CN116554538A - 一种多功能天然高分子多孔材料的制备方法 - Google Patents
一种多功能天然高分子多孔材料的制备方法 Download PDFInfo
- Publication number
- CN116554538A CN116554538A CN202210114412.2A CN202210114412A CN116554538A CN 116554538 A CN116554538 A CN 116554538A CN 202210114412 A CN202210114412 A CN 202210114412A CN 116554538 A CN116554538 A CN 116554538A
- Authority
- CN
- China
- Prior art keywords
- natural polymer
- solution
- porous material
- chitosan
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011148 porous material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000499 gel Substances 0.000 claims abstract description 75
- 229920005615 natural polymer Polymers 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000000017 hydrogel Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002861 polymer material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 17
- 230000008014 freezing Effects 0.000 claims abstract description 17
- 238000010257 thawing Methods 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000013538 functional additive Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 93
- 229920001661 Chitosan Polymers 0.000 claims description 69
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- 229920002101 Chitin Polymers 0.000 claims description 42
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 37
- 229920002678 cellulose Polymers 0.000 claims description 37
- 239000001913 cellulose Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 239000004202 carbamide Substances 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 230000000850 deacetylating effect Effects 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 45
- 238000010382 chemical cross-linking Methods 0.000 abstract description 15
- 230000036961 partial effect Effects 0.000 abstract description 13
- 239000000654 additive Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 description 20
- 230000007935 neutral effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000001172 regenerating effect Effects 0.000 description 11
- ZQXSFZAMFNRZOQ-UHFFFAOYSA-N 2-methylpropan-2-ol;hydrate Chemical compound O.CC(C)(C)O ZQXSFZAMFNRZOQ-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-UHFFFAOYSA-N 0.000 description 6
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 6
- 235000017491 Bambusa tulda Nutrition 0.000 description 6
- FZHXIRIBWMQPQF-UHFFFAOYSA-N Glc-NH2 Natural products O=CC(N)C(O)C(O)C(O)CO FZHXIRIBWMQPQF-UHFFFAOYSA-N 0.000 description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 6
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 241001330002 Bambuseae Species 0.000 description 5
