuous oil-water separation can be carried out by the assistance of vacuum equipment, and the method is expected to be applied to industrial oil-water separation.
The present application also provides a fluororesin sponge prepared by the method for preparing a fluororesin sponge as described in the second example.
The above embodiments are merely illustrative of the principles and utilities of the present application and are not intended to limit the application. Any person skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present application. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical concepts disclosed in the present application shall be covered by the claims of the present application.
Claims (15)
1. A method for preparing a fluororesin sponge, comprising:
a. uniformly mixing fluororesin powder and pore-forming particles according to a proportion;
b. heating the mixture to melt the fluororesin powder;
c. and cooling, putting into an acid solution, and dissolving and removing the pore-forming particles by reaction generated gas to obtain the fluororesin sponge.
2. The method of preparing a fluororesin sponge according to claim 1, wherein the fluororesin powder comprises at least one of polyvinylidene fluoride powder, polychlorotrifluoroethylene powder, polyvinyl fluoride powder, polytetrafluoroethylene powder, ethylene-tetrafluoroethylene copolymer powder, ethylene-chlorotrifluoroethylene copolymer powder.
3. The method for preparing a fluororesin sponge according to claim 1, wherein the pore-forming particles comprise at least one of calcium carbonate particles, potassium carbonate particles, sodium carbonate particles, magnesium carbonate particles, barium carbonate particles, potassium bicarbonate particles, and sodium bicarbonate particles, and the acid solution is an aqueous acetic acid solution having a concentration of 5 to 10% by mass.
4. The method of preparing a fluororesin sponge according to claim 1 or 3, the pore-forming particles having a particle diameter of 1nm to 1 mm.
5. The method of producing a fluororesin sponge according to claim 1, wherein in step a, the mass ratio of the fluororesin powder to the pore-forming particles is 1: 5-1: 9;
in step b, the mixture is heated to 350 ℃ for 10-60 min.
In step c, the cooled material is put into a circulating acid solution at the temperature of 20-80 ℃ to enable the pore-forming particles to react to generate gas to be dissolved and removed.
6. A method for preparing a fluororesin sponge, comprising:
a. uniformly mixing fluororesin powder, functional material powder and pore-forming particles according to a proportion;
b. heating the mixture to melt the fluororesin powder;
c. and cooling and placing the obtained product into an acid solution to enable the pore-forming particles to react to generate gas to be dissolved and removed, thus obtaining the fluororesin sponge dispersed with the functional material.
7. The preparation method of the fluororesin sponge according to claim 6, wherein the functional material comprises at least one of an adsorption material, a heat dissipation material, a wave-absorbing material, a conductive material, a sound-insulating material and a chemical catalytic material.
8. The method for producing a fluororesin sponge according to claim 7, wherein the adsorbing material comprises at least one of fullerene, expanded graphite, carbon nanotube, activated carbon; the heat dissipation material comprises at least one of graphene, carbon black, carbon nano tubes, boron nitride, aluminum nitride, silicon carbide and aluminum oxide; the wave-absorbing material comprises at least one of iron, cobalt, nickel and alloy thereof, and ferrite; the conductive material comprises at least one of metal, graphene, carbon black and carbon nano tubes; the sound-insulation and heat-preservation material is at least one of hollow glass beads, glass fibers and silicon dioxide; the chemical catalytic material comprises at least one of Pt nanoparticles, Au nanoparticles and Ag nanoparticles.
9. The method for producing a fluororesin sponge according to claim 6, 7 or 8, characterized in that the functional material powder is at least one of spherical, spheroidal, polyhedral, rod-like, tubular; wherein the particle size of the spherical powder, the quasi-spherical powder and the polyhedral powder is 1nm-100 mu m; the length of the rod-shaped powder and the tubular powder is 1 μm-100 μm, and the diameter is 1-100 nm.
10. The method for preparing a fluororesin sponge according to claim 6, wherein the functional material is an adsorbing material, and before step a, the method further comprises:
d. and carrying out surface modification on the adsorption material by adopting a silane coupling agent.
11. The method of preparing a fluororesin sponge according to claim 10, wherein the silane coupling agent comprises at least one of vinyltriethoxysilane, γ -aminopropyltriethoxysilane, and γ -glycidoxypropyltrimethoxysilane.
12. The method for producing a fluororesin sponge according to claim 6, wherein the fluororesin powder comprises at least one of polyvinylidene fluoride powder, polychlorotrifluoroethylene powder, polyvinyl fluoride powder, polytetrafluoroethylene powder, ethylene-tetrafluoroethylene copolymer powder, ethylene-chlorotrifluoroethylene copolymer powder;
the pore-forming particles comprise at least one of calcium carbonate particles, potassium carbonate particles, sodium carbonate particles, magnesium carbonate particles, barium carbonate particles, potassium bicarbonate particles and sodium bicarbonate particles, and the acid solution is an acetic acid water solution with the mass percentage concentration of 5-10%.
13. The method of producing a fluororesin sponge according to claim 6 or 12, the pore-forming particles having a particle diameter of 1nm to 1 mm.
14. The method of producing a fluororesin sponge according to claim 8, wherein in step a, the mass ratio of the fluororesin powder to the pore-forming particles is 1: 5-1: 9, the mass ratio of the fluororesin powder to the adsorbent powder is 20: 3-20: 1;
in step b, heating the mixture to 350 ℃ at 180 ℃ and keeping the temperature for 10-60 min;
in step c, the cooled material is put into a circulating acid solution at the temperature of 20-80 ℃ to enable the pore-forming particles to react to generate gas to be dissolved and removed.
15. A fluororesin sponge produced by the process for producing a fluororesin sponge according to any one of claims 1 to 14.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113185748A (en) * | 2021-03-31 | 2021-07-30 | 哈尔滨工业大学（深圳） | Super-hydrophobic and super-oleophylic sponge material and preparation method and application thereof |
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