CN107653747B - Enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper and preparation method thereof - Google Patents
Enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper and preparation method thereof Download PDFInfo
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- CN107653747B CN107653747B CN201710917420.XA CN201710917420A CN107653747B CN 107653747 B CN107653747 B CN 107653747B CN 201710917420 A CN201710917420 A CN 201710917420A CN 107653747 B CN107653747 B CN 107653747B
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- lignosulfonic acid
- conductive paper
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 100
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 28
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 25
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920005610 lignin Polymers 0.000 claims abstract description 46
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 238000002791 soaking Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 102000003992 Peroxidases Human genes 0.000 claims abstract description 18
- 108040007629 peroxidase activity proteins Proteins 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000000123 paper Substances 0.000 claims description 172
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 238000004537 pulping Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 108010054320 Lignin peroxidase Proteins 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 108010059896 Manganese peroxidase Proteins 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 3
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000002655 kraft paper Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 24
- 239000000835 fiber Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000011065 in-situ storage Methods 0.000 description 16
- 238000005452 bending Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000001338 self-assembly Methods 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 235000019357 lignosulphonate Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000012064 sodium phosphate buffer Substances 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006872 enzymatic polymerization reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000008030 superplasticizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- ONGGURNBDHMMTE-UHFFFAOYSA-N ClCC(C[Na])O Chemical compound ClCC(C[Na])O ONGGURNBDHMMTE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- -1 Hydroxypropyl Chemical group 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEHIPPDDMCEYPI-UHFFFAOYSA-L disodium propanedioate propanedioic acid Chemical compound [Na+].[Na+].OC(=O)CC(O)=O.[O-]C(=O)CC([O-])=O IEHIPPDDMCEYPI-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/23—Lignins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/65—Acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of functional materials, and discloses a lignin sulfonic acid/polypyrrole composite conductive paper modified by enzyme catalysis polymerization and a preparation method thereof. The method comprises the following steps: separating lignosulfonate with ultrafiltration membrane, purifying with cation exchange resin, and drying to obtain lignosulfonate solid powder; soaking paper in a mixed solution of lignosulfonic acid and peroxidase for 10-30 min, transferring the paper to a hydrogen peroxide solution, and reacting for 1-2 h at 20-40 ℃; then soaking the substrate in a pyrrole solution for 10-30 min; and soaking the paper in a mixed solution of an oxidant and an inorganic acid to react for 10-120 min to obtain the self-assembled layer of composite conductive paper. Repeating the steps to obtain the self-assembled multilayer conductive paper. The conductive paper has the advantages of high conductivity, good stability, adjustable load capacity, difficult powder falling and the like, and can be applied to the aspects of planar heating materials, electromagnetic shielding materials, flexible electrode materials and the like.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper and a preparation method thereof.
Background
The conductive paper is functional paper with good conductivity, has functions of heat conduction, electromagnetic shielding, electrostatic shielding and the like, and can be widely applied to the fields of planar heating materials, electromagnetic shielding materials, antistatic packaging materials, sensing materials, electrochemical materials and the like. Polypyrrole (PPy) is used as a typical conductive polymer, has simple synthesis process and low cost, has excellent conductivity, optical property and mechanical property, and can be used for preparing multifunctional conductive paper. However, because polypyrrole is hydrophobic and the fiber is hydrophilic, the bonding force between the polypyrrole and the fiber is very weak, which causes the problem of 'dusting'. The polypyrrole is deposited on the surface and inside of the fiber/paper by an in-situ polymerization method, so that the fiber/paper is endowed with excellent conductivity, the problem of difficulty in processing can be solved, the adhesion between the fiber and the polypyrrole is improved, but an oxidant, acid and the like used in the in-situ polymerization process damage the fiber, the strength of the finished paper is reduced, and the conductivity and the mechanical property thereof need to be further improved. In addition, the in-situ polymerization method for preparing the conductive paper has the problems of low load capacity and poor conductivity. Polymer conductive paper can also be prepared by alternately adsorbing multiple layers of polyelectrolytes (at least one of which is a conductive polymer) with opposite charges on fibers by an electrostatic layer-by-layer self-assembly technology, but a suitable anionic polyelectrolyte needs to be found to simultaneously improve the conductivity and the mechanical property of the polypyrrole conductive paper. In addition, the soluble polypyrrole used in the self-assembly process is complex to synthesize, increasing the preparation cost of the conductive paper.
wIn addition, the lignin is taken as a main component of cell walls and has good functions of oxidation resistance, ultraviolet resistance, corrosion resistance and the like, and in the industry, the lignin is mainly from the pulping and papermaking industry, wherein sulfonated products of acid pulping red liquor (lignosulfonate) and alkaline pulping black liquor (alkaline lignin) can be used as a doping agent and a dispersing agent in the preparation process of polypyrrole due to the fact that a large number of sulfonic acid groups are contained in the molecular structure of sulfonated products, namely, sulfonated lignin sulfonate (such as potassium, sodium or ammonium salt) solution of sulfonated lignin is purified by cation exchange resin to prepare a lignosulfonate solution, and oxidation polymerization reaction of polymer monomers is initiated to prepare a water-soluble conductive polymer, the lignosulfonate is used as a template and a doping agent of the oxidation polymerization reaction, the relative mass of the industrial sulfonate is low, the dispersion degree of the lignosulfonate is large, the lignin molecular weight is high, the dispersion degree of the lignosulfonate is large, and the modified lignin sulfonate has high commercial conductive molecular weight (PSS) which is more than that the lignosulfonate is used as a template and a conductive polymer with high dispersion property of the lignin sulfonate which is more uniform and has a high price limit the lignin sulfonate (PSS) and the dispersion of the lignin sulfonate which is used as a template and a high conductive polymer.