- 239000011425 bamboo Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 244000025254 Cannabis sativa Species 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002042 Silver nanowire Substances 0.000 description 4
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 4
- 238000003381 deacetylation reaction Methods 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 230000002439 hemostatic effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000219146 Gossypium Species 0.000 description 3
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 3
- OVRNDRQMDRJTHS-RTRLPJTCSA-N N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-RTRLPJTCSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 235000009120 camo Nutrition 0.000 description 3
- 235000005607 chanvre indien Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011487 hemp Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical group CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- WFAJBYGUONQMCI-UHFFFAOYSA-N acetic acid urea Chemical compound NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.NC(=O)N.C(C)(=O)O WFAJBYGUONQMCI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000023597 hemostasis Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical group COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 1
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000209128 Bambusa Species 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 208000028389 Nerve injury Diseases 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- DLKSDVVEGFXDQU-UHFFFAOYSA-N azane;carbonic acid;urea Chemical compound N.NC(N)=O.OC(O)=O DLKSDVVEGFXDQU-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000008764 nerve damage Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 210000003455 parietal bone Anatomy 0.000 description 1
- MYHOHFDYWMPGJY-UHFFFAOYSA-N pentafluorobenzoyl chloride Chemical compound FC1=C(F)C(F)=C(C(Cl)=O)C(F)=C1F MYHOHFDYWMPGJY-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- VBJNVMKVMZUFLD-UHFFFAOYSA-M potassium;hydrogen carbonate;urea Chemical compound [K+].NC(N)=O.OC([O-])=O VBJNVMKVMZUFLD-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- JUKPJGZUFHCZQI-UHFFFAOYSA-N undecanoyl chloride Chemical compound CCCCCCCCCCC(Cl)=O JUKPJGZUFHCZQI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C08J9/28—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
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- C08J9/0066—Use of inorganic 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08J2397/00—Characterised by the use of lignin-containing materials
- C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及制备环保材料的技术领域，具体涉及一种多功能天然高分子多孔材料的制备方法，将功能性添加剂、稳定剂、天然高分子材料及碱性溶剂混合至完全溶解，得到天然高分子溶液；向天然高分子溶液中加入交联剂，搅拌均匀后放置至形成部分化学交联的碱凝胶，将碱凝胶冷冻预成孔，待解冻后将所得凝胶浸泡于天然高分子材料的非溶剂中进行再生后再水洗得到水凝胶；将水凝胶除去液体，得到多功能天然高分子多孔材料。本发明中不仅能用绿色环保的溶剂体系快速溶解天然高分子，柔性的化学交联结构还能赋予材料优异的湿弹性，将天然高分子材料多功能添加剂复合改性后，能得到一系列有特异性功能、大尺寸、高强度、可降解多孔材料。
Description
技术领域
本发明涉及制备环保材料的技术领域，具体涉及一种多功能天然高分子多孔材料的制备方法。
背景技术
环境污染的日益加剧和石油资源的逐渐短缺使人们迫切需要新的资源替代品，纤维素这一自然界中含量最丰富的天然高分子正逐渐登上历史舞台，广泛存在于树木、竹子、棉麻等材料中的纤维素正以其取之不尽用之不竭的来源和优良的生物相容性、可降解性等绿色环保的特性而备受青睐。不仅如此，人们对材料的性能要求更为丰富，多功能材料在科技高速发展的先进更受青睐。而纤维素分子链上的羟基有优异的反应活性，可用于醚化、酯化、接枝共聚反应或与其他材料复合而形成有特定功能的材料，如持续醚化的纤维素具有出色的紫外线阻隔和荧光效应(Green Chem.,2021,23,479)，水溶性的羧甲基纤维素及其衍生物能做为3D打印的生物墨水(Carbohydrate Polymers 256(2021)117561)，将绿藻中分离得到的纤维素纳米纤维与金属有机框架通过静电相互作用结合能制备用于储能的柔性电极(J.Mater.Chem.A,2018,6,24050–24057)等。而除了纤维素，自然界中还有甲壳素这一含量仅次于纤维素的天然高分子，广泛存在于虾蟹等甲壳动物外壳、乌贼鱿鱼等软体动物中的甲壳素除了有和纤维素类似的羟基，还有乙酰氨基能作为炭材料的氮源；将甲壳素脱乙酰后得到的壳聚糖含有丰富的氨基，是自然界中唯一的碱性多糖。相比于羟基，氨基不仅反应活性更高，在酸性条件下还能被质子化形成具有阳离子特性的铵离子，与带负电的成分如细菌细胞膜结合达到抗菌消炎的效果，或与红细胞和血小板中带负电的成分发生粘附聚集达到快速止血的效果，从而与材料本身的绿色无毒特性结合，拓宽其在生物医用材料领域中的应用。
然而，尽管天然高分子分子间和分子内大量的氢键和高结晶度赋予了材料优异的理化性质和广泛的应用潜能，并为解决海洋和农林废弃物提供了新思路，但这些强相互作用阻碍了高分子在水和常见有机溶剂中的溶解及熔融加工，目前常用的溶剂体系包括LiCl/DMAc体系、离子液体、碱/尿素体系等，但LiCl价格昂贵，难以完全回收并容易残留在再生甲壳素中，离子液体在溶解甲壳素时需要在110℃保持较长时间，而碱/尿素体系不仅能避免毒性的问题，还能实现对高分子的快速溶解，如KOH/尿素溶剂对不同脱乙酰度甲壳素的溶解(Macromolecules 2020,53,13,5588–5598)、(Green Chemistry,2021,23)；另一方面，尽管壳聚糖能被酸质子化而快速溶解，但形成的凝胶力学性能较差，且酸性环境易有毒性残留，而酸-碱联用制备的壳聚糖溶液性质稳定，力学性质优异(专利201710353066.2)，能更好地利用高分子本身的结构特点。
而在材料应用方面，除了常见的水凝胶(Adv.Mater.2016,28,5844)、膜(Adv.Funct.Mater.2017,27,1701100)和丝(Adv.Funct.Mater.2021,31,2104368)，低密度和高孔隙度等结构特点也让多孔材料成为研究的热点，例如在止血材料领域，水凝胶容易黏附在皮肤且溶胀后压迫神经并导致神经损伤，以沸石为代表的无机颗粒止血剂放热严重，容易灼烧伤口甚至造成血栓，而多孔止血材料不仅有孔结构能容纳液体成分，吸液后堵塞伤口达到快速止血的效果，以天然高分子为原材料制备的多孔止血材料更是能避免与人体的生物相容性等问题。另外，在环境领域，这些结构特点使多孔材料能更好地适应环境，在海水淡化和染料吸附、水油分离中都有广阔的应用前景，例如用疏水性试剂改性天然高分子表面的氨基等基团不仅能用于油水分离、吸附等领域，还能降低吸湿性对吸附效率和建筑物外围保温材料的影响，超弹性使材料在完成吸收过程后很轻松地将被吸成分挤出并回收，提高材料的循环使用性，与还原氧化石墨烯复合能提高材料对水的蒸发效率，且多孔结构吸附的热量也有一部分用于加热水体，从而提高光热转化效率。多孔结构还能为微波反射和散射提供更大的表面积，与一些光电材料如MXene复合能显著提高材料的电磁屏蔽功能，在国防、航空航天和柔性电子器件等领域都具有巨大应用潜力。不仅如此，当材料在外力驱动下内部孔结构会发生弹性形变、塑性屈服及密实化来吸收应力，避免结构破损的风险，在电极材料的制备中这种三维网络结构有利于容纳电极体积的变化。
目前制备多孔材料的方式主要有冷冻干燥、超临界、铸造法、燃烧法等等，其中以冷冻干燥这一方法最为环保简便，通过改变预冻温度或者前驱体浓度还能调节孔结构，得到一系列性能可调的多孔材料。目前冷冻干燥所用的前驱体多为悬浮液如纳米纤维悬浮液，但无论是自上而下还是自下而上制备天然高分子纳米纤维都需要较繁琐的过程，直接用水凝胶在冻干时由于内部结构过于密实，冰晶在生长过程体积膨胀会挤压整个凝胶网络，造成骨架收缩甚至在干燥后凝胶结构坍塌、破裂，难以得到结构完整的多孔材料。为了保持多孔材料的完整形貌，叔丁醇等低表面张力溶剂置换、退火等方式均被用于降低毛细管力，而置换浓度、退火温度等都需要根据实验条件优化。
发明内容
本发明的目的在于提供一种多功能天然高分子多孔材料的制备方法，充分利用了天然高分子的结构特点，通过在制备的多孔材料中引入柔性的化学网络让材料有湿弹性，并在柔性的化学网络中预先形成大孔，减少最终冻干时材料内部的毛细管张力，得到结构规整的多孔材料。