The chemical modification method is usually adopted in industry to prepare the lignosulfonate with high molecular weight, and the common chemical modification method comprises a polycondensation method, a graft copolymerization method, an alkyl bridging method and the like. CN101575418A discloses a lignin-based superplasticizer with high sulfonation degree and high molecular weight and a preparation method thereof, wherein a lignin-based superplasticizer with weight-average molecular weight more than 10000Da is synthesized by reacting with dihydroxy ketone to introduce a branched chain on lignin and then adding a condensing agent. Qin et al (ACS Sustainable chemistry & Engineering,2015,3(12):3239-3244.) use 3-chloro-2-hydroxypropyl sodium to graft sulfonate alkali lignin to prepare high sulfonation degree Hydroxypropyl Sulfonated Lignin (HSL), and further increase its molecular weight through etherification reaction and reduce its phenolic hydroxyl and carboxyl content, the modified product can be used as dye dispersant. Zenmei et al (Proc. Chem., 2016,67(1):331-338.) use 1, 4-butanesultone as sulfonating agent and 1, 6-dibromohexane as alkylating bridge, and realize sulfonation and alkyl chain bridge of alkali lignin by one-step reaction to increase sulfonation degree and molecular weight. The chemical modification of lignin has the advantages of short reaction time and mature process, and has the disadvantages of needing to add a large amount of chemical reagents, more reaction byproducts and limited molecular weight improvement.
The biocatalysis method has mild reaction conditions, does not need to add a large amount of chemical reagents, is green and environment-friendly, and is the direction of lignin modification in the future. The peroxidase is an enzymatic polymerization catalyst capable of generating active free radicals, can catalyze the polymerization of oxidizing phenols and aromatic amines by hydrogen peroxide, and has the advantages of mild reaction conditions, high selectivity, high catalysis efficiency and the like. As a phenolic substrate, lignin can also be modified with biological enzymes. Liu's equalizer flood, etc. (J. polymer material science and engineering, 2001,3:83-86.) adopts horseradish peroxidase to catalyze lignin and phenol to carry out copolymerization reaction in a reverse microemulsion system, the reaction rate is fast, and the thermal property of the copolymer is greatly improved. CN103088067A adopts peroxidase to catalyze and synthesize high molecular weight sodium lignosulfonate polymer, the prepared sodium lignosulfonate polymer has the weight average molecular weight of 30000 Da-100000 Da, and the dispersibility of the sodium lignosulfonate polymer in a solid particle suspension system is improved. Our earlier studies show that the modification of horseradish peroxidase (HRP) can significantly improve the molecular weight of lignosulfonic acid, and is beneficial to the improvement of the dispersion performance and the electrical conductivity of a lignin/polyaniline (lignin/PANI) composite material ([ J ]. Applied Surface Science,2017,426: 287-293.). However, the high molecular weight polymer obtained by HRP catalyzed polymerization of lignosulfonic acid in solution is spherical structure, which is not favorable for adsorption of aniline monomer and ordered polymerization of monomer, so the improvement of PANI conductivity is not as good as polystyrene sulfonic acid with linear structure. In addition, the polymerization of lignosulfonic acid in solution is disordered, resulting in a large dispersion of the polymerization product, which is not favorable for its use as a dopant and dispersant for conductive polymers.
The invention prepares the lignin sulfonic acid/polypyrrole composite conductive paper modified by enzyme catalysis polymerization by taking lignin sulfonic acid which has wide sources, low price and regeneration as a reinforcing agent. The method realizes the synchronous in-situ polymerization and electrostatic self-assembly, namely the adsorption polymerization of pyrrole monomers on paper and the alternate adsorption self-assembly of polypyrrole and lignosulfonic acid are simultaneously carried out, and the two methods play a role in synergy. In addition, the lignosulfonic acid can be combined with hydroxyl on the surface of the fiber through hydrogen bonds to strengthen the paper base, the effect is similar to that of nailing nails at the connecting position between the fiber and the fiber, and the problem of reduced paper forming strength caused by the damage of conductive material coating or oxidizing agent, acid and the like to the fiber in the subsequent step is solved. The lignin can be orderly crosslinked into a lignin polymer with a high molecular weight net structure through the peroxidase catalytic polymerization reaction of the lignin on the paper base, so that the adsorption points and the adsorption strength of the lignin on fibers are increased, and the paper forming strength is further improved. The electrostatic adsorption effect exists between the lignosulfonic acid and the polypyrrole, so that the lignosulfonic acid can play a role in bonding reinforcement in a polypyrrole conductive paper system, avoid the phenomenon of powder falling, and improve the tensile strength and bending stability of the conductive paper. Because the lignosulfonic acid is antioxidant and uvioresistant and is not easy to dedope, the conductivity stability of the polypyrrole conductive paper can be improved. The enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper prepared by the self-assembly-in-situ polymerization method has the advantages of high conductivity, good stability, adjustable load capacity, difficulty in powder falling and the like, and can be applied to the aspects of planar heating materials, electromagnetic shielding materials, flexible electrode materials and the like. Therefore, the lignin is applied to the field of polymer conductive paper, and has double meanings of realizing the value-added utilization of the lignin and improving the performance of the polymer conductive paper.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide the lignin sulfonic acid/polypyrrole composite conductive paper modified by enzyme catalysis polymerization. The conductive paper has the advantages of high conductivity, good stability, adjustable loading capacity, difficult powder falling and the like, and can be applied to the aspects of planar heating materials, electromagnetic shielding materials, flexible electrode materials and the like.