本发明实现目的所采用的方案是：一种多功能天然高分子多孔材料的制备方法，包括以下步骤：
A1、将功能性添加剂、稳定剂、天然高分子材料及碱性溶剂混合至完全溶解，得到天然高分子溶液；
A2、向步骤A1中所得天然高分子溶液中加入交联剂，搅拌均匀后放置至形成部分化学交联的碱凝胶，将碱凝胶冷冻，待解冻后将所得凝胶浸泡于天然高分子材料的非溶剂中进行再生后再水洗得到水凝胶；
A3、将步骤A2中的水凝胶除去液体，得到多功能天然高分子多孔材料。
优选地，所述步骤A1中，天然高分子材料为纤维素、甲壳素、壳聚糖、海藻酸盐中的至少一种，天然高分子溶液中天然高分子材料的浓度为1wt％～10wt％，碱性溶剂为碱性氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、碱金属碳酸氢盐、碱土金属碳酸氢盐、氨水、碳酸铵、碳酸氢铵的水溶液中的至少一种，稳定剂为尿素、硫脲、聚乙烯醇中的至少一种；天然高分子溶液中，碱的浓度为2wt％～30wt％，稳定剂的浓度为0～20wt％。
优选地，当所述天然高分子材料为壳聚糖时，配制天然高分子溶液主要包括以下步骤：将功能性添加剂、稳定剂、弱碱水溶液混合均匀，加入壳聚糖，搅拌均匀得到壳聚糖溶液；或将功能性添加剂、稀酸水溶液、稳定剂混合均匀，加入壳聚糖并均匀搅拌，再加入适量碱中和，搅拌得到壳聚糖溶液。
优选地，所述弱碱水溶液为单一碳酸氢盐水溶液或多种碳酸氢盐水溶液的混合物，稀酸为无机酸、有机酸中的一种或多种的混合物，稀酸水溶液的浓度为1wt％～4wt％；中和的碱为碱性氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、碱金属碳酸氢盐、碱土金属碳酸氢盐、氨水、碳酸铵、碳酸氢铵中的任意一种或多种的混合物，壳聚糖溶液中稳定剂的浓度为2wt％～20wt％。
所述的稀酸为盐酸、硝酸、甲酸、乙酸、乳酸、柠檬酸中的一种或多种的混合物。一般，壳聚糖溶液中碳酸氢盐的浓度为2wt％～10wt％，壳聚糖溶液中中和碱的浓度为2wt％～30wt％。
优选地，所述甲壳素或壳聚糖均为甲壳素在氢氧化钾或氢氧化钠的水溶液中脱乙酰后从混合物中分离固体而得到。
所述甲壳素或壳聚糖均为甲壳素在氢氧化钾或氢氧化钠的水溶液中脱乙酰后从混合物中分离固体而得到，所述碱水溶液浓度高于20wt％，甲壳素和碱水溶液的固液比为1：(10-20)，脱乙酰温度为60℃～170℃。
优选地，所述步骤A1中，所述功能性添加剂为无机氧化物、无机氮化物、无机碳化物、金属氧化物、金属碳化物、金属氮化物、导电高分子、一维纳米材料、二维纳米材料中的至少一种，天然高分子溶液中功能性添加剂的浓度为0-20wt％。
所述功能性添加剂包括蒙脱土、黏土、二氧化硅、四氧化三铁、三氧化二铁、一维纳米材料如银纳米线、碳纳米管及其衍生物、导电高分子如聚吡咯、聚噻吩、聚苯胺及其衍生物、有机框架化合物、二维纳米材料如石墨烯及其衍生物、MXene等。
优选地，所述碱性氢氧化物为氢氧化钠、氢氧化钾或氢氧化锂，当采用氢氧化钠时，天然高分子溶液中氢氧化钠的浓度为5wt％～10wt％，当采用氢氧化锂时，天然高分子溶液中氢氧化锂的浓度为3.8wt％～6.3wt％，当采用氢氧化钾时，天然高分子溶液中氢氧化钾的浓度为5wt％～30wt％。
优选地，所述交联剂为环氧化合物、缩水甘油醚类化合物、丙烯酸酯类化合物中的至少一种，交联剂与天然高分子材料的摩尔比为0.1～5:1。
所述的交联剂为环氧氯丙烷、乙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、双酚A二缩水甘油醚聚、聚丙二醇二缩水甘油醚、聚(乙二醇)二丙烯酸酯中的一种或多种的混合物。
优选地，所述非溶剂为水、盐水溶液、可溶于水的低粘度有机液体中的任一种或多种的混合液体。
所述盐为含有一价阳离子、阴离子或二价阳离子、阴离子的盐；所述可溶于水的低黏度有机液体是醇、酮、酯中的至少一种。
所述盐为钾盐、钠盐、镁盐、氯盐、醋酸盐、硝酸盐、硫酸盐、碳酸盐；所述醇为乙醇；所述酮为丙酮；所述酯为甲酸甲酯或乙酸乙酯。
优选地，所述除去液体的具体方法为二氧化碳超临界干燥或冷冻干燥。
优选地，所述的超临界干燥是先将水凝胶用无水乙醇或丙酮置换后再超临界二氧化碳干燥；所述的冷冻干燥是将水凝胶用浓度为0～80wt％叔丁醇-水溶液置换后冷冻干燥。
优选地，还包括以下步骤：对所得多功能天然高分子多孔材料进行疏水改性，得到疏水性多孔材料。
所述疏水改性的方法为通过化学气相沉积、化学剂接枝法或物理涂覆法，在富含较多羟基或氨基的高分子表面沉积、接枝或涂覆上表面化学能较低的疏水性化合物。
所述表面化学能较低的化合物包括无机氧化物、硅烷类、长链烷烃酰氯类、氟化物等。所述无机氧化物包括二氧化钛、二氧化硅等；硅烷类包括二氯硅烷、三氯硅烷、甲基三甲氧基硅烷、辛基三氯硅烷、十六烷基三氯硅烷、十八烷基三氯硅烷和辛基三甲氧基硅烷等；酰氯类包括十一烷酰氯、棕榈酰氯、十八烷酰氯等；氟化物类包括全氟苯甲酰氯、全氟辛酰氯等。
本发明具有以下优点和有益效果：
(1)本发明的制备方法在于制备了一种可大尺寸制造的多功能多孔材料。本发明首先通过化学交联在碱凝胶内部形成了柔性的化学网络，并借助“冰模板”法在碱凝胶内部预先成孔，冰晶生长过程中凝胶内部的溶质会受到冰晶挤压而局部聚集形成孔壁，冰晶生长的区域在解冻后会被溶质内液体占据，在干燥过程中，体系内的大孔结构显著降低了毛细管张力，保证预先形成的孔结构被保留在干燥后的材料中，有效防止材料内部密实的结构导致干燥时结构收缩而造成缺陷；大孔结构还能保证了添加剂均匀分布，有助于质荷传递。另一方面，物理和化学双交联结构能使天然高分子-添加剂区域形成非共价相互作用而使材料同时兼具高强度和高韧性，前者通过物理再生而形成物理交联区承载应力，后者通过不可逆共价交联耗散应力，两者协同作用保证材料在受到外部应力时结构能保持结构完整性。
(2)本发明的制备方法所用的天然高分子均取之于环境并用之于环境，所用的溶剂体系及制备过程都安全无毒，所制备的材料均能在自然环境下降解，符合“绿色化学”的特点。不仅如此，本发明中所制备的材料能充分发挥天然高分子的结构特点，如氨基与金属离子间的螯合作用，丰富的羟基能形成共价或非共价相互作用而提高材料的强度并赋予材料特定功能。最终得到的多孔材料不仅保持完整的形貌、质轻、高比表面积、高孔隙度等结构特点，与还能极大地扩展材料在环境、医学、航空航天、建筑等领域中的应用。
附图说明
图1为实施例1制备的样品图；
图2为实施例1制得材料的扫描电镜图。
具体实施方式
为更好的理解本发明，下面的实施例是对本发明的进一步说明，但本发明的内容不仅仅局限于下面的实施例。
本发明中，作为纤维素来源，可以是分离自树木、竹子、棉花、草类、麻类和其它高等植物的纸浆、竹浆、棉浆、草浆、麻浆等，以及分离自动物、细菌的精制纤维素的一种，或多种的混合物。
作为甲壳素的来源，可以是虾壳、蟹壳、鱿鱼顶骨、昆虫或菌类细胞中的一种或几种。制备不同脱乙酰度的甲壳素/壳聚糖前将甲壳素经过已知技术的方法纯化而没有特别的限制，如碱处理除去蛋白质，酸除去钙盐等矿物质，氧化脱色处理等。
实施例1：
向LiOH-尿素混合液中加入脱脂棉搅拌得到纤维素溶液，最终溶液中包括6.3wt％LiOH、4wt％尿素、2wt％纤维素，余量为水。按照交联剂与纤维素脱水葡萄糖单元AGU摩尔比为0.5:1加入环氧氯丙烷，混合均匀后将溶液倒入模具形成部分化学交联的纤维素碱凝胶。然后将凝胶在-40℃冷冻，解冻后再将凝胶置入去离子水中再生，最后水洗至中性得到纤维素水凝胶，经过20wt％叔丁醇-水溶液置换后冷冻干燥，得到的可快速吸液的纤维素多孔材料。本实施例制备的产物样品图如图1所示，所得块体材料尺寸为7.0cm*3.7cm*0.7cm，从图中可以看出冷冻干燥后的材料形貌规整，无明显收缩。材料内部的形貌图如图2所示，可以观察到微米级的孔结构。
实施例2：
将蒙脱土与LiOH-尿素水溶液混合，再加入竹浆搅拌得到纤维素溶液，最终溶液中包括3.8wt％LiOH、6wt％尿素，2wt％蒙脱土，2wt％纤维素，余量为水。下按照交联剂与纤维素脱水葡萄糖单元AGU摩尔比为5:1加入环氧氯丙烷，混合均匀后将溶液倒入模具形成部分化学交联的纤维素碱凝胶。然后将凝胶在-40℃冷冻，解冻后再将凝胶在去离子水中再生并水洗至中性得到纤维素水凝胶，经过80wt％叔丁醇-水溶液置换并冷冻干燥后得到高强度、隔热和阻燃效果优异的纤维素/蒙脱土多孔材料。当材料被压缩至80％时，其压缩强度为1.6MPa，模量为7.6MPa。当材料用甲基三甲基硅烷疏水改性后，其压缩强度和模量分别提升至2.2MPa和9.8MPa，且材料为超疏水材料。
实施例3：
将碳纳米管与NaOH-硫脲水溶液混合，再加入竹浆搅拌得到纤维素溶液，最终溶液中包括10wt％NaOH、2wt％硫脲，0.8wt％碳纳米管，2wt％纤维素，余量为水。按照交联剂与纤维素脱水葡萄糖单元AGU摩尔比为5:1加入环氧氯丙烷，混合均匀后将溶液倒入模具形成部分化学交联的纤维素碱凝胶。然后将凝胶在-30℃冷冻，解冻后再将凝胶置入15wt％KCl水溶液中再生24h，最后水洗至中性得到纤维素水凝胶，冷冻干燥得到隔热、导电效果优异的纤维素/碳纳米管多孔材料。
实施例4：
将二氧化硅与NaOH-尿素水溶液混后再加入竹浆搅拌得到纤维素溶液，最终溶液中包括5wt％NaOH、8wt％尿素，0.5wt％二氧化硅，2wt％纤维素，余量为水。按照交联剂与纤维素脱水葡萄糖单元AGU摩尔比为0.5:1加入1,4-丁二醇二缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的纤维素碱凝胶。然后将凝胶在-40℃冷冻，解冻后再将凝胶在50wt％乙醇-水溶液中再生24h，最后水洗至中性得到纤维素水凝胶，经过30wt％叔丁醇-水溶液置换后冷冻干燥得到隔热纤维素/二氧化硅多孔材料，热稳定性优于聚苯乙烯等合成高分子。
实施例5：
将聚吡咯与KOH水溶液混合后加入甲壳素搅拌得到甲壳素溶液，最终溶液中包括30wt％KOH、2wt％聚吡咯，5wt％甲壳素，余量为水。按照交联剂与甲壳素N-乙酰氨基葡萄糖单元GlcNAc的摩尔比为2:1加入乙二醇缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的甲壳素碱凝胶。然后将凝胶在-70℃冷冻，解冻后再将凝胶用10wt％NaCl-水溶液再生24h，水洗至中性得到甲壳素水凝胶，经过20wt％叔丁醇-水溶液置换后冷冻干燥得到生物相容性优异的导电甲壳素/聚吡咯多孔材料。当材料被压缩至80％时，其压缩强度为1.6MPa，模量为8.3MPa。
实施例6：
将MXene与KOH-尿素水溶液混合后加入甲壳素搅拌得到甲壳素溶液，最终溶液中包括20wt％KOH、4wt％尿素，20wt％MXene，3wt％甲壳素，余量为水。按照交联剂与甲壳素N-乙酰氨基葡萄糖单元GlcNAc的摩尔比为2:1加入环氧氯丙烷，混合均匀后将溶液倒入模具形成部分化学交联的甲壳素碱凝胶。然后将凝胶在-70℃冷冻，解冻后再将凝胶用40wt％乙醇-水溶液再生24h，水洗至中性得到甲壳素水凝胶，冷冻干燥得到甲壳素/MXene多孔材料的多孔材料不仅有优异的电磁屏蔽功能，同时还具有光热转化、抗菌等功能。
实施例7：
将氧化石墨烯与KOH-尿素水溶液混合再加入壳聚糖搅拌得到壳聚糖溶液，最终溶液中包括12wt％KOH、20wt％尿素，4wt％氧化石墨烯，10wt％壳聚糖，余量为水。按照交联剂与壳聚糖基葡萄糖单元GlcN的摩尔比为0.2:1加入环氧氯丙烷，混合均匀后将溶液倒入模具形成部分化学交联的壳聚糖碱凝胶。然后将凝胶在-70℃冷冻，解冻后再将凝胶用15wt％NaCl-水溶液再生24h，水洗至中性得到壳聚糖水凝胶，经过无水乙醇置换超临界二氧化碳干燥得到能光热抗菌的壳聚糖/氧化石墨烯多孔材料。
实施例8：
将四氧化三铁与KOH-尿素水溶液混合后加入壳聚糖搅拌得到壳聚糖溶液，最终溶液中包括20wt％KOH、8wt％尿素，1wt％四氧化三铁，10wt％壳聚糖，余量为水。按照交联剂与壳聚糖葡萄糖单元GlcN的摩尔比为0.1:1加入乙二醇缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的壳聚糖碱凝胶。然后将凝胶-70℃冷冻，解冻后再将凝胶用5wt％乙醇-水溶液再生24h，水洗至中性得到壳聚糖水凝胶，经过40wt％叔丁醇-水溶液置换后冷冻干燥得到磁性壳聚糖/四氧化三铁多孔材料，能利用外部磁铁调控材料的位置并定向吸附废水中金属离子。