The invention also aims to provide a preparation method of the catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper. The preparation method of the invention takes the lignin sulfonic acid with wide source, low price and reproducibility as the reinforcing agent to prepare the enzyme catalysis polymerization modified lignin sulfonic acid/polypyrrole composite conductive paper by the self-assembly-in-situ polymerization method.
The purpose of the invention is realized by the following scheme:
A preparation method of catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper comprises the following steps:
(1) Separating lignosulfonate with ultrafiltration membrane, purifying with cation exchange resin, and drying to obtain lignosulfonate solid powder;
(2) Soaking paper in a mixed solution of lignosulfonic acid and peroxidase for 10-30 min, transferring the paper to a hydrogen peroxide solution, and reacting for 1-2 h at 20-40 ℃;
(3) Then soaking the substrate in a pyrrole solution for 10-30 min;
(4) And soaking the paper in a mixed solution of an oxidant and an inorganic acid for reaction for 10-120 min to obtain the self-assembled layer of the catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper.
Further, the self-assembled multilayer enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper can be obtained by repeating the steps (2) to (4) in the preparation method.
In the preparation method of the invention, the lignosulfonate can be, but is not limited to, sodium lignosulfonate, calcium lignosulfonate and magnesium lignosulfonate in acid pulping red liquor, or at least one of sulfonated alkali lignin and sulfomethylated alkali lignin obtained by sulfonating/sulfomethylating alkaline pulping black liquor.
the pulp of the acid pulping and the alkaline pulping is wood pulp, straw pulp or bamboo pulp.
The molecular weight cut-off of the ultrafiltration membrane in the step (1) is preferably 10000-50000, and more preferably 20000-30000.
The lignin sulfonate in paper making industry has wide distribution of relative molecular mass and large dispersion degree, which causes non-uniformity of structure and physical and chemical properties and greatly limits industrial modification and utilization of the lignin sulfonate, when the lignin sulfonate is used as a raw material, an ultrafiltration membrane separation technology is utilized, firstly, an ultrafiltration membrane with the membrane cut-off molecular weight of 10000-50000 is used for separating the lignin sulfonate to prepare the lignin sulfonate with the polydispersity index of M w/M n less than 2, if the molecular weight of the lignin sulfonate is too low, the doping and dispersion of polypyrrole are not facilitated, if the molecular weight of the lignin sulfonate is too high, the reaction activity is low, the condensation reaction is not facilitated, therefore, the cut-off molecular weight is preferably controlled at 10000-50000 (M w/M n is less than 2).
The cation exchange resin purification in the step (1) aims to remove most of impurity cations in the lignosulfonate, improve the performance of the lignosulfonate in doping preparation of a conductive polymer, and dry the collected lignosulfonate solution for later use.
The paper in step (2) may be any conventionally used paper, such as but not limited to ordinary qualitative filter paper, quantitative filter paper, printing paper, kraft paper, and the like.
the peroxidase in the step (2) can be, but is not limited to, at least one of horseradish peroxidase, soybean peroxidase, lignin peroxidase and manganese peroxidase.
And (3) adding solid lignosulfonic acid powder and peroxidase into a buffer solution with the pH of 4.0-7.0 to prepare a mixed solution of lignosulfonic acid and peroxidase.
In the mixed solution, the mass percent concentration of the lignosulfonic acid is 20-50%, and the mass percent concentration of the peroxidase is 1-5%.
The buffer solution may be, but is not limited to, at least one of acetic acid-sodium acetate, phosphoric acid-sodium phosphate, citric acid-sodium citrate, and malonic acid-sodium malonate.
The mass percentage concentration of the hydrogen peroxide solution in the step (2) is 10-30%.
Soaking paper in a mixed solution of lignosulfonic acid and peroxidase to make the solution reach saturated adsorption on the paper; then the hydrogen peroxide solution is used for starting the enzyme catalytic polymerization reaction.