实施例9：
将还原氧化石墨烯与碳酸氢钾-尿素水溶液混合后再加入壳聚糖搅拌得到壳聚糖溶液，最终溶液中包括10wt％碳酸氢钾、20wt％尿素，2wt％还原氧化石墨烯，4wt％壳聚糖，余量为水。按照交联剂与壳聚糖基葡萄糖单元GlcN的摩尔比为1:1加入乙二醇缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的壳聚糖碱凝胶。然后将凝胶在-70℃冷冻，解冻后后再将凝胶用60wt％乙醇-水溶液再生24h，水洗至中性得到壳聚糖水凝胶，经过40wt％叔丁醇-水溶液置换后冷冻干燥得用于太阳能海水淡化的壳聚糖/还原氧化石墨烯复合多孔材料。
实施例10：
将银纳米线与碳酸氢铵-尿素水溶液混合后再加入壳聚糖搅拌得到壳聚糖溶液，最终溶液中包括2wt％碳酸氢铵、16wt％尿素，4wt％银纳米线，3wt％壳聚糖，余量为水。按照交联剂与壳聚糖基葡萄糖单元GlcN的摩尔比为1:1加入乙二醇缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的壳聚糖碱凝胶。然后将凝胶在-40℃冷冻，解冻后后再将凝胶用60wt％乙醇-水溶液再生24h，水洗至中性得到壳聚糖水凝胶，经过40wt％叔丁醇-水溶液置换后冷冻干燥得到的导电壳聚糖/银纳米线多孔材料。
实施例11：
将二氧化钛与醋酸-尿素水溶液混合后再加入壳聚糖搅拌得到壳聚糖溶液，再加入碳酸氢钾混合固体中和，最终溶液中包括1wt％醋酸、2wt％尿素，2wt％二氧化钛，1wt％壳聚糖，2wt％碳酸氢铵，余量为水。按照交联剂与壳聚糖基葡萄糖单元GlcN的摩尔比为1:1加入乙二醇缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的壳聚糖碱凝胶。然后将凝胶在-40℃冷冻，解冻后再将凝胶用60wt％乙醇-水溶液再生24h，水洗至中性得到壳聚糖水凝胶，经过40wt％叔丁醇-水溶液置换后冷冻干燥得到能有效抑制并杀灭微生物的壳聚糖/二氧化钛多孔材料。
实施例12：
将MXene与醋酸-尿素水溶液混合后再加入壳聚糖搅拌得到壳聚糖溶液，再加入碳酸氢钾-氢氧化钾混合固体中和，最终溶液中包括4wt％醋酸、2wt％尿素，10wt％MXene，2wt％壳聚糖，7wt％碳酸氢钾，23wt％氢氧化钾，余量为水。按照交联剂与壳聚糖基葡萄糖单元GlcN的摩尔比为1:1加入乙二醇缩水甘油醚，混合均匀后将溶液倒入模具形成部分化学交联的壳聚糖碱凝胶。然后将凝胶在-40℃冷冻，解冻后再将凝胶用60wt％乙醇-水溶液再生24h，水洗至中性得到壳聚糖水凝胶，经过40wt％叔丁醇-水溶液置换后冷冻干燥得到的壳聚糖/MXene多孔材料不仅有优异的导电性，还具有电热/光热双重响应性。
对比例1：
将MXene与KOH水溶液混合后加入甲壳素搅拌得到甲壳素溶液，最终溶液中包括20wt％KOH、4wt％尿素，20wt％MXene，3wt％甲壳素，余量为水。按照交联剂与甲壳素N-乙酰氨基葡萄糖单元GlcNAc的摩尔比为2:1加入环氧氯丙烷，混合均匀后将溶液倒入模具形成部分化学交联的甲壳素碱凝胶，再将凝胶用40wt％乙醇-水溶液再生24h，水洗至中性得到甲壳素水凝胶，冷冻干燥过程中由于凝胶内部为纳米尺寸多孔结构，毛细管张力会使凝胶发生不均匀收缩，而且水凝胶冷冻过程中冰晶膨胀导致材料在内应力作用下发生破裂，无法得到均匀规整的壳聚糖材料，电磁屏蔽效果较差。
对比例2：
将MXene与KOH-尿素水溶液混合后加入甲壳素搅拌得到甲壳素溶液，最终溶液中包括20wt％KOH、4wt％尿素，20wt％MXene，3wt％甲壳素，余量为水。加热凝胶后在-70℃冷冻，解冻过程中碱凝胶逐渐变为溶液状态，无法保持块体形貌。
以上所述是本发明的优选实施方式而已，当然不能以此来限定本发明之权利范围，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和变动，这些改进和变动也视为本发明的保护范围。
Claims (10)
1.一种多功能天然高分子多孔材料的制备方法，其特征在于，包括以下步骤：
A1、将功能性添加剂、稳定剂、天然高分子材料及碱性溶剂混合至完全溶解，得到天然高分子溶液；
A2、向步骤A1中所得天然高分子溶液中加入交联剂，搅拌均匀后放置至形成部分化学交联的碱凝胶，将碱凝胶冷冻，待解冻后将所得凝胶浸泡于天然高分子材料的非溶剂中进行再生后再水洗得到水凝胶；
A3、将步骤A2中的水凝胶除去液体，得到多功能天然高分子多孔材料。
2.根据权利要求1所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述步骤A1中，天然高分子材料为纤维素、甲壳素、壳聚糖、海藻酸盐中的至少一种，天然高分子溶液中天然高分子材料的浓度为1wt％～10wt％，碱性溶剂为碱性氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、碱金属碳酸氢盐、碱土金属碳酸氢盐、氨水、碳酸铵、碳酸氢铵的水溶液中的至少一种，稳定剂为尿素、硫脲、聚乙烯醇中的至少一种；天然高分子溶液中，碱的浓度为2wt％～30wt％，稳定剂的浓度为0～20wt％。
3.根据权利要求2所述的多功能天然高分子多孔材料的制备方法，其特征在于：当所述天然高分子材料为壳聚糖时，配制天然高分子溶液主要包括以下步骤：将功能性添加剂、稳定剂、弱碱水溶液混合均匀，加入壳聚糖，搅拌均匀得到壳聚糖溶液；或将功能性添加剂、稀酸水溶液、稳定剂混合均匀，加入壳聚糖并均匀搅拌，再加入适量碱中和，搅拌得到壳聚糖溶液。
4.根据权利要求3所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述弱碱水溶液为单一碳酸氢盐水溶液或多种碳酸氢盐水溶液的混合物，稀酸为无机酸、有机酸中的一种或多种的混合物，稀酸水溶液的浓度为1wt％～4wt％；中和的碱为碱性氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、碱金属碳酸氢盐、碱土金属碳酸氢盐、氨水、碳酸铵、碳酸氢铵中的任意一种或多种的混合物，壳聚糖溶液中稳定剂的浓度为2wt％～20wt％。
5.根据权利要求2所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述甲壳素或壳聚糖均为甲壳素在氢氧化钾或氢氧化钠的水溶液中脱乙酰后从混合物中分离固体而得到。
6.根据权利要求1所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述步骤A1中，所述功能性添加剂为无机氧化物、无机氮化物、无机碳化物、金属氧化物、金属碳化物、金属氮化物、导电高分子、一维纳米材料、二维纳米材料中的至少一种，天然高分子溶液中功能性添加剂的浓度为0-20wt％。
7.根据权利要求2所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述碱性氢氧化物为氢氧化钠、氢氧化钾或氢氧化锂，当采用氢氧化钠时，天然高分子溶液中氢氧化钠的浓度为5wt％～10wt％，当采用氢氧化锂时，天然高分子溶液中氢氧化锂的浓度为3.8wt％～6.3wt％，当采用氢氧化钾时，天然高分子溶液中氢氧化钾的浓度为5wt％～30wt％。
8.根据权利要求1所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述交联剂为环氧化合物、缩水甘油醚类化合物、丙烯酸酯类化合物中的至少一种，交联剂与天然高分子材料的摩尔比为0.1～5:1。
9.根据权利要求1所述的多功能天然高分子多孔材料的制备方法，其特征在于：所述非溶剂为水、盐水溶液、可溶于水的低粘度有机液体中的任一种或多种的混合液体。
10.根据权利要求1所述的多功能天然高分子多孔材料的制备方法，其特征在于：还包括以下步骤：对所得多功能天然高分子多孔材料进行疏水改性，得到疏水性多孔材料。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210114412.2A CN116554538A (zh) | 2022-01-30 | 2022-01-30 | 一种多功能天然高分子多孔材料的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210114412.2A CN116554538A (zh) | 2022-01-30 | 2022-01-30 | 一种多功能天然高分子多孔材料的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116554538A true CN116554538A (zh) | 2023-08-08 |
Family
ID=87490389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210114412.2A Pending CN116554538A (zh) | 2022-01-30 | 2022-01-30 | 一种多功能天然高分子多孔材料的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116554538A (zh) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184919A (en) * | 1976-03-31 | 1980-01-22 | Snow Brand Milk Products Co., Ltd. | Method of gelling microbial mycelia |
| US20110262489A1 (en) * | 2008-09-10 | 2011-10-27 | Xiaobin Zhao | Hyaluronic acid cryogel - compositions, uses, processes for manufacturing |
| CN104387597A (zh) * | 2014-11-28 | 2015-03-04 | 武汉大学 | 化学和物理双重交联的高强度甲壳素凝胶系材料及其制备方法 |
| CN104448396A (zh) * | 2014-11-28 | 2015-03-25 | 武汉大学 | 一种基于化学和物理交联的双网络纤维素凝胶系材料 |
| CN106256938A (zh) * | 2016-08-18 | 2016-12-28 | 浙江真爱毯业科技有限公司 | 一种羊绒拉舍尔毛毯的生产工艺 |
| CN109251451A (zh) * | 2018-08-30 | 2019-01-22 | 太原理工大学 | 一种pH敏感型黄原胶/聚乙烯醇水凝胶的制备方法 |
| CN110606992A (zh) * | 2019-08-13 | 2019-12-24 | 浙江跃维新材料科技有限公司 | 基于生物质纳米材料的多孔泡沫材料的制备方法及其应用 |
| CN112940287A (zh) * | 2021-02-03 | 2021-06-11 | 武汉大学 | 一种形状记忆壳聚糖水凝胶及其制备方法 |
-
2022
- 2022-01-30 CN CN202210114412.2A patent/CN116554538A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184919A (en) * | 1976-03-31 | 1980-01-22 | Snow Brand Milk Products Co., Ltd. | Method of gelling microbial mycelia |