The enzymatic polymerization reaction of the lignosulfonic acid in the solution is usually disordered, and finally lignin molecules are cross-linked and aggregated into a sphere to form a large steric hindrance, which is not beneficial to the adsorption polymerization of pyrrole monomers in the subsequent steps. According to the preparation method, the mixed solution of the lignosulfonic acid and the peroxidase is uniformly adsorbed on the paper base, and then the paper base is transferred to the hydrogen peroxide solution for polymerization reaction, so that lignin molecules are orderly crosslinked into a lignin polymer with a high molecular weight net structure, the adsorption points and the adsorption strength of the lignin polymer on fibers are increased, and the strength of the finished paper is further improved. The method is carried out under the condition from weak acidity to neutrality (pH is 4.0-7.0), and retention of paper strength is facilitated. Compared with the traditional chemical condensation method, the enzyme catalysis polymerization reaction is obtained under the mild reaction condition without using formaldehyde, and hydrogen peroxide is used as an oxygen source, so that other byproducts polluting the environment are not generated; the reaction solvent is water, and has the characteristics of safety, low cost, environmental friendliness and the like.
Meanwhile, the polymerization temperature is controlled to be 20-40 ℃. If the temperature is lower than 20 ℃, the polymerization reaction rate is slower; if the temperature is higher than 40 ℃, enzyme inactivation may result; in view of the demand for low energy consumption for industrialization, it is more preferably carried out at room temperature (25 ℃ C.).
After the reaction in the step (2), the paper is preferably taken out, washed and dried for further treatment. The unadsorbed lignosulfonic acid can be removed by washing, so that the influence of the unadsorbed lignosulfonic acid on the adsorption of the subsequent cationic conductive polypyrrole and the stability of the adsorption layer is reduced.
The volume concentration of the pyrrole solution in the step (3) is preferably 5-40%, and more preferably 10-30%; the solvent of the solution is an organic solvent, and may be, but is not limited to, at least one of ethanol, ethylene glycol, and acetone.
In the step (3), the paper is soaked in a pyrrole solution to ensure that pyrrole is saturated and adsorbed in the paper. The system concentration of the pyrrole solution is preferably controlled in the invention because if the volume concentration of pyrrole is lower than 5%, the adsorption efficiency is lower, the adsorption amount is smaller, and the conductivity of the prepared polypyrrole conductive paper is lower; if the volume concentration of the pyrrole is higher than 40%, the adsorption is easy to be uneven, the subsequent in-situ polymerization reaction rate is too high, and the polypyrrole is aggregated, so that the uniformity degree of the prepared polypyrrole conductive paper is reduced; more preferably 10 to 30%.
The preparation method of the invention mainly prepares the polypyrrole conductive paper by adsorbing and depositing polypyrrole on a paper substrate through an in-situ polymerization method. Therefore, the concentration of the inorganic acid, the molar ratio of the oxidizing agent to the inorganic acid have a very important influence on the properties of the resulting conductive paper.
The concentration of the inorganic acid in the mixed solution in the step (4) is preferably 0.1-0.5 mol/L, and more preferably 0.2-0.4 mol/L.
in the invention, the inorganic acid can play a doping role, and if the concentration of the inorganic acid is lower than 0.1mol/L, the conductivity of the polypyrrole is lower; if the concentration of the inorganic acid is higher than 0.5mol/L, the rate of the in-situ polymerization reaction is too fast, and the polypyrrole is aggregated, so that the uniformity degree of the prepared polypyrrole conductive paper is reduced. In addition, too high a concentration of mineral acid can also damage the fibers, resulting in a significant reduction in paper strength.
The molar ratio of the oxidant to the inorganic acid in the step (4) is preferably 1: 2-2: 1, and more preferably 1: 1-2: 1.
In the present invention, the oxidizing agent may serve to initiate polymerization of the azole monomer in an amount which is an important factor affecting the properties of the polymerization product. If the molar ratio of the oxidizing agent to the inorganic acid is less than 1:2, the pyrrole monomer is not sufficiently polymerized, and the conductivity is low; if the molar ratio of the oxidant to the inorganic acid is higher than 2:1, the in-situ polymerization reaction rate is too high, and the polypyrrole is aggregated, so that the uniformity degree of the prepared polypyrrole conductive paper is reduced; more preferably 1:1 to 2: 1.
The oxidant in the step (4) can be at least one of but not limited to ferric chloride, ferric sulfate and ammonium persulfate; preferably at least one of ferric chloride and ammonium persulfate. When ferric chloride is used as an oxidant, the conductivity of the obtained conductive paper is optimal; in the case of using ammonium persulfate as the oxidizing agent, the conductive paper obtained has the best conductive stability, and therefore, it is preferable to use at least one of ferric chloride and ammonium persulfate as the oxidizing agent.
The inorganic acid in step (4) may be, but is not limited to, at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
the reaction time in the step (4) is preferably 30-60 min. The method has the advantages that the control time is 10-120 min, if the reaction time is too short, the pyrrole monomer cannot be fully polymerized, and the conductivity is lower; if the reaction time is too long, the oxidation degree of the pyrrole monomer is deepened, the conjugation degree is reduced, and the conductivity is reduced; more preferably 30 to 60 min.
The paper after the reaction in the step (4) is preferably washed with water and dried. And washing the paper subjected to adsorption and deposition of the conductive polypyrrole with water until the washing liquid is neutral to remove the unadsorbed polypyrrole.
and (3) repeating the steps (2) to (4) in the preparation method to obtain the self-assembled multilayer enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper, preferably washing the paper after the reaction in the step (4) with water, drying and then repeatedly treating. As above, washing can remove unadsorbed polypyrrole, thereby reducing its effect on the adsorption of anionic lignosulfonic acid and the stability of the final adsorbed layer upon subsequent repeated assembly.
By using the method, the number of self-assembled layers can be controlled according to the requirement to prepare the polypyrrole conductive paper with different loading amounts and different conductivities, so that the requirements of different application fields are met. The number of self-assembled layers is an important factor affecting the performance of the conductive paper, and the damage of the oxidizing agent and acid to the fibers during the in-situ polymerization process can reduce the strength of the paper. Therefore, the self-assembled multilayer lignin sulfonic acid/polypyrrole composite conductive paper modified by enzyme catalysis polymerization preferably has 2-8 self-assembled layers, and more preferably has 3-6 self-assembled layers.
in the preparation method, the adsorption polymerization of pyrrole monomers on paper and the alternate adsorption self-assembly of polypyrrole and lignosulfonic acid are carried out simultaneously. In the process of electrostatic layer-by-layer self-assembly, lignosulfonic acid as an anionic polyelectrolyte can electrostatically adsorb cationic conductive polypyrrole, so that a conductive coating with adjustable loading capacity and conductivity is formed on a paper base. During the in-situ polymerization process, lignosulfonic acid can act as a dopant and dispersant for the conductive polypyrrole. In addition, the lignosulfonic acid can be combined with hydroxyl on the surface of the fiber through hydrogen bonds to strengthen the paper base, the effect is similar to that of nailing nails at the connecting position between the fiber and the fiber, and the problem of reduced paper forming strength caused by the damage of conductive material coating or oxidizing agent, acid and the like to the fiber in the subsequent step is solved. The condensation reaction of the lignosulfonic acid and the aldehydes on the paper base can lead the lignosulfonic acid and the aldehydes to be orderly crosslinked into a net structure, increase the adsorption points and the adsorption strength of the lignin on the fibers, and further improve the strength of the finished paper. The electrostatic adsorption effect exists between the lignosulfonic acid and the polypyrrole, so that the lignosulfonic acid can play a role in bonding reinforcement in a polypyrrole conductive paper system, avoid the phenomenon of powder falling, and improve the tensile strength and bending stability of the conductive paper. Because the lignosulfonic acid is antioxidant and uvioresistant and is not easy to dedope, the conductivity stability of the polypyrrole conductive paper can be improved. The catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper prepared by the self-assembly-in-situ polymerization method has the advantages of high conductivity, good stability, controllable loading capacity, difficulty in powder falling and the like, and can be applied to the aspects of planar heating materials, electromagnetic shielding materials, flexible electrode materials and the like.
The invention also provides the lignosulfonic acid reinforced polypyrrole conductive paper prepared by the method, which has the advantages of high conductivity, good stability, controllable loading capacity, difficulty in powder falling and the like, and can be applied to the aspects of planar heating materials, electromagnetic shielding materials, flexible electrode materials and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. The preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper is simple, the reaction is carried out at normal temperature, the pyrrole monomer and the lignosulfonic acid are cheap and easy to obtain, and the problem of high cost of the conductive paper is solved.
2. The peroxidase catalytic polymerization reaction of the lignin is carried out on the paper base under neutral/weak acid and room temperature conditions, which is beneficial to orderly crosslinking the lignin into a lignin polymer with a high molecular weight net structure, increases the adsorption point and the adsorption strength of the lignin on fibers, and further improves the strength of finished paper.
3. according to the invention, the lignosulfonic acid is applied to the polypyrrole conductive paper system, so that the effects of doping and dispersing are achieved, the bonding enhancement is also achieved, the conductivity and mechanical properties of the conductive paper can be improved, and the advantages of the lignosulfonic acid are more prominent through multilayer self-assembly.
4. The enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper prepared by the invention has the advantages of high conductivity, good stability, adjustable loading capacity, difficulty in powder falling and the like, and can be applied to the aspects of planar heating materials, electromagnetic shielding materials, flexible electrode materials and the like.
drawings
fig. 1 shows the effect of the number of self-assembled layers on the loading of the lignosulfonic acid/polypyrrole composite conductive paper.
Fig. 2 is a graph showing the effect of the number of self-assembled layers on the conductivity of the lignosulfonic acid/polypyrrole composite conductive paper.
Fig. 3 to 4 show the bending stability of the self-assembled 6-layer polypyrrole conductive paper.
Detailed Description
the present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
example 1:
separating the straw pulp sulfonated alkali lignin (obtained by sulfonating straw pulp alkaline pulping black liquor) by using an ultrafiltration membrane with the cut-off molecular weight of 10000-50000, purifying by using cation exchange resin, and drying to obtain the lignosulfonic acid solid. Adding solid lignosulfonic acid powder and horseradish peroxidase into a phosphoric acid-sodium phosphate buffer solution with the pH of 6.0 to prepare a mixed solution, wherein the mass percentage concentration of the solid lignosulfonic acid powder is 50%, and the mass percentage concentration of the horseradish peroxidase is 5%. Soaking 18cm qualitative filter paper in the mixed solution for 10min, transferring to 30% hydrogen peroxide solution by mass percent, soaking for 10min, reacting for 1h at 25 ℃, taking out, washing with deionized water, and drying. Then soaking the mixture in 20mL of mixed solution of pyrrole and ethanol for 10min, wherein the volume ratio of pyrrole to ethanol is 30%, taking out the mixture and transferring the mixture to 20mL of mixed solution of hydrochloric acid and ferric trichloride for reaction for 40min, the concentration of hydrochloric acid is 0.3mol/L, and the molar ratio of hydrochloric acid to ferric trichloride is 1: 1. The paper loaded with the reaction product was taken out, washed with deionized water and dried. Repeating the steps to prepare the self-assembled multilayer enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper.
Example 2:
Separating the wood pulp sodium lignosulfonate (which is red liquor produced by the acid pulping of wood pulp) by using an ultrafiltration membrane with the molecular weight cutoff of 10000-50000, purifying by using cation exchange resin, and drying to obtain the lignosulfonic acid solid. Adding solid lignosulfonic acid powder and lignin peroxidase into a phosphoric acid-sodium phosphate buffer solution with the pH value of 6.0 to prepare a mixed solution, wherein the mass percentage concentration of the solid lignosulfonic acid powder is 40%, and the mass percentage concentration of the lignin peroxidase is 4%. Soaking 18cm qualitative filter paper in the mixed solution for 10min, transferring to 30% hydrogen peroxide solution by mass percent, soaking for 10min, reacting for 1h at 25 ℃, taking out, washing with deionized water, and drying. Then soaking the mixture in 20mL of mixed solution of pyrrole and ethanol for 10min, wherein the volume ratio of pyrrole to ethanol is 30%, taking out the mixture and transferring the mixture to 20mL of mixed solution of hydrochloric acid and ferric trichloride for reaction for 40min, the concentration of hydrochloric acid is 0.3mol/L, and the molar ratio of hydrochloric acid to ferric trichloride is 1: 1. The paper loaded with the reaction product was taken out, washed with deionized water and dried. Repeating the steps to prepare the self-assembled multilayer enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper.
Example 3: comparative example
Soaking 18cm of qualitative filter paper in 20mL of mixed solution of pyrrole and ethanol for 10min, wherein the volume ratio of pyrrole to ethanol is 30%, taking out and transferring to 20mL of mixed solution of hydrochloric acid and ferric trichloride for reaction for 40min, wherein the concentration of hydrochloric acid is 0.3mol/L, and the molar ratio of hydrochloric acid to ferric trichloride is 1: 1. The paper loaded with the reaction product was taken out, washed with deionized water and dried. And repeating the steps to prepare the hydrochloric acid doped polypyrrole conductive Paper (HCl-PPy/Paper).
Example 4:
The preparation method comprises the steps of separating bamboo pulp calcium lignosulfonate (which is red liquor produced by acid pulping of bamboo pulp) by using an ultrafiltration membrane with the molecular weight cutoff of 10000-50000, purifying by using cation exchange resin, and drying to obtain lignosulfonic acid solid, adding lignosulfonic acid solid powder and lignin peroxidase into phosphoric acid-sodium phosphate buffer solution with the pH of 5.0 to prepare mixed solution, soaking lignosulfonic acid solid powder in a mass percentage concentration of 30% and lignin peroxidase in a mass percentage concentration of 3%, 80g/m 2, soaking 15cm × 17cm printing paper in the mixed solution for 20min, transferring the printing paper to 20% hydrogen peroxide solution for soaking for 20min, reacting at 30 ℃ for 1.5h, taking out the printing paper, washing the printing paper with deionized water, drying, transferring the printing paper to 20mL mixed solution of pyrrole and ethylene glycol for reacting for 30min, taking out the concentration of hydrochloric acid to 0.2mol/L, and the molar ratio of hydrochloric acid to ammonium persulfate to 2:1, taking out the paper loaded with reaction products, drying by using deionized water, and preparing the multi-layer conductive polypyrrole/lignin polymerized paper which is repeatedly assembled by the steps.
Example 5:
The method comprises the steps of separating wood pulp sulfomethylated alkali lignin (obtained by sulfomethylation of wood pulp alkaline pulping black liquor) by using an ultrafiltration membrane with the molecular weight cutoff of 10000-50000, purifying by using cation exchange resin, and drying to obtain lignosulfonic acid solid, adding lignosulfonic acid solid powder and manganese peroxidase into a citric acid-sodium citrate buffer solution with the pH of 4.0 to prepare a mixed solution, soaking the lignosulfonic acid solid powder in a 20% by mass concentration and the manganese peroxidase in a 2% by mass concentration, 80g/m 2, soaking a printing paper with the thickness of 15cm multiplied by 17cm in the mixed solution for 30min, transferring the printing paper into a 10% hydrogen peroxide solution for soaking for 30min, reacting for 2h at 40 ℃, taking out the printing paper, washing the printing paper with deionized water, drying the paper, transferring the paper to a mixed solution of 20mL of sulfuric acid and ferric trichloride, reacting for 60min, taking out the concentration of the sulfuric acid to 0.4mol/L, and performing polymerization on the paper with the ionic water to obtain the multi-layer polymerized polypyrrole/ferric chloride paper.
Description of the effects of the examples:
The loading amount, conductivity, air stability, tensile strength and bending stability of the polypyrrole conductive papers prepared in examples 1 to 3 were experimentally measured, and the results are shown in fig. 1 to 4, tables 1 and 2.
FIG. 1 analysis:
(1) The load is the mass of the lignosulfonic acid/polypyrrole complex deposited on a unit area of paper, and is the ratio of the paper weight gain to the paper area before and after reaction.
As can be seen from fig. 1, the load amounts of example 1 and example 2 significantly increased as the number of self-assembled layers increased. And the loading amounts of the two materials and the number of self-assembly layers of the two materials have a good linear relationship, namely the loading amounts in each assembly period are basically equal, which shows that the high-loading and load-controllable enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper can be prepared by a self-assembly-in-situ polymerization method.
FIG. 2 analysis:
(1) The room temperature square resistance R (omega/sq) of the conductive paper is measured by a double-electrical measuring four-probe resistivity tester, the thickness W (nm) of a corresponding test point is measured by a Dektak 150 step tester, then the conductivity of the conductive paper is calculated by the formula sigma 10 7/(RW), and the measurement is repeated for 10 times.
As can be seen from fig. 2, the conductivity of examples 1 and 2 is significantly improved with the increase of the number of self-assembled layers, indicating that the enzyme-catalyzed polymerization modified lignosulfonic acid/polypyrrole composite conductive paper with high conductivity can be prepared by the self-assembly-in-situ polymerization method.
Table 1 and table 2 show:
(1) The initial conductivity of the conductive paper was recorded as σ 0, the room temperature conductivity of the conductive paper measured by leaving the conductive paper open in the air for a certain period of time (3 months) was recorded as σ 1, and the conductivity retention of the conductive paper was calculated by the formula σ r ═ σ 1/σ 0) × 100% for evaluation of the air stability of the conductive paper.
(2) The tensile strength T (kN/m) of the conductive paper was measured using an L & W CE062 tensile strength tester, the tensile strength of the blank paper was recorded as T 0, the tensile strength of the conductive paper was recorded as T 1, and the tensile strength retention of the conductive paper was calculated by the formula T r ═ T 1/T 0 × 100% for evaluating the tensile strength of the conductive paper.
(3) Wherein HCl-PPy/Paper refers to hydrochloric acid doped polypyrrole conductive Paper (example 3: comparative).
As can be seen from tables 1 and 2, when the number of self-assembled layers is the same, the conductivity retention rate of the self-assembled Paper is higher than that of the HCl-PPy/Paper in the examples 1 and 2, which shows that the air stability of the polypyrrole conductive Paper can be improved by doping the lignosulfonic acid. The degradation of conductivity of polypyrrole conductive paper due to aging under ambient conditions is mainly caused by two factors, namely oxidative degradation of the polypyrrole (oxygen and moisture) and a reduction in the amount of dopant species (the anion-doped polypyrrole may undergo a dedoping process due to decomposition or removal of the anion, or due to reaction of the polymer backbone with the anion or its fragments). Therefore, doping lignosulfonic acid can enhance the air stability of polypyrrole conductive paper: on one hand, the lignin macromolecules have antioxidant aging performance and can reduce the oxidative degradation rate of the polypyrrole conductive paper; on the other hand, the lignosulfonic acid dopant is a biopolymer with a three-dimensional network structure, and a dedoping process is not easy to occur. In addition, the fibers are porous and have a high affinity for moisture, which is one of the main causes of rapid decrease in conductivity of the polypyrrole conductive paper. The dense conductive polypyrrole granules can protect or prevent the permeation of oxygen and moisture, and can also effectively prevent the volatilization of the doping agent. Therefore, with the increase of the number of self-assembly layers, the oxidation degradation and the dedoping rate of the polypyrrole conductive paper are reduced, and the air stability is improved.
TABLE 1 air stability of polypyrrole conductive paper with different layers
TABLE 2 tensile Strength of polypyrrole conductive paper with different layers
The tensile strength of examples 1, 2 and HCl-PPy/Paper self-assembled at different layers all showed different reductions compared to the blank Paper, with the highest retention of tensile strength for both self-assembled at 3 layers. This is because, on the one hand, damage to the fibers by oxidizing agents, acids, etc. leads to a decrease in the strength of the paper; on the other hand, the conductive polymer has certain mechanical strength, and can improve the strength of paper to a certain extent. The tensile strength retention of examples 1 and 2 was higher than that of HCl-PPy/Paper for the same number of self-assembled layers. This is because strong interaction exists between lignosulfonic acid and cellulose, polypyrrole, and can play a role in bond enhancement in polypyrrole conductive paper systems.
Fig. 3 and 4 show the bending stability of the self-assembled 6-layer polypyrrole conductive paper. A CHI 660E electrochemical workstation is adopted, a reference electrode and a counter electrode are connected to form an electrode and a working electrode to form a two-electrode system, a copper sheet or a lead is contacted with a sample and used as an electrode lead during testing, and the change condition of the conductivity of the conductive paper under the conditions of different bending angles (0 degrees, 30 degrees, 60 degrees and 90 degrees) (shown in figure 3) and 20-100 repeated bending conditions is tested by a linear scanning voltammetry method and used for evaluating the bending stability of the conductive paper (shown in figure 4).
As can be seen from the figure, the conductivity of the HCl-PPy/Paper is continuously reduced under different bending angles, especially after 20-100 times of repeated bending. And the conductivity of the conductive material in the embodiment 2 is almost unchanged under the conditions of different bending angles and 20-100 times of repeated bending, which shows that the bending stress has almost no influence on the conductivity of the conductive material. Because the lignosulfonic acid plays a role in bonding reinforcement in a polypyrrole conductive paper system, the bending stability of the conductive paper is improved. Therefore, the catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper prepared by the self-assembly-in-situ polymerization method has a huge application prospect in flexible electronic products.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper is characterized by comprising the following steps:
(1) Separating lignosulfonate with ultrafiltration membrane, purifying with cation exchange resin, and drying to obtain lignosulfonate solid powder;
(2) Soaking paper in a mixed solution of lignosulfonic acid and peroxidase for 10-30 min, transferring the paper to a hydrogen peroxide solution, and reacting for 1-2 h at 20-40 ℃;
(3) Then soaking the substrate in a pyrrole solution for 10-30 min;
(4) Soaking the paper in a mixed solution of an oxidant and an inorganic acid to react for 10-120 min to obtain a self-assembled layer of the lignin sulfonic acid/polypyrrole composite conductive paper modified by enzyme catalytic polymerization;
The cut-off molecular weight of the ultrafiltration membrane in the step (1) is 10000-50000;
the volume concentration of the pyrrole solution in the step (3) is 5-40%;
The concentration of the inorganic acid in the mixed solution in the step (4) is 0.1-0.5 mol/L; the molar ratio of the oxidant to the inorganic acid is 1: 2-2: 1.
2. the preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that: the lignosulfonate is sodium lignosulfonate, calcium lignosulfonate and magnesium lignosulfonate in acid pulping red liquor, or at least one of sulfonated alkali lignin and sulfomethylated alkali lignin obtained by sulfonating/sulfomethylating alkaline pulping black liquor; the paper is at least one of common qualitative filter paper, quantitative filter paper, printing paper and kraft paper.
3. the preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that: the peroxidase in the step (2) is at least one of horseradish peroxidase, soybean peroxidase, lignin peroxidase and manganese peroxidase.
4. The preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that: in the mixed solution of the lignosulfonic acid and the peroxidase in the step (2), the mass percentage concentration of the lignosulfonic acid is 20-50%, and the mass percentage concentration of the peroxidase is 1-5%.
5. The preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that: and (3) the solvent of the pyrrole solution is at least one of ethanol, glycol and acetone.
6. The preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that: the reaction time in the step (4) is 30-60 min.
7. The preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that: the oxidant in the step (4) is at least one of ferric chloride, ferric sulfate and ammonium persulfate; the inorganic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
8. the preparation method of the catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 1, characterized in that the self-assembled multilayer catalytic polymerization modified lignosulfonic acid/polypyrrole composite conductive paper is obtained by repeating steps (2) to (4) in the preparation method.
9. the preparation method of the enzyme catalysis polymerization modified lignosulfonic acid/polypyrrole composite conductive paper according to claim 8, characterized in that: and (4) washing the reacted paper in the step (4) with water, drying and then repeatedly treating.
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| CN103088067A (en) * | 2013-01-22 | 2013-05-08 | 华南理工大学 | Method for catalytically synthesizing sodium lignin sulfonate with high molecular weight by peroxidase |
| CN105702483A (en) * | 2016-01-13 | 2016-06-22 | 华中科技大学 | Paper-base polypyrrole composite film and preparation method thereof |
| CN106241780A (en) * | 2016-07-19 | 2016-12-21 | 华南理工大学 | A kind of method preparing Graphene for raw material with lignin |
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| CN103088067A (en) * | 2013-01-22 | 2013-05-08 | 华南理工大学 | Method for catalytically synthesizing sodium lignin sulfonate with high molecular weight by peroxidase |
| CN105702483A (en) * | 2016-01-13 | 2016-06-22 | 华中科技大学 | Paper-base polypyrrole composite film and preparation method thereof |
| CN106241780A (en) * | 2016-07-19 | 2016-12-21 | 华南理工大学 | A kind of method preparing Graphene for raw material with lignin |
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