| US20110262489A1 (en) * | 2008-09-10 | 2011-10-27 | Xiaobin Zhao | Hyaluronic acid cryogel - compositions, uses, processes for manufacturing |
| CN104387597A (zh) * | 2014-11-28 | 2015-03-04 | 武汉大学 | 化学和物理双重交联的高强度甲壳素凝胶系材料及其制备方法 |
| CN104448396A (zh) * | 2014-11-28 | 2015-03-25 | 武汉大学 | 一种基于化学和物理交联的双网络纤维素凝胶系材料 |
| CN106256938A (zh) * | 2016-08-18 | 2016-12-28 | 浙江真爱毯业科技有限公司 | 一种羊绒拉舍尔毛毯的生产工艺 |
| CN109251451A (zh) * | 2018-08-30 | 2019-01-22 | 太原理工大学 | 一种pH敏感型黄原胶/聚乙烯醇水凝胶的制备方法 |
| CN110606992A (zh) * | 2019-08-13 | 2019-12-24 | 浙江跃维新材料科技有限公司 | 基于生物质纳米材料的多孔泡沫材料的制备方法及其应用 |
| CN112940287A (zh) * | 2021-02-03 | 2021-06-11 | 武汉大学 | 一种形状记忆壳聚糖水凝胶及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kostag et al. | Sustainable biomaterials based on cellulose, chitin and chitosan composites-A review | |
| Khajavian et al. | Chitin and derivative chitosan-based structures—Preparation strategies aided by deep eutectic solvents: A review | |
| Yang et al. | Recent progress in preparation and application of nano‐chitin materials | |
| Bao et al. | Fabrication of cellulose nanowhiskers reinforced chitosan-xylan nanocomposite films with antibacterial and antioxidant activities | |
| Schnepp | Biopolymers as a flexible resource for nanochemistry | |
| Barikani et al. | Preparation and application of chitin and its derivatives: a review | |
| CN102417606B (zh) | 一种甲壳素气凝胶的制备方法 | |
| Fu et al. | Natural polysaccharide-based aerogels and their applications in oil–water separations: a review | |
| Nogi et al. | Preparation of nanofibrillar carbon from chitin nanofibers | |
| CN103059319B (zh) | 甲壳素纳米纤维制备方法 | |
| Singh et al. | From cellulose dissolution and regeneration to added value applications—Synergism between molecular understanding and material development | |
| CN1940153A (zh) | 壳聚糖接枝海藻纤维及其制备方法与用途 | |
| JPH02277545A (ja) | 成形用活性炭組成物及び活性炭成形物 | |
| Budtova et al. | Biorefinery approach for aerogels | |
| Jung et al. | Preparation and structural investigation of novel β-chitin nanocrystals from cuttlefish bone | |
| Rameshthangam et al. | Chitin and Chitinases: biomedical and environmental applications of chitin and its derivatives | |
| CN109158058B (zh) | 凹土-壳聚糖复合凝胶及其制备方法 | |
| CN104927070A (zh) | 一种壳聚糖膜的制备方法 | |
| CN111518296B (zh) | 一种壳聚糖膜材料的制备方法 | |
| Ofem et al. | Properties of chitin reinforces composites: a review | |
| CN114316375B (zh) | 一种多级孔结构复合气凝胶及其制备方法 | |
| Ullah et al. | Introduction to nanocellulose | |
| Xu et al. | Hemicellulose-based hydrogels for advanced applications | |
| CN114907592B (zh) | 一种高效制备甲壳素膜材料的方法 | |
| CN115142263B (zh) | 阳离子竹纤维素纳米纤维及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |