CN1798890A - Process for producing a fibrous composition - Google Patents
Process for producing a fibrous composition Download PDFInfo
- Publication number
- CN1798890A CN1798890A CNA200480015103XA CN200480015103A CN1798890A CN 1798890 A CN1798890 A CN 1798890A CN A200480015103X A CNA200480015103X A CN A200480015103XA CN 200480015103 A CN200480015103 A CN 200480015103A CN 1798890 A CN1798890 A CN 1798890A
- Authority
- CN
- China
- Prior art keywords
- fiber
- water
- polymer
- paper
- aniline
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 67
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 32
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
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- 229920001059 synthetic polymer Polymers 0.000 claims abstract 2
- 239000000835 fiber Substances 0.000 claims description 374
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 176
- 229920000767 polyaniline Polymers 0.000 claims description 88
- 239000000126 substance Substances 0.000 claims description 63
- 239000002322 conducting polymer Substances 0.000 claims description 62
- 150000002500 ions Chemical class 0.000 claims description 61
- 229920001131 Pulp (paper) Polymers 0.000 claims description 29
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 16
- 229920002678 cellulose Polymers 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 15
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 13
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 13
- 239000011111 cardboard Substances 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
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- 239000011087 paperboard Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
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- 239000002019 doping agent Substances 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 94
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 42
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 42
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 41
- 238000004140 cleaning Methods 0.000 description 34
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- 239000000376 reactant Substances 0.000 description 23
- 239000005457 ice water Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
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- 230000001590 oxidative effect Effects 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229920002522 Wood fibre Polymers 0.000 description 10
- -1 aromatic phosphoric acid diester Chemical class 0.000 description 10
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- 230000008030 elimination Effects 0.000 description 8
- 238000003379 elimination reaction Methods 0.000 description 8
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- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 7
- 241000218691 Cupressaceae Species 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
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- 229950004288 tosilate Drugs 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- KYHUYFPGVJKKLM-UHFFFAOYSA-N aniline dodecyl benzenesulfonate Chemical compound C(CCCCCCCCCCC)OS(=O)(=O)C1=CC=CC=C1.NC1=CC=CC=C1 KYHUYFPGVJKKLM-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
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- 230000002829 reductive effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920001410 Microfiber Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
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- 230000001936 parietal effect Effects 0.000 description 3
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- 230000000717 retained effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
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- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- GGFOZRQCNXQCLO-UHFFFAOYSA-N aniline;methanesulfonic acid Chemical class CS(O)(=O)=O.NC1=CC=CC=C1 GGFOZRQCNXQCLO-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
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- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 2
- XUYJLQHKOGNDPB-UHFFFAOYSA-N phosphonoacetic acid Chemical compound OC(=O)CP(O)(O)=O XUYJLQHKOGNDPB-UHFFFAOYSA-N 0.000 description 2
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- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- KEPQJZFODFSHBY-UHFFFAOYSA-N 2-amino-6-methoxybenzenesulfonic acid Chemical compound COC1=CC=CC(N)=C1S(O)(=O)=O KEPQJZFODFSHBY-UHFFFAOYSA-N 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
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- 240000006240 Linum usitatissimum Species 0.000 description 1
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- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- XEBXIPKRYSEPHS-UHFFFAOYSA-N aniline;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound NC1=CC=CC=C1.OC(=O)CC(O)(C(O)=O)CC(O)=O XEBXIPKRYSEPHS-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- ZKIHLVYBGPFUAD-UHFFFAOYSA-N quinoline-2-sulfonic acid Chemical compound C1=CC=CC2=NC(S(=O)(=O)O)=CC=C21 ZKIHLVYBGPFUAD-UHFFFAOYSA-N 0.000 description 1
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- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- 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
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A process of producing a fibrous composition, which includes a first component that comprises vegetable fibres and a second component that consists of a synthetic, electrically conductive polymer. According to the method, the vegetable fibres comprise porous, loose and separate fibres, and the electrically conductive polymer is an independently electrically conductive polymer which is doped in order to generate charge carriers in the polymeric material, the synthetic polymer being produced by in situ - polymerization inside the fibres and on their surfaces. The doping agent is an organic sulphonic acid which is allowed to absorb into the fibres in an aqueous medium, and after that a monomer corresponding to the polymer is brought into contact with the fibres and polymerised. By means of the invention, the electrically conductive polymers are attached to fibres so firmly that they are not substantially out-washable by water.
Description
The present invention relates to production method according to the described fiber composition of preorder of claim 1.
This composition comprises the porous fibre and the synthetic conducting polymer of plant origin usually, and it is produced by making conducting polymer polymerization in fiber.
From patent documentation, know the paper and the paper products that contain conducting polymer.For example, U.S. Patent number 5421959 discloses the composite that is made of paper and conducting polymer, the product that it for example is suitable as electrode, the antistatic packaging material of galvanic cell or secondary cell and is used for electromagnetic radiation shielding.The production method of this composite is as follows: paper is immersed in the solution, and this solution contains the precursor of the conjugated polymer of conduction, and solution soaks in the paper feed then, then paper is heat-treated consequently and form polymer on the paper surface.
The disclosed number of patent application 19826800 of Germany discloses a kind of safety paper, and it contains the shaft-like pigment or the transparent polymer of conduction.By they being added in the batching in the paper machine headbox, described pigment or polymer can be sneaked in the paper, thereby it is evenly distributed in paper pulp.
Proposed a kind of wallpaper in EP patent application publication number 1139710, it can be protected from the radiation magnetic radiation.Described wallpaper is to make by the mixture coating wallpaper with the additive component that contains matrix polymer, conducting polymer and mix with it.
In known paper products, polymer phase is worked as loosely attached on the fibre substrate.When polymer mixed with fibre machinery, polymer was faint with being connected of fiber because polymer normally hydrophobic and fiber is hydrophilic.Immersed precursor in the paper by polymerization, above fiber, because only there is a spot of precursor to be penetrated in the fibre substrate that paper made, this is meant that polymerization occurs in the surface of fibre substrate with the polymer major sedimentary.Moreover when paper scribbled one deck and contains the coating of conducting polymer, this conducting polymer was not directly to combine with cellulose fibre but combine with matrix polymer, thus conducting polymer still is positioned at the surperficial of product and with coating color from wherein discharging.About the present invention, we have found that conducting polymer and cellulose fibre be firm, and to be connected for the production technology of reality and the use of product be important.From fiber, discharge recovery and recirculation that any polymer will impair aqueous recycle stream body in the paper machine, and will weaken the function of product thus soon.In addition, in process of production, preferably directly conducting polymer is introduced fibre.Therefore, consider to have only when polymer and being connected of fiber are enough firm and avoid with activation in general paper machine being reduced to detectability following time owing to cleaning cleaning polyalcohol causes electric conductivity from technological standpoint, production conductive paper or cardboard are only wisdom.
U.S. Patent number 5,211,810 disclose a kind of fried packing that can be used in micro-wave oven, and it contains the fiber that has deposited conducting polymer on fiber surface.Polymerization can strong inorganic acid, be 1N hydrochloric acid in the presence of carry out in position.The electric conductivity of the product that generates thus of fiber openly wherein.
Even this known solution shows considerable shortcoming.As the result of polymerization, the polymer of quite a few homopolymerization in solution.This homopolymers will separate from reactant mixture.Under the described situation of above-mentioned United States Patent (USP), the inorganic acid of low pH can further be harmful to the character of cellulose fiber peacekeeping lignocellulose fiber.Therefore, acid for example can change the amorphous region of fiber.When pH is lower than 2, the intensity of fibre will significantly reduce.Low pH will make fiber angle materialization, and the water-retaining property of infringement fiber.This cornified fiber also needs many a lot of energy that beat.Fiber also can be harder.Low pH handles and almost is equivalent to dried fibres paper pulp.
The present invention aims to provide a kind of paper that contains conducting polymer or cardboard of newtype, and described polymer firmly is connected with network of fibers, so that it can not be cleaned basically.In the present invention, this electric conductivity that is meaning this product can be recovered, though during washing when adulterant dissolving and electric conductivity may temporarily descend the time.
According to the present invention, at paper machine or make in the board machine before natural fabric by free porous forms fiber web, the natural fabric of polymer with the porous of dissociating is connected.Said composition can be according to following method production: porous fibre is closely contacted with conducting polymer, make conducting polymer be connected on the fiber then, thereby obtain fiber composition, wherein polymer firmly is connected with fiber, so that it can not be washed by water basically.If desired, this fiber composition is recovered.
In the methods of the invention, be aggregated in the porous fibre " original position " of conducting polymer carries out.To treat that at first the monomer of polymerization and the adulterant of conducting polymer soak into porous fibre, allow their salifies then.Add catalyst or oxidant that polymerisation is taken place afterwards, make the doping monomer in fiber with fiber surface on polymerization and monomer is connected with fiber.Crucially to the present invention be, employed adulterant is an organic sulfonic acid, at first allow it be impregnated in the pending fiber, will add in the reactant mixture corresponding to the monomer of polymer then, this monomer carries out polymerization and is connected with fiber surface, especially fibrous inside.
More specifically, the inventive method is characterised in that claim 1 characteristic is described.
Obtained sizable advantage by the present invention.Therefore, made a kind of mixture that forms conductive network in paper and the cardboard that is used in by the present invention.By the quantity of adjusting conducting polymer, the conductivity level that can obtain to select, for example scope is 10
4-10
11Ohm/side, normally 10
4-10
8Ohm/side.When square resistance is equal to or less than 10
8The time, can be easily with product and the difference of non-conductive product.By conductive network being introduced paper or cardboard, according to its conductivity degree, can obtain the function of number of different types, these functions and antistatic application, to enter identification data, safety label etc. relevant.
Particularly, the invention provides a kind of fibre with electric conductivity, its electric conductivity is long-term to be kept and reservation, and electric conductivity is also good in lead.For described fibroreticulate composition and production, only there is a spot of non-adhesive polymer to be transferred in the discarded recirculated water respectively.
When for example in the paper machine headbox, when described conducting polymer firmly is connected with fiber, polymer become smooth and equably molecule in whole paper batching.This has following advantage: use than polymer to be present in, for example the polymer that is present in less amount under the situation in the fiber with the form of disperseing just can obtain suitable electric conductivity.Shown in following embodiment, can obtain about 10 by the polyaniline of 10 weight % (in the paper pulp) altogether
4The satisfactory electrical conductivity of ohm.
Patent application publication number EP0783015 discloses the microfiber that has applied polypyrrole.The size of this kind fiber is normally 2-30 nanometer of micron order and its diameter.But according to the present invention, microfiber is not the fiber of modification, but natural fabric, i.e. " string ", for example cellulose fibre or lignocellulose fiber.The structure of this fibrid generally includes that its length generally is about 3mm in five kinds of different parietal layers and the cork.Parietal layer contains lignin, hemicellulose and cellulose.In these components, cellulosic molecule is bonded to each other by hydrogen bond, forms short microfiber, and it is not formed bundle successively and is formed in the various fiber parietal layers fiber with different direction orientations.In the present invention, conducting polymer is in the infiltrated fiber.
Can use the fiber and the wood fibre of the modification according to the present invention equally, in other words, they can be recovered, dry and mix with other host material, perhaps need not separate and reclaim described fiber, can form fiber web by the slurries that contain these fibers.Conductive fiber can make up with different types of fibre such as paper, cardboard, fiberboard (as MDF-and HDF-plate) and other stampings such as pressing mold.This can be used for the manufacturing of composite, for example with thermoplastic and cold solidity plastics and with inorganic filler and construction material combination.According to the present invention, for example may make thus can be by the building panel of electrical measurement evaluation.
The pH of fiber dispersion need not be reduced to less than 2, also can be to conducting polymer organic adulterant that mixes.Can avoid the durability of the thin plate of fiber angle materialization and formation to descend like this.In addition, can select organic acid, particularly aromatic sulphonic acid according to pending fiber, so conducting polymer can be incorporated on the fiber.
To under the help of detailed description and a few thing embodiment, more carefully check the present invention below.
In an embodiment, describe with reference to the accompanying drawings, accompanying drawing comprises the micrograph of the cross section that has wherein presented the fiber that polyaniline handles, as we know from the figure, and polyaniline infiltrated fiber inside how in the presence of different equilibrium ions.
Fig. 1 and 2 has shown the cross section of the fiber of handling with the polyaniline of mixed toluenesulfonic acid (TSA), amplifies 200 times (Fig. 1) respectively and amplifies 500 times.
Fig. 3 and 4 shown mixed DBSA (DBSA) polyaniline corresponding microphoto and
Fig. 5 and 6 has shown the microphoto of the polyaniline of mixed hydrochloric acid (counter-example).
Fiber composition of the present invention comprises a kind of substrate, and this substrate is comprised of the porous natural fiber with coupled conducting polymer. As mentioned above, the concentration of conducting polymer should be enough to make the resistivity (surface resistivity) of this substrate to reduce to 1011Ohm preferably is lower than this value, most preferably reduces to 108Ohm is if need to even be reduced to 104Ohm. Therefore, with respect to the amount of fiber, can add about 0.1-150 % by weight, preferably the polymer of about 1-100 % by weight. Preferably, the 5-70% of the amount fibrous material gross weight of conducting polymer, most preferably from about 7.5-50%.
According to the present invention, in one way polymer is connected to by consequently it can not be cleaned basically in the fibrous substrate. Therefore, they are for example at paper machine or make in the short recirculated water of lap machine and can not be cleaned.
Usually, suppose in this solution that the electric conductivity that contains the fiber of conducting polymer can remain essentially in original level after washing, even cause the equilibrium ion of polymer to be cleaned owing to washing. Preferably, in most of the cases the electric conductivity of conducting polymer can remain on than 30 times level (being that surface resistivity has enlarged 30 times) a little less than the original level. In order to keep electric conductivity, can use identical equilibrium ion or some other materials, described in detail as follows.
Generally, clean each time at 25 ℃ of lower water with pH 7 ± 3 and wash maximum about 20 % by weight, preferably less than about 10 % by weight, even less than the conducting polymer of about 5 % by weight. In washing, the immersion fiber also is mixed in the water of above-mentioned pH and temperature conditions, after about 10 minutes, gets rid of water, and fiber is separately also dry.
According to adulterant and rigid condition and because the cleaning of adulterant goes out, for each cleaning, electric conductivity (surface resistivity) 4-8 the order of magnitude that can descend for example after 6 cleanings of water, drops to 104-10
8Ohm.
The electric conductivity of fiber can be determined by following method: forms a uniform fibrage by fibrous suspension, then by the vacuum filtration wipe dry and measure front under the temperature of 50 ℃ of maximums dried fibres layer (referring to the following examples 7 and 8). Electric conductivity can also be by being measured by the scraps of paper of standard method (for example SCAN C26:76) preparation.
For the conducting polymer that obtains to be connected so that can not to wash off with fiber, fiber should be comprised of the natural fiber of porous, and before randomly consisting of described fiber by uniform fibre substrate, the natural fiber of porous is and separates and loose fibers form. At first allow the precursor of polymer, polymerisation is carried out in the salt infiltrated fiber hole (entering fibrous inside) that is for example formed by monomer and adulterant then, thereby realizes being connected of polymer and fiber with being connected on fiber. When for example by paper machine or make lap machine with separating and loose fiber when forming fibre substrate, and comprise uniform fibrage when matrix, when for example being the Paper or cardboard form, this causes following situation: conducting polymer infiltrated fiber and most polymers is positioned at the inside of fibre substrate. Thus, polymer is evenly dispersed in the fibrage. Disperse equably to refer to change approximately 10% as the surface resistivity of the Paper or cardboard of the function of position is maximum, preferably maximumly change about 5%.
The weight that forms every square metre of net of fibre substrate is generally about 5-700g/m2, be generally about 20-500g/m2, for example be 30-150g/m2(paper) and 80-300g/m2(cardboard).
Being used for porous fibre of the present invention is cellulose fibre, lignocellulose fiber, cellulose fibres of cereal, cereal pentosan, velveteen, Luzon hemp, sisal fiber, ramee, flax fiber, reed canary grass fiber or flaxen fiber. Most preferably use cellulose pulp or the lignocellulose pulp made by fiber separation annual plant or perennial plant, for example chemical pulp or mechanical pulp or mechanochemistry paper pulp. The below is the chemical pulping method that can mention: sulfate pulp-making, continuously sulfate pulp-making, sulphite slurrying, polysulfide slurrying, organosolv pulping (for example Milox-slurrying) and soda slurrying. Most important mechanical pulp-making method is: grind (GW), press and grind (PGW), heat engine tool slurrying (TMP) and refining (RMP), and most important mechanochemistry method is CTMP and CMP method. Can be with association with pulp bleaching or do not bleach.
Used porous fibre is characterised in that it can absorb at least water corresponding to himself weight (before polymer and/or its precursor immerse fiber). Only is that used fiber can absorb the water that its weight 1.5-20 doubly measures. Usually, fiber is of a size of about 0.01-10mm. According to required dewatering efficiency, fiber usually after beaing drainability be 80-650ml CSF, be preferably about 120-560ml CSF. Fiber is " separation and loose ", and this refers to that they can processed drying be villosity. Compare with known technical scheme, wherein polymer links to each other with fabric, and the present invention has reached the uniformity of remarkable improvement.
In the present invention, " conducting polymer " or " conducting polymer " refers to the polymer (ICP) of inherent conduction, and it has been carried out " doping " (batching, processing) to produce charge carrier (hole and electronics). The common ground of all conducting polymers is conjugated double bonds (Dan Shuanjian alternately, the silicon electron system of delocalization) of skeletal chain, and this can move charge carrier. Conducting polymer has ionic conductivity and electron conduction, and this can be applied to various fields. The electric conductivity of conducting polymer can fluctuateed and adjusting to the whole conduction scope of metallic conductor by insulating materials. Usually, if the maximum resistance of polymer is 1011Ohm (as sheet resistance) thinks that then this polymer conducts electricity.
Conducting polymer can be combined with fiber with the form with non-conductive of conduction. Therefore, below term " conducting polymer " in the claim also refer to when reference it is non-conductive, but can make it become the polymer of conductive state by using suitable adulterant to process.
Polyaniline, polypyrrole, polyacetylene or polythiophene or their derivative or mixture are used as conducting polymer.In derivative, especially what deserves to be mentioned is the chlorine of alkyl and aryl derivatives and above-mentioned polymer and the derivative that bromine replaces.If desired, also can add conductive particle, for example graphite or carbon black.
Preferred especially in the present invention polyaniline.The monomer of aniline polymer is the aniline or derivatives thereof, in most of the cases the para-position carbon bonding of the phenyl ring of nitrogen-atoms wherein and next unit.Unsubstituted polyaniline can be different forms, and wherein emeraldine form (it is characterized in that the emerald green color clarified, this represents its title) often is used to the application of conducting polymer.
By mixing, electroneutral polyaniline can be transformed into the polyaniline-compound of conduction.The adulterant that uses among the present invention can change widely, and they use generally in conjugated polymer being doped to conduction or semiconductive form the time.
In the conducting polymer field, Bronsted acid is known adulterant interior, as appears in the list of references of J.-C.Chiang and Alan G.MacDiarmid and the document that W.R.Salaneck quotes:
People such as o Chiang, Synth.Metals (1986) 13:193-205
People such as o MacDiarmid are from the 6th European Physical SocietyIndustrial Workshop Eur.Phys.Soc.
People such as o Salaneck, Synth.Metals (1986) 13:291-297 is not known month.
Above-mentioned adulterant comprises organic acid and derivative thereof, and wherein typical example is sulfonic acid, picric acid, n-nitrobenzoic acid, dichloroacetic acid and polymeric acid.If desired, can use more than one adulterants.
Preferably, functional acid is used for mixing, for example sulfonic acid, especially aromatic sulphonic acid, it comprises an aromatic rings or two fused rings, and wherein at least one ring can have polarity or nonpolar cyclic substituents, for example functional group (as hydroxyl) or hydrocarbon chain, as have the alkyl chain of 1-20 carbon.The example is benzene sulfonic acid, aromatic phosphoric acid diester of alkyl-benzene sulfonic acid and dialkyl benzene sulfonic acids (wherein alkyl comprises 1-20 carbon atom), other side chain etc.
Can should be mentioned that following substances especially:
MSAs (pyrovinic acid),
Ethylsulfonic acid
BSAs (benzene sulfonic acid)
TSAs (toluenesulfonic acid)
DBSAs (DBSA)
Ethyl phenenyl azochlorosulfonate acid
PSAs (phenolsulfonic acid or hydroxy benzene sulfonic acid)
CSAs (camphorsulfonic acid)
AMPSA (2-acrylamide-1-propane sulfonic acid)
Vinyl sulfonic acid
M-phthalic acid sulfonic acid and ester
PPA (phenyl phosphinic acid)
Phosphonoacetic acid
DIOHP (two (2-ethylhexyl phosphoric acid hydrogen ester))
Phenalgin sulfonic acid
Pyridine-sulfonic acid
Aminoanisole sulfonic acid
Aniline sulfonic acid
Quinoline sulfonic acid
Naphthalene sulfonic acids
Sulfosalicylic acid
Phosphonic acids
As the example of polymeric acid can mention be at its end by the polymer of sulfonic acid functional [polystyrene (PSSA), polyolefin, poly(ethylene oxide), polyethylene], and the aromatic polyamide of the polyparaphenylene of sulfonation and sulfonation and analog.
Preferred acid is DBSA (DBSA), camphorsulfonic acid, p-methyl benzenesulfonic acid and phenolsulfonic acid.
The preparation of polyaniline compound has for example described in detail in patent application publication number EP545 729 and EP582 919 and FI932557,932578 and 940626, and the content of above-mentioned patent is introduced into herein as a reference.
According to the preferred embodiments of the invention, the adulterant of conducting polymer is selected so that the salt that is formed by conducting polymer parent material (monomer) and described adulterant dissolves in the medium that is used to be connected polymer, for example in the water.Particularly, this relates to situation about wherein conducting polymer being connected in the fiber of being produced by chemical pulping.
When pending fiber comprises lignin,, also can use to have surface-activity and/or hydrophobic adulterant even when the salt that is formed by adulterant and conducting polymer parent material is slightly soluble in semi-commercial (semiworks) production.This fibrid is the lignocellulose fiber that is obtained by machinery pulping.That can mention as the example of adulterant is DBSA (DBSA).
Oxidant is generally used for monomeric compound is aggregated in the reaction of corresponding conducting polymer.Preferred oxide is polyatom slaine such as iron (III) salt and mistake-compound, as peroxide, peracid, persulfate, perborate, permanganate, perchlorate and chlorate, nitrate and quinones.The ratio of oxidant and monomer is generally 10: 1-1: 1, most preferably from about 5: 1-2: 1 (weight portion) or 4: 1-1: 1 (molar fraction) (oxidant/monomer).
Polyaniline can be connected with the fiber of conduction form and non-conductive form.Polyaniline must be balanced ion doping makes it change the conduction form into.Especially preferably the fiber of polyaniline with the conduction form is connected, because it is contemplated that under the help of adulterant, combination takes place polyaniline at least in part, this will be described in greater detail below.
The resistivity of fiber composition manufactured according to the present invention is generally about 50-10
8Ohm.
Described product can especially in the water-bearing media, make porous fibre closely contact with the monomer that forms conducting polymer and prepare by at suitable medium.Except water and aqueous solution, can also use organically, polarity and non-polar solven." closely contact " is meant that the meticulous slurries that will comprise fiber and polymer monomer precursor and/or polymer-doped dose firmly mix, and obtain the monomer and/or the adulterant that effectively distribute in fibrous material.Therefore, " water-bearing media " represents the water and the aqueous solution, and fiber is pulp therein.Usually, the denseness of aqueous slurry is 0.1-50% (w/w), is preferably about 0.5-30%, particularly about 0.7-20%.After this, equilibrium ion or treat that the monomer of the conduction reagent of polymerization is dissolved in aqueous phase respectively.The amount of adulterant changes with the amount of monomer.Usually, the amount of monomer is the amount of 0.1-200% fiber, is generally about 1-150 weight %, is preferably about 5-120 weight %, particularly about 10-100 weight %.Usually, the amount of equilibrium ion can with mole such as the amount of monomer, but it can also be about monomer molar amount ± 30%.
Temperature is generally greater than 0 ℃ but is lower than room temperature.Usually, temperature is about 1-18 ℃, is preferably about 2-15 ℃.
Usually, use acid equilibrium ion, and the pH of employed water most suitably is absolutely clear acidity in the pairing of fiber and polymer/monomer, preferred pH is lower than 5 and most preferably greater than 2.Too low pH value can influence the engineering properties of fiber unfriendly, and Here it is, and why preferred pH environment is about 2-5, and optimum is the reason of 2-3.
As mentioned above, according to the present invention, at first the aggregation (compound or salt) of monomer and adulterant formation is introduced fiber, after this monomer polymerization is so that polymer is connected in such a way with fiber, and consequently polymer can not be washed off under system paper conditions needed.Porous fibre and conducting polymer can improve by the consideration following characteristics to the affinity that mutually combines respectively:
A) type of equilibrium ion
B) dissolubility of monomer and salt that equilibrium ion forms
C) concentration of monomer and equilibrium ion and
D) type of fiber.
Back one project was discussed in front: in order to increase the affinity that mutually combines between porous fibre and the conducting polymer, in containing the water-bearing media of porous fibre, carry out polymerisation, so that the polymer that forms is connected with porous fibre by polymerisation.Usually, at first allow monomer and the adulterant waiting to be aggregated in the conducting polymer react to each other, in aqueous solution, form salt or compound, make it contact and allow its infiltrated fiber with porous fibre then.After this, allow monomer polymerization in fiber, obtain homodisperse polymer in paper pulp.The reaction of monomer and polyalcohol catalyst can be carried out in the presence of fiber.Even can before adding monomer, add adulterant, it was absorbed in the fiber before monomer.By this solution, can further improve being connected of the connection of monomer and polymer and fiber.
When selecting adulterant, be intended to reach following situation: the affinity that mutually combines of porous fibre and conducting polymer is strong as much as possible.In the present invention, have been found that the surface of the selection of adulterant being depended on cellulose fibre.According to an embodiment preferred, increase the affinity that mutually combines of porous fibre and conducting polymer by the fiber of selecting its surface to cover lignin at least in part.Thus, this is meant machinery or the mechanical-chemical paper pulp fiber that for example has lamination intermediate layer lignin on the surface.Known lignin contains phenyl and phenol structure, therefore observes preferred dopant and has the hydrophobic aliphatic hydrocarbon structure of this adulterant of increasing.In the test of having implemented, have been found that by using DBSA or similar compounds polyaniline is reasonably well combined with the mechanical pulp fiber as adulterant." similar compounds " is meant to have more than 4 and preferably have the alkyl of about 5-20 carbon atom or the compound that the dialkyl group side chain links to each other with aromatic group.Obviously this will increase combination by arrange at mating surface adjacent aliphatic hydrocarbon and aromatic hydrocarbon.
Among the embodiment that provides below, can also use conventional chemical pulp (by the bleached softwood cellulose of sulfate process shortening).Have a large amount of aliphatic anhydrohexoses or dehydration pentose chain on the surface of this kind paper pulp, it is from cellulose or hemicellulose, and these chains have common aliphatic characteristic.In order to improve their combination, advantageously use the adulterant more hydrophilic than alkyl benzene sulphonate, promptly a kind of at the most low alkyl group is as the substituent reagent of aromatic rings.On the contrary, this ring can contain increases the hydrophilic functionalized group of this material.In view of the above, P-TOLUENE SULFO ACID 99 and analog thereof are especially preferred above-mentioned adulterants.As if under this kind situation, adjacent aliphatic structure and aromatic hydrocarbon structure form on the binding site of adulterant and fiber for this.
According to the present invention, conductive cellulose and lignocellulose fiber advantageously are used to the production of conductive paper or paperboard products.Can produce recycled fiber afterwards, drying also is used for required Application Areas or is re-used as the suspension utilization with dried forms subsequently., after handling, can further transmitting fiber tow be passed in the manufacturing of paper or cardboard according to the present invention.Then, conveying fiber the most sufficiently in water-containing pulp, and for example in the paper machine headbox with them and other mixed with fibers.Key is by with fiber of the present invention and the conventional plant mixed with fibers that does not contain the electrically conductive composition component, has obtained a kind of conductive fiber composition, and it contains homodisperse conductive component.Generally speaking, the addition of fiber of the present invention is about 1-50 weight % of fibre dry matter, preferably about 2-30 weight %.When by paper machine or when making board machine and producing product, obtained the fibre substrate that conducting polymer distributes very equably.
The product that makes can be applicable to the ESD application or is used to make safety label.
Following embodiment illustrates the present invention.They have indicated the more detailed details of the preferred embodiment of the invention.
The embodiment general introduction
In this work, used different equilibrium ions, in the pine and cypress cellulose fibre of pulverizing, carry out aniline polymerization.The purpose of this work mainly is by polymerization polyaniline to be connected on the fiber surface, after this produces the conductive fiber paper that has adsorbed polyaniline.
The parent material that uses in this work is the softwood cellulose slurry (TKK, Technical University of Helsinki) of water, aniline, DBSA (A), p-methyl benzenesulfonic acid (B), citric acid (C), ammonium persulfate (Degussa) and pulverizing.In the glass marble of 5L, implement this work, wherein in ice-water bath, cool off this glass marble, so that during entire reaction, make the temperature of exothermic reaction keep stable with emulsion polymerization way.Three kinds of equilibrium ions for all carry out polymerization in the same way.
As a comparison, also use hydrochloric acid as equilibrium ion.
Adding denseness in water is the slurries of 5-30%, to form 1% mixture (for example, in the 3000g water 30g fiber being arranged) about fiber.Then, (A, B or C) is dissolved in wherein with equilibrium ion, and its consumption is the molar weight corresponding with the aniline amount.Add then fibre weight 10-100 weight % aniline (for example, 3g).Next, this mixture is cooled to below 10 ℃.The APS-aqueous solution (7.4%) is used as 1.03 times corresponding to the aniline molar weight of oxidant and APS consumption.After this, in about 3 hours, described oxidant is progressively added in the mixture, be elevated to room temperature with the relief temperature.
Paper pulp in the mixture of being made up of polyaniline, chemical paper fiber and water by centrifugation extrudes water then.Once and centrifugal once more wash product pulp in water off residual APS-salt this moment.The product of finishing and cleaning is delivered to TKK be used for paper production.The dry fiber that filters on filter paper and the surface resistivity of those fibers are as follows:
PAN-DBSA 100% fibre weight: 10
3Ohm
PAN-DBSA 10% fibre weight: 10
4Ohm
PAN-TSA 10% fibre weight: 10
7Ohm
PAN-TSA 25% fibre weight: 10
4Ohm
PAN-TSA 50% fibre weight: 10
5Ohm
PAN-citric acid 10% fibre weight: 10
5-11Ohm
(PAN=polyaniline)
Appended microphoto has shown the cross-sectional view of the fiber that PAN handles, i.e. the polyaniline inside of infiltrated fiber how in the presence of the different equilibrium ions.Fig. 1,3 and 5 is toluenesulfonic acid (TSA) and DBSA (DBSA) as equilibrium ion and HCl 200 times of enlarged drawings as counter-example.Fig. 2,4 and 6 is respectively 500 times of enlarged drawings.
Observe following situation by figure: when PAN be positioned at the surface and partly as fiber between during particle, DBSA and aniline form water-fast salt.TSA has infiltrated in the fibre structure well as soluble aniline salt.HCl also forms soluble salt, but PAN is positioned at fiber surface as hyaline layer.In fact, at fibrous inside, promptly almost be difficult to see any PAN that contains any equilibrium ion in the inner chamber.Therefore, can think that with outside the fiber angle materialization, when organic adulterant makes polyaniline can be in the fibrous inside polymerization time, polyaniline is retained in the surface of fiber as strength hydrochloric acid except inorganic acid.As a result, polyaniline is retained in the fiber better, even when mechanical erosion is pointed to them.
Measure surface resistivity (VTT) by the equipment of measuring two resistance between the parallel metal bar, every long 6.5cm of described rod and being put on the surface of sample.Described excellent space 4cm.Less than 10
5In the scope of ohm, be 10V, greater than 10 in the measuring voltage of conductive region
5In the zone of ohm, be 100V in the measuring voltage of conductive region.
Because the mechanism that keeps between equilibrium ion and the fiber and cause the mechanism of this situation still unclear in this case, therefore wood fibre and the TMP/GW-fiber for chemical paper fiber and TMP substandard products carried out more polymerization.Except phenolsulfonic acid (PSA), camphorsulfonic acid (CSA) and Loprazolam (MSA) are used as the equilibrium ion, these polymerizations are according to carrying out with the corresponding mode of aforementioned polymerization.By filtering wash products and water elutriation once more.For filtration, directly prepare filter cake by reactant mixture and after cleaning with the 6th time for the third time.Wash products is elevated to greater than 6 until pH.By dried filter cake meter surface resistivity, and take out sample, being connected in KCl with optics microscopic analysis polymer and fiber from slurries.In annex II, provided displaing micro picture.The summary of using different equilibrium ions and fiber to handle is listed in the Table I.
Table I. do not contain wooden with contain wooden fiber in the presence of contain the polymerization of the aniline of different equilibrium ions
| Wood fibre: TMP substandard products or TMP/GW-fiber | |||||
| DBSA Tmp | TSA Tmp | PSA Tmp (tmp/gw) | PSA Tmp | MSA Tmp/gw | |
| Aniline salt | Solid | Water miscible | Water miscible | Water miscible | Water miscible |
| Color reaction is to green | 2-4h | ＞12h | 10min-＞1h (10-50min) | 4-6h | 3-8h |
| The concentration of aniline | 0.25％ | 0.08％ | 0.17％ (0.25％) | 0.18％ | 0.5％ |
| Initial pH | 2 | 2 | 2.57 | ||
| Clean to＞pH6 | 9 | 8 | 6 | 6 | 7 |
| The resistivity of initial filter cake, Ω | 10 4 | 10 4 | 10 4 (10 3) | 10 5 | 10 3 |
| Clean the resistivity after 3 times, Ω | 10 4 | 10 4...10 6 (10 4) | 10 7 | 10 5 | |
| Clean the resistivity after 6 times, Ω | 10 5 | 10 8 | 10 7 (10 5...10 6) | 10 12 | 10 6...10 7 |
| Be connected with fiber * | 2...3 | 2 | 2(1) | 2 | 2 |
| Chemical paper fiber | |||||
| Color reaction is to green | 3h | 4h | 3h | 4h | 6h |
| The concentration of aniline | 0.13％ | 0.32％ | 0.25％ | 0.25％ | 0.25％ |
| Initial pH | 1.66 | 1.83 | 1.71 | 2.9 | |
| Clean to＞pH6 | 5 | 12 | 10 | 8 | 7 |
| The resistivity of initial filter cake, Ω | 10 4...10 5 | 10 4 | 10 4 | 10 4 | 10 4 |
| Clean the resistivity after 3 times, Ω | 10 4 | 10 5 | 10 6 | 10 6 | |
| Clean the resistivity after 6 times, Ω | 10 12 | 10 5 | 10 7 | 10 7 | 10 9 |
| Be connected with fiber * | 3...4 | 1 | 1 | 1 | 1 |
*Use microscopic to estimate and being connected of fiber: 1=is at fibrous inside, and the 2=part is in fiber, and 3=connects from the teeth outwards, and the 4=polymer is loose and be positioned at the centre
In Table I, the listed reaction, also carried out using the reaction of sulfuric acid as equilibrium ion.When the reaction that realized with water-insoluble and aniline salt that can be water-soluble, two kinds of reactions that different aniline-equilibrium ion concentration is carried out have been implemented to use.
Table II. in the presence of fiber, in reactant mixture, use sulfuric acid (H
2SO
4) carry out the polymerization of aniline as equilibrium ion
| The TMP/GW-fiber | Chemical paper fiber | Chemical paper fiber | |
| Aniline salt | Water-soluble | Water-soluble | Solid |
| Color reaction is to green | The 2h yellow-＞green | 1.5h blue-＞green | 10 minutes |
| Aniline concentration | 0.25％ | 0.25％ | 13％ |
| Initial pH | 2.85 | 2.88 | 2.08 |
| Clean to＞pH6 | 9 | 9 | 17 |
| The resistivity of initial filter cake, Ω | 10 4 | 10 4 | 10 3 |
| Clean the resistivity after 3 times, Ω | 10 5 | 10 5 | 10 3 |
| Clean the resistivity after 6 times, Ω | 10 7 | 10 7 | 10 4 |
| Be connected with fiber * | 2 and 4 | 1 | 1 and 3, on inside and surface |
*Use microscopic to estimate and being connected of fiber: 1=is at fibrous inside, and the 2=part is in fiber, and 3=connects from the teeth outwards, and the 4=polymer is loose and be positioned at the centre
According to the reaction and display of Table II the solubility of salt also can be depending on salinity.The purpose of test is in order to confirm that water-insoluble aniline-equilibrium ion salt is not connected with fiber and soluble salt.But this demonstration has been failed, because compare with pending chemical paper fiber, amount that can not dissolved salt is more than 10 times.In other reaction, used the aniline that exceeds fibre weight 25% at most.This causes following situation: it is complicated having too many polyaniline so that it is washed from fiber.In addition, before aniline polymerization, the sulfuric acid of high concentration can change the structure of fiber.
In the connection embodiment of Table I, only the DBSA aniline salt is water-insoluble and is low concentration.Because its macromolecular structure and surface-active property solid-state and dodecyl sodium sulfonate (DBSA), the infiltration of polyaniline in chemical paper fiber is faint.In turn, wood fibre also comprises the active group of number of different types, is connected with these active groups to be easier to, even for long-chain DBSA.
About water-soluble aniline-equilibrium ion, with being connected and all being easier to of fiber by the water infiltrated fiber.In addition, it is easier than infiltrating wood fibre to infiltrate chemical paper fiber, and this is because the chemistry and the physical nature of lignin.
Only when polyaniline and mixed with fibers (embodiment 13, and wherein the polyaniline of 25% fibre weight mixes with chemical paper fiber), polyaniline is less than in the infiltrated fiber suitably.Therefore, the mixture during with preparation polyaniline in the presence of fiber is compared, and polyaniline is easier significantly to wash from fiber.
The electric conductivity of conductive fiber product can be subjected to the selection (water-soluble/solid, size and the shape of equilibrium ion) of fiber type (cellulose slurry or woody pulp), equilibrium ion, with respect to the influence of the aniline-equilibrium ion amount of fibre weight, and under the situation of slightly soluble salt, be subjected to the influence of salinity in the reactant mixture.In post processing, thereby water-washed away when causing the agent of product dedoping when the partial equilibrium ion, mainly be subjected to the influence of the amount and the wash number of used rinse water.
Preparation embodiment
Embodiment 1 is polymerization aniline in the presence of chemical paper fiber, and wherein DBSA is used as equilibrium ion.The amount of aniline equals the amount of fiber.
1500ml water adds in the flask altogether, adds the 52.5g DBSA then.Next, allow DBSA be dissolved in the water, after this adding 1015g does not have wooden slurries.This does not have the every 1000g water of wooden slurries and contains 15g pine and cypress chemical paper fiber.After 15 minutes, add 15g aniline.Aniline and DBSA mixed 30 minutes and form water-insoluble salt.Cooling this mixture to temperature is 12 ℃ in ice-water bath.Then, the 36.8g ammonium persulfate is dissolved in the 200ml water, this solution is added in the mixture with 3 hours.After add ammonium persulfate, mixed continuously 2.5 hours, obtain very dark green, almost the water slurry of the chemical paper fiber-polyaniline of black.From product, remove reaction water by centrifugal, and it is eluriated in water once more, obtain having the suspension of about 7.4% dry.The surface resistivity that contains with respect to the chemical paper fiber of fiber 100% polyaniline is 10
3Ohm.This product is delivered to TKK to test in paper production.
Embodiment 2 is polymerization aniline in the presence of chemical paper fiber, and wherein DBSA is used as equilibrium ion.The amount of aniline equal fiber amount 10%.
400ml water adds in the flask altogether, adds the 5.25g DBSA then.Next, allow DBSA be dissolved in the water, after this add 1.5g aniline.Aniline and DBSA mixed 15 minutes and form water-insoluble salt.The cold dispersion chemistry pine slurries of 983.3g that in mixture, add pH5.5.This does not have every liter of slurries of wooden slurries and contains the 15g fiber.Cooling this mixture to temperature is 8 ℃ in ice-water bath.Then, the 3.7g ammonium persulfate is dissolved in the 50ml water, this solution is added in the mixture with 1.5 hours.Add after the ammonium persulfate, mixed continuously 5 hours, obtain very dark green, almost the water slurry of the chemical paper fiber-polyaniline of black.From product, remove reaction water by centrifugal, and it is eluriated in water once more, obtain having the suspension of about 1.6% dry.The surface resistivity of having cleaned once and having contained the chemical paper fiber of 10% polyaniline of having an appointment is 10
4Ohm.This product is delivered to TKK to test in paper production.
Embodiment 3 is polymerization aniline in the presence of chemical paper fiber, and wherein DBSA is used as equilibrium ion.The amount of aniline equal fiber amount 10%.Before adding equilibrium ion, add fiber.
500g water adds in the flask altogether, adds the chemical pine slurries of the cold dispersion of 1000g then.The every 1000g slurries of these slurries contain the 15g fiber.Add the 5.3g DBSA then and make its dissolving 10 minutes.After this add 1.5g aniline and form water-insoluble, white aniline-dodecyl benzene sulfonate at this moment.Cooling this mixture to temperature is 8 ℃ in ice-water bath.Then, the 3.7g ammonium persulfate is dissolved in the 50ml water, this solution is added in the mixture with 1.5 hours.Add after the ammonium persulfate, mixed continuously 4 hours, obtain very dark green, almost the water slurry of the chemical paper fiber-polyaniline of black.From product, remove reaction water by centrifugal, and it is eluriated in water once more, obtain having the suspension of about 1.6% dry.The surface resistivity of having cleaned once and having contained the chemical paper fiber of 10% polyaniline of having an appointment is 10
4Ohm.
Embodiment 4 is polymerization aniline in the presence of chemical paper fiber, and wherein DBSA is used as equilibrium ion.The amount of aniline equals the amount of 10% fiber.Diluted reaction mixture more.
2780g water adds in the flask altogether, adds the chemical pine slurries of the cold dispersion of 300g then.The every 100g slurries of these slurries contain the 10g fiber.Add the 10.5g DBSA then and make its dissolving 20 minutes.After this add 3g aniline, form water-insoluble, white aniline-dodecyl benzene sulfonate this moment.Cooling this mixture to temperature is 11 ℃ in ice-water bath.Then, the 7.4g ammonium persulfate is dissolved in the 100ml water, this solution is added in the mixture with 2.5 hours.Add after the ammonium persulfate, mixed continuously 5 hours, obtain very dark green, almost the water slurry of the chemical paper fiber-polyaniline of black.From product, remove reaction water by centrifugal, and it is eluriated in water once more, obtain having the suspension of about 2.3% dry.At TKK, contain the scraps of paper of the processing cellulose slurries of different amounts by the chemical paper fiber preparation that comprises 10% polyaniline.
Embodiment 5 is polymerization aniline in the presence of chemical paper fiber, and wherein p-methyl benzenesulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 10%.
1970g water adds in the flask altogether, and the pine that adds the cold dispersion of 295g does not then have wooden slurries.The every 100g slurries of these slurries contain the 10g fiber.Add the 6.13g p-methyl benzenesulfonic acid then and make its dissolving 50 minutes.After this add 3g aniline, form water-soluble aniline-tosilate this moment, and this mixture slightly brown that becomes.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, the 7.4g ammonium persulfate is dissolved in the 100ml water, this solution is added in the mixture with 1 hour.Add after the ammonium persulfate, mix continuously also to place in 5 hours and spend the night, obtain the almost water slurry of black, virellous chemical paper fiber-polyaniline.By the centrifugal reaction water of from product, removing.Product is filtered cleaning once and with it in water, eluriate once more, obtain having the suspension of about 7.1% dry.Contain 10% polyaniline and be 10 of having an appointment by the surface resistivity of filtering the scraps of paper that chemical paper fiber makes
7Ohm.At TKK, contain the scraps of paper of the processing cellulose slurries of different amounts by described product preparation.
Embodiment 6 is polymerization aniline in the presence of chemical paper fiber, and wherein citric acid is used as equilibrium ion.The amount of aniline equals the amount of 10% fiber.
1970g water adds in the flask altogether, and the pine that adds the cold dispersion of 294.8g does not then have wooden slurries.The every 100g slurries of these slurries contain the 10g fiber.Add the 6.19g citric acid then and make its dissolving 40 minutes.After this add 3g aniline, form water-soluble aniline-citrate this moment.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, the 7.4g ammonium persulfate is dissolved in the water (100ml), this solution is added in the mixture with 1.5 hours.Add after the ammonium persulfate, mixed continuously 6 hours, obtain the brown product.With this mixture place spend the night after, obtain the water slurry of the chemical paper fiber-polyaniline of black.By the centrifugal reaction water of from product, removing.Product is eluriated in water once more, obtained having the suspension of about 6.1% dry.Contain 10% polyaniline and be 10 of having an appointment by the surface resistivity of filtering the scraps of paper that chemical paper fiber makes
5Ohm.At TKK, contain the scraps of paper of the processing cellulose slurries of different amounts by described product preparation.
Embodiment 7 is polymerization aniline in the presence of chemical paper fiber, and wherein p-methyl benzenesulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
1700g water adds in the flask altogether, and the pine that adds the cold dispersion of 300g does not then have wooden slurries.The every 100g slurries of these slurries contain the 10g fiber.Add the 15.3g p-methyl benzenesulfonic acid then and make its dissolving 15 minutes.After this add 0.02g phenyl diamines, mixed subsequently 15 minutes.Then, add 7.5g aniline.Form water-soluble aniline-tosilate, and this mixture slightly brown that becomes.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, ammonium persulfate (18.5g) is dissolved in the 200ml water, this solution is added in the mixture with 1 hour.Add after the ammonium persulfate, mixed continuously 3 hours, place then and spend the night, obtain the almost water slurry of black, virellous chemical paper fiber-polyaniline.By the centrifugal reaction water of from product, removing.Product is filtered cleaning once, and this moment, the pH of rinse water was 2.0.Described product is eluriated in water once more, obtained having the suspension of about 5.5% dry.Contain 25% polyaniline and be 10 of having an appointment by the surface resistivity of filtering the scraps of paper that chemical paper fiber makes
4Ohm.At TKK, contain the scraps of paper of the processing cellulose slurries of different amounts by described product preparation.
Embodiment 8 is polymerization aniline in the presence of chemical paper fiber, and wherein p-methyl benzenesulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 50%.
1700g water adds in the flask altogether, and the pine that adds the cold dispersion of 300g does not then have wooden slurries.The every 100g slurries of these slurries contain the 10g fiber.Add the 30.6g p-methyl benzenesulfonic acid then and make its dissolving 15 minutes.After this add 0.04g phenyl diamines, mixed subsequently 15 minutes.Then, add 15g aniline.Form water-soluble aniline-tosilate, and this mixture slightly brown that becomes.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, ammonium persulfate (37g) is dissolved in the 400ml water, this solution is added in the mixture with 2 hours.Add after the ammonium persulfate, mixed continuously 2 hours, place then and spend the night, obtain the almost water slurry of black, virellous chemical paper fiber-polyaniline.By the centrifugal reaction water (pH=1.3) of from product, removing.Product is filtered cleaning once, and this moment, the pH of rinse water was 1.7.Described product is eluriated in water once more, obtained having the suspension of about 7.0% dry.Contain 50% polyaniline and be 10 of having an appointment by the surface resistivity of filtering the scraps of paper that chemical paper fiber makes
3Ohm.At TKK, contain the scraps of paper of the processing cellulose slurries of different amounts by described product preparation.
Embodiment 9 is polymerization aniline in the presence of chemical paper fiber, and wherein p-methyl benzenesulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
2400g wood fibre slurries (TMP substandard products) add in the flask altogether, and per 1 premium on currency of this fiber slurry has closed the 4.27g fiber, promptly contains the 20g fiber altogether.Add the 10.2g p-methyl benzenesulfonic acid then and make its dissolving 25 minutes.After this add 5g aniline. form water-soluble aniline-tosilate, and this mixture becomes glassy yellow.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, the 14.7g ammonium persulfate is dissolved in the 150ml water, this solution is added in the mixture with 3.5 hours.Add after the ammonium persulfate, mixed continuously 2 hours, this mixture is placed spent the night then.During this period, golden fiber appears in the brown solution of product.Product refrigeration is placed, and almost black, virellous mixture appear in reaction gradually in about 1 week.By the centrifugal reaction water of from product, removing.Product water (rinse water pH is 1.7) is cleaned once.To make surface resistivity be 10 by filtering a part of product
4The scraps of paper of ohm.In addition, with described product cleaning 8 times, how to separate with fiber surface with the observation polyaniline.The pH of the 8th rinse water is 6.3, is 10 by the surface resistivity of filtering the scraps of paper that product thus makes
9Ohm.Produced the microphoto of the treated fiber after cleaning and clean for the 8th time for the 1st time.
Embodiment 10 is polymerization aniline in the presence of chemical paper fiber, and wherein p-methyl benzenesulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
The no wood fibre slurries that the dispersion that 200g is cold altogether is wooden add in the flask, and this fiber slurry contains 20g pine fiber.Then 1400g water is added in the slurries.In mixture, add altogether the 10.22g p-methyl benzenesulfonic acid and make its dissolving 15 minutes.After this add 5g aniline, form water-soluble aniline-tosilate this moment.Under agitation, cooling this mixture to temperature is 10 ℃ in ice-water bath.Then, the 12.9g ammonium persulfate is dissolved in the 120ml water, this solution is added in the mixture with 1 hour 15 minutes.Add after the ammonium persulfate, mixed continuously 3.5 hours, this mixture is placed spent the night then.Obtain black, virellous reactant mixture.By the centrifugal reaction water of from product, removing.Product water (rinse water pH is 1.8) is cleaned once.To make surface resistivity be 10 by filtering a part of fiber
4The scraps of paper of ohm.In addition, with described product cleaning 10 times, how to separate with fiber surface with the observation polyaniline.The pH of the 10th rinse water is 5.0, is 10 by the surface resistivity of filtering the scraps of paper that respective fiber makes
6Ohm.After this, make fiber remove adulterant yesterday by adding 2% ammonia spirit and allowing fiber place.Elimination ammonia spirit and water clean fiber once, and do not have electric conductivity by the scraps of paper that the fiber after filtering makes this moment.In the slurries (about 10g) of remnants, add the H of 30ml0.2M altogether
2SO
4, and allow its placement spend the night.The surface resistivity of the scraps of paper that make by the fiber that filters new doping is 10
5Ohm.The fiber that removes adulterant of processing after the 1st time is cleaned and clean for the 10th time and the microphoto of the fiber that mixes have again been produced.
Embodiment 11 is polymerization aniline in the presence of chemical paper fiber, and wherein DBSA is used as equilibrium ion.The amount of aniline equal fiber amount 20%.
The dispersion chemical pulp that 100g is cold is altogether added in the flask, and this paper pulp contains the 10g fiber.Add the 7.0g DBSA then and make its dissolving 1 hour.Afterwards, add 2.0g aniline, form water-insoluble white aniline-dodecyl benzene sulfonate this moment.Under agitation, cooling this mixture to temperature is 7 ℃ in ice-water bath.Then, the 5.15g ammonium persulfate is dissolved in the 60ml water, this solution is added in the mixture, be very light blueness with afterproduct with 0.5 hour.Add after the ammonium persulfate, mixed continuously 5 hours, reaction reaches its terminal point and product is very dark green during this.Again reactant mixture is placed and spent the night.By the centrifugal reaction water of from product, removing.The product water is cleaned once.To make surface resistivity be 10 by filtering this product of a part
4-5The scraps of paper of ohm.In addition, with described product cleaning 5 times, how to separate with fiber surface with the observation polyaniline.The pH of the 5th rinse water is 6.2, and the surface resistivity of the scraps of paper that make by filtration is 10
12Ohm.After this, by adding 2% ammonia spirit also after making fiber remove adulterant yesterday.Produced after the 1st cleaning and the 5th cleaning and the microphoto of the fiber of handling after removing adulterant.
Embodiment 12 is polymerization aniline in the presence of wooden chemical paper fiber, and wherein DBSA is used as equilibrium ion.The amount of aniline equal fiber amount 20%.
2000g wood fibre slurries (TMP substandard products) add in the flask altogether, and per 1 premium on currency of this fiber slurry contains the 10g fiber, promptly contains the 20g fiber altogether.Add the 17.5g DBSA then and make its dissolving spend the night (15 hours).After this add 5g aniline, form water-insoluble white aniline-dodecyl benzene sulfonate this moment, and this mixture becomes glassy yellow.Under agitation, cooling this mixture to temperature is 7 ℃ in ice-water bath.Then, the 14.1g ammonium persulfate is dissolved in the 150ml water, this solution is added in the mixture with 1 hour.Add after the ammonium persulfate, mixed continuously 5 hours, reactant mixture is bottle green afterwards.Allowing reactant mixture place spends the night.By the centrifugal reaction water of from product, removing.The product water is cleaned three times.To make surface resistivity be 10 by filtering this product of a part
4The scraps of paper of ohm.After the 5th was cleaned, surface resistivity was still 10
4Ohm.With described product cleaning 9 times, how to separate with fiber surface with the observation polyaniline.The pH of the 9th rinse water is 6.24, is 10 by the surface resistivity of filtering the scraps of paper that described product makes
11Ohm.Produced the microphoto of the fiber of after the 5th is cleaned and cleaned for the 9th time, handling.
The mixture of embodiment 13 polyaniline pastes and chemical paper fiber
The chemical pulp of the dispersion that 100g is cold is altogether added in the flask, and per 1 premium on currency of this paper pulp contains the 10g fiber, promptly contains the 10g fiber altogether.Add 1250g water and 30.5g polyaniline then, this polyaniline be by the p-methyl benzenesulfonic acid polymerization and contain 8.2% dry.This mixture was mixed 24 hours.After this, remove by filter the water of pH 3.3, and to make surface resistivity be 10 by filtering this product of a part
7-8The scraps of paper of ohm.The slurries of remnants are cleaned 5 times altogether.The pH of the 5th rinse water is 6.4, and is 10 by the surface resistivity of filtering the scraps of paper that described product makes
12Ohm.After the 1st time and the 5th are cleaned, produced microphoto, can see that wherein polyaniline is connected to the surface of fiber.
Embodiment 14 is polymerization aniline in the presence of wooden chemical paper fiber, and wherein p-methyl benzenesulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.After adding aniline, add fiber.
1000g water adds in the flask altogether, wherein is dissolved with the 7.66g p-methyl benzenesulfonic acid.Then, add 3.75g aniline, form erythroid solution this moment.In this solution, add the wooden chemical pulp of 1500g altogether, wherein comprise the 15g fiber.Subsequently, mixture yellowing.Under agitation, cooling this mixture to temperature is 11 ℃ in ice-water bath.Then, the 9.1g ammonium persulfate is dissolved in the 95ml water, this solution is added in the mixture with 50 minutes.Add after the ammonium persulfate, mixed continuously 5 hours.Golden fiber appears in the brown solution of product afterwards.The product placement is spent the night, and this moment, it became black, virellous mixture slowly.The purpose of this test is in order to observe before adding oxidant, changes the order that adds reagent and whether can quicken polymerisation in the wood fibre slurries.After this test, can draw reaction and not obtain quickening.
Embodiment 15 is polymerization aniline in the presence of wooden hot mechanical fiber, and wherein phenolsulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
The hot mechanical slurries (TMP/GW) that contain the 20g fiber of 2000g are altogether added in the flask.Then, add the 65% phenolsulfonic acid aqueous solution and the 0.02g phenylenediamine of 14.4g in slurries, this moment, mixture became maize yellow.Mixed 30 minutes, and added 5g aniline then, this moment forms water-soluble aniline-phenolsulfonate and reactant mixture becomes glassy yellow.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, the 12.3g ammonium persulfate is dissolved in the 120ml water, this solution is added in the mixture with 40 minutes.Add after the ammonium persulfate, mixed continuously 5 hours, at this moment, product is black and slightly green, this means that reaction finishes.The product placement is spent the night.After this sky, elimination paper pulp extrudes water, and this moment is by filtering and dry preparation filter cake.The surface resistivity of filter cake is 10
3Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 10 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
4Ohm, and the surface resistivity of the filter cake that makes after cleaning for the 6th time is 10
5-6Ohm.
Reactant mixture that does not have wooden slurries and the microphoto (annex II) that cleans for the 6th time have been produced.Photo shows that polymer is connected with fiber well, and whole fiber to be the typical case of polyaniline green, when owing to clean that color transition is blueness when causing the equilibrium ion amount to reduce.
Embodiment 16 is polymerization aniline in the presence of wooden hot mechanical fiber, and wherein phenolsulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
With the hot mechanical slurries that contain the 7g fiber of 1000g are (non--as TMP) to add in the flask altogether.Then, the 65% phenolsulfonic acid aqueous solution and the 0.008g phenylenediamine that in slurries, add 5.1g.Mixed 30 minutes, and added 1.75g aniline then, this moment forms water-soluble aniline-phenolsulfonate and reactant mixture becomes glassy yellow.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, the 4.6g ammonium persulfate is dissolved in the 50ml water, this solution is added in the mixture with 25 minutes.Add after the ammonium persulfate, mixed continuously 4 hours, at this moment, product is black and slightly blue, this means that reaction finishes.The product placement is spent the night.After this sky, elimination paper pulp extrudes water, and this moment is by filtering and dry preparation filter cake.The surface resistivity of filter cake is 10
4Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 6 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
5-6Ohm, and the surface resistivity of cleaning the filter cake make for the 6th time is 10
7Ohm.Reactant mixture that does not have wooden slurries and the microphoto (annex II) that cleans for the 6th time have been produced.
It is green that microphoto has shown that most of fibers and filament have been dyed polyaniline.But, wherein exist in the fiber that its surface does not react.In any case these unreacted fibers have been dyed yellow, this can illustrate that aniline-equilibrium ion salt is connected with them.Under any circumstance, the quantity not sufficient of oxidant is with in the polymerization of described site, because for example consumed oxidant in lignin oxidation's reaction in reactant mixture in some competitive reactions.Owing to clean, equilibrium ion is also washed off from the fiber and polyaniline has been removed adulterant and has become blueness, and this can observe from the fiber photo that cleans for the 6th time.But the color of fiber is obviously than being connected to the of light color of polyaniline on the chemical paper fiber among the embodiment 17.
Embodiment 17 is polymerization aniline in the presence of the wooden chemical paper fiber of pulverizing, and wherein phenolsulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
The wooden chemical paper fiber that contains the 10g fiber of 100g is altogether added in the flask.Then, the 65% phenolsulfonic acid aqueous solution that adds 900g water and 7.2g.Hybrid reaction mixture 10 minutes adds 2.5g aniline then, and this moment forms water-soluble aniline-phenolsulfonate and reactant mixture becomes glassy yellow.At this moment reactant mixture is still white.Under agitation, cooling this mixture to temperature is 9 ℃ in ice-water bath.Then, the 6.4g ammonium persulfate is dissolved in the 60ml water, this solution is added in the mixture with 35 minutes.Add after the ammonium persulfate, mixed continuously 4 hours, at this moment, product is black and slightly blue.The product placement is spent the night.After this sky, elimination paper pulp extrudes water, and this moment is by filtering and dry preparation filter cake.The surface resistivity of filter cake is 10
4Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 10 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
5Ohm, and the surface resistivity of cleaning the filter cake make for the 6th time is 10
7Ohm.The microphoto (annex II) of having produced reactant mixture and having cleaned for the 10th time.
It is green that microphoto has shown that fiber and filament have been dyed the typical case of polyaniline fully, and also keep this color during cleaning, the minimizing of surface resistivity is at this moment only depended on the doping effect that removes of p-poly-phenyl amine rather than is depended on polyaniline and fiber separation.
Embodiment 18 is polymerization aniline in the presence of wooden hot mechanical fiber, and wherein camphorsulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
The hot mechanical slurries that contain the 7g fiber (TMP substandard products) of 1000g are altogether added in the flask.Then, add the camphorsulfonic acid of 4.4g, this moment, mixture became maize yellow.Hybrid reaction mixture 20 minutes adds 1.75g aniline then, and this moment forms water-soluble aniline-camsilate and reactant mixture becomes glassy yellow.Under agitation, cooling this mixture to temperature is 10 ℃ in ice-water bath.Then, the 4.6g ammonium persulfate is dissolved in the 45ml water, this solution is added in the mixture with 20 minutes.Add after the ammonium persulfate, mixed continuously 4 hours, at this moment, product is brown.The product placement is spent the night.After this sky, product is bottle green and elimination paper pulp extrudes water.Simultaneously, by filtering and dry preparation filter cake, the surface resistivity of filter cake is 10
5Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 6 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
7Ohm, and the surface resistivity of cleaning the filter cake make for the 6th time is 10
12Ohm.The microphoto (annex II) of having produced reactant mixture and having cleaned for the 6th time.
Microphoto has shown the many golden zone that does not have the polyaniline green.Even in reactant mixture, the color of fiber/polyaniline also is a celadon, and after the 6th time is cleaned, and observes fiber and is shallow aquamarine and even the zone of more being unstained is arranged.Here, the same with embodiment 16, the zone of being unstained is yellow, and this is meant that aniline-equilibrium ion is connected with fiber, and polymerization is not finished, and this moment, oxidant consumed in the competitive reaction of some lignin.
Embodiment 19 is polymerization aniline in the presence of the wooden chemical paper fiber of pulverizing, and wherein camphorsulfonic acid is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
The pine and cypress chemical paper fiber of the pulverizing that contains the 10g fiber of 100g is altogether added in the flask.Then, add the 6.3g camphorsulfonic acid.Hybrid reaction mixture 20 minutes adds 2.5g aniline then, forms water-soluble aniline-camsilate this moment.Under agitation, cooling this mixture to temperature is 8 ℃ in ice-water bath.Then, the 6.4g ammonium persulfate is dissolved in the 62ml water, this solution is added in the mixture with 30 minutes.Add after the ammonium persulfate, mixed continuously 5 hours, at this moment, product is black and slightly blue.Allowing product place spends the night.After this sky, elimination paper pulp extrudes water from the bottle green mixture, and this moment is by filtering and dry preparation filter cake.The surface resistivity of filter cake is 10
4Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 8 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
6Ohm, and the surface resistivity of cleaning the filter cake make for the 6th time is 10
7Ohm.The microphoto (annex II) of having produced reactant mixture and having cleaned for the 6th time.
It is green that microphoto has shown that fiber and filament have been dyed the typical case of polyaniline fully, and also kept this color during cleaning, the minimizing of surface resistivity is at this moment only depended on the doping effect that removes of p-poly-phenyl amine rather than is depended on separating of polyaniline and fiber.
Embodiment 20 is polymerization aniline in the presence of wooden hot mechanical fiber, and wherein Loprazolam is used as equilibrium ion.The amount of aniline equal fiber amount 50%.
The hot mechanical slurries (TMP/GW) that contain the 5g fiber of 500g are altogether added in the flask.Then, add the 2.6g Loprazolam.After this add 2.5g aniline, this moment forms water-soluble aniline-methane sulfonates and reactant mixture becomes glassy yellow.Under agitation, cooling this mixture to temperature is 6 ℃ in ice-water bath.Then, the 6.14g ammonium persulfate is dissolved in the 60ml water, this solution is added in the mixture with 15 minutes.Add after the ammonium persulfate, mixed continuously 3 hours, at this moment, it is dark orange that product is.The product placement is spent the night.After this sky, elimination paper pulp extrudes water from the bottle green product.By filtering and dry preparation filter cake, the surface resistivity of filter cake is 10 simultaneously
3Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 7 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
5Ohm, and the surface resistivity of cleaning the filter cake make for the 6th time is 10
6-7Ohm.The microphoto (annex II) of having produced reactant mixture and having cleaned for the 6th time.
It is green that microphoto has shown that filament and part fiber are tangible polyaniline, but the part fiber is still yellow, and promptly aniline salt is present in the fiber, remains unfulfilled but react, and lignin has consumed oxidant before aniline polymerization finishes simultaneously.But established polyaniline is retained in the fiber well during cleaning, and only removes adulterant and just cause the filter cake surface resistivity to reduce.
Embodiment 21. is polymerization aniline in the presence of the wooden chemical paper fiber of pulverizing, and wherein Loprazolam is used as equilibrium ion.The amount of aniline equal fiber amount 25%.
The hot mechanical slurries (TMP/GW) that contain the 10g fiber of 100g are altogether added in the flask.Then, in slurries, add 900g water and 2.6g Loprazolam.After this add 2.5g aniline, form water-soluble aniline-methane sulfonates this moment.Under agitation, cooling this mixture to temperature is 6 ℃ in ice-water bath.Then, the 6.14g ammonium persulfate is dissolved in the 60ml water, this solution is added in the mixture with 35 minutes.Add after the ammonium persulfate, mixed continuously 4 hours, at this moment, product is green black.Allowing product place spends the night.After this sky, elimination paper pulp extrudes water from product.By filtering and dry preparation filter cake, the surface resistivity of filter cake is 10 simultaneously
4Ohm.By water eluriate and filter the described product of continuous wash until the pH of rinse water greater than 6.This needs to clean for 7 times altogether.By the surface resistivity of cleaning the filter cake that makes for the third time is 10
6Ohm, and the surface resistivity of cleaning the filter cake make for the 6th time is 10
9Ohm.
The conduction scraps of paper of making by fiber
At TKK (the Techincal University of Helsinki), according to the samples of embodiment 1 and 2 preparations, directly by the slurries of handling or wherein mix untreated pine and cypress cellulose slurries and prepare the scraps of paper.By using scraps of paper preparation standard SCAN-C 26:27 to produce the described scraps of paper.In KCl, utilize the standard method ASTM D257-93 that measures paper resistivity to measure the surface resistivity of scraps of paper both sides.In the method, sample is between two electrodes.Lower circular central electrode by another circular electrode around, and come the meter surface resistivity by lower central electrode and the voltage between the circular electrode, described top electrode has been eliminated the error that vertical conduction caused by the scraps of paper simultaneously.This equipment is made of HP 4339A-type high definition electric resistivity meter and HP1600B-type measurement structure.Measuring temperature is 23 ℃, and relative air humidity is 20%RH, and measuring voltage is 100V DC, and the charging interval is 30.0s.
Contain with the polyaniline of chemical paper fiber equivalent and the scraps of paper that directly make by sample 1 because too crisp and can not become paper.When wherein mixing 50% pure chemistry paper pulp fiber, obtaining surface resistivity is 10
5-6Ω/side's other scraps of paper of level.When fiber of handling when polyaniline and 25% pure mixed with fibers, surface resistivity rises to 10
9-10Ω/square rank.
In addition, the scraps of paper that prepare the sample of embodiment 4,5,6,7 and 8 at TKK.By with half pure mixed with fibers in the chemical paper fiber of handling, directly prepare the scraps of paper by sample 4,5 that uses different equilibrium ions to make and 6 fiber sample.
The sample 7 and 8 that directly needn't add any pure fiber by the fiber of handling and obtain prepares the scraps of paper.In these embodiments, contain 25% and 30% polyaniline in the fiber.But during producing the scraps of paper, a part of polyaniline is cleaned, so the amount of the polyaniline of combination is 17% (sample 7) and 30% (sample 8).
Temperature be 23 ℃, relative humidity be 20% and voltage be under the 100V, measure the surface resistivity of the scraps of paper.Measured the surface resistivity of scraps of paper tops (ts) and bottom (bs).In addition, also measured the surface resistivity of the scraps of paper that make by pure pine fibre pulp.The results are shown in the Table III, wherein shown the measured surface resistivity of the scraps of paper of using different equilibrium ions to make by the chemical paper fiber of the polyaniline processing of polymerization.The scraps of paper that made by pure pine fibre pulp are used as reference.
Before making the scraps of paper, contained 5%, 10%, 25% or 50% polyaniline in the fiber.In twice measurement, measuring voltage is 100V and 10V.Measure at scraps of paper top (ts) and bottom (bs).What the result provided is the mean value of measuring for 10 times altogether, and except the bottom of embodiment 6+50% chemical paper fiber was measured, it had carried out 9 times altogether and has measured.
Table III
| Sample | The average Ω in Ts/ top/side | Ts/ top deviation Ω/side | The average Ω in Bs/ bottom/side | Bs/ bottom deviation Ω/side |
| Ref_a | 6.16E+13 | 2.88E+13 | 1.94E+14 | 1.3E+14 |
| Ref_bc | 1.23E+15 | 2.22E+15 | 1.33E+15 | 2.8E+15 |
| Pan-dbsa 5%, embodiment 4+50% chemical paper fiber | 3.37E+8 | 2.41E+8 | 1.29E+9 | 1.03E+9 |
| Pan-dbsa 10%, and embodiment 4 | 5.33E+7 | 1.21E+7 | 3.74E+7 | 1.45E+7 |
| Pan-p-tsa 5%, embodiment 5+50% chemical paper fiber | 8.23E+10 | 1.17E+10 | 5.17E+10 | 1.45E+10 |
| Pan-p-tsa 10%, and embodiment 5 | 4.08E+9 | 4.69E+8 | 2.21E+9 | 3.22E+8 |
| Pan-sa 5%, embodiment 6+50% chemical paper fiber | 4.26E+14 | 4.34E+14 | 2.65E+14 | 2.53E+14 |
| Pan-sa 10%, and embodiment 6 | 6.05E+14 | 5.52E+14 | 1.3E+15 | 2.36E+15 |
| Pan-p-tsa 25%, and embodiment 7 | 6.11E+8 | 1.18E+8 | 7.01E+8 | 9.02E+7 |
| Pan-p-tsa 25%, and embodiment 7,10V | 5.26E+8 | 1.2E+8 | 6.15E+8 | 6.6E+7 |
| Pan-p-tsa 50%, and embodiment 8,10V | 3.1E+6 | 7.27E+5 | 3.24E+6 | 4.66E+5 |
Table III shown, when preparation comprises the scraps of paper with the polyaniline of DBSA polymerization, is to obtain suitable electric conductivity at 5% o'clock in polyaniline concentration.This good electrical conductivity especially can be used by wood fibre (for example passing through thermomechanical pulp), is connected with the suitable of this fibrid because obtained DBSA-polyaniline.
In the presence of p-methyl benzenesulfonic acid, the polyaniline of polymerization is connected well with chemical paper fiber, has therefore reduced the danger that is cleaned.In fiber, need this polyaniline more more a little than DBSA-polyaniline, preferred 10% or more, to realize suitable electric conductivity in the fiber.
Therefore,, the conduction chemical paper fiber can be produced, the conduction scraps of paper can be further produced thus by means of appropriate fiber type and polyaniline-equilibrium ion combination.
But in paper production, must consider to make the engineering properties of paper, therefore measure density (SCAN-P 7:75), tensile strength (SCANP 38:80) and Scott in conjunction with z-intensity (TAPPI T 569pm-00 method).The results are shown in the Table IV of engineering properties.
Table IV
| Density kg/m 3 | The tension coefficient, Nm/g | Scott is in conjunction with z-intensity, J/m 2 | Surface resistivity, ohm/side | |
| The pine and cypress fibre pulp Reference, embodiment 1 | 676 | 67.8 | 356 | 6.20E+13 |
| Contain the paper (dbsa) of 25% aniline, embodiment 1 | 631 | 44.1 | 146 | 3.40E+08 |
| Contain the paper (dbsa) of 50% aniline, embodiment 1 | 656 | 37.5 | 114 | 5.30E+07 |
| The pine and cypress fibre pulp Reference, embodiment 5 With 6 | 638 | 76.5 | 271 | 1.20E+15 |
| Contain the paper (p-TSA) of 10% aniline, embodiment 5 | 579 | 46.5 | 214 | 4.10E+09 |
| Contain the paper (citric acid) of 10% aniline, embodiment 6 | 588 | 47.8 | 214 | 6.10E+14 |
| The pine and cypress fibre pulp Reference, embodiment 7 With 8 | 676 | 67.8 | 356 | 6.30E+13 |
| Contain the paper (p-TSA) of 25% aniline, embodiment 7 | 502 | 42.2 | 244 | 5.60E+08 |
| Contain the paper (p-TSA) of 50% aniline, embodiment 8 | 477 | 34.2 | 161 | 3.10E+06 |
In the scraps of paper are produced, notice that the reservation of polyaniline in paper is faint when using DBSA as equilibrium ion.Wherein observe spot colors intensive in the scraps of paper.When using p-methyl benzenesulfonic acid or citric acid, do not observe this class problem.
Table 2 has shown by using 10% p-methyl benzenesulfonic acid to obtain obvious much lower paper resistivity as equilibrium ion than the use citric acid.
As can be seen, for employed all equilibrium ions, compare with the reference sample that does not have any polyaniline from the result, the adhesion of paper and the intensity (tension coefficient and Scott combination) that produces therefrom all reduce significantly.
Claims (16)
1. producd fibers method for compositions, this fiber composition comprise first component that comprises string and second component that is made of synthetic conducting polymer, according to this method:
-described string comprises fiber porous, loose and that separate, and
-used conducting polymer is a kind of polymer of independent conduction, in order in polymeric material, to produce charge carrier, and the adulterant that mixed in this polymer, and
-described synthetic polymer makes by in-situ polymerization in fiber and on its surface, and
By described conducting polymer firmly is connected with fiber, make it can not be washed by water basically,
It is characterized in that using organic sulfonic acid as adulterant, it is absorbed in the fiber in water-bearing media, and the monomer corresponding to polymer is contacted with fiber and polymerization.
2. according to the method for claim 1, it is characterized in that allowing the adulterant of described monomer and polymer be absorbed in the fiber, afterwards by adding polyalcohol catalyst and making this salt or compound polymerization by elevated temperature when needing to form salt or compound.
3. according to the method for claim 1 or 2, it is characterized in that using the aromatic sulphonic acid that comprises an aromatic rings or two fused rings to be used for mixing, wherein at least one ring randomly has polarity or nonpolar ring substituents.
4. according to the method for claim 3, it is characterized in that using the aromatic sulphonic acid that contains functional group or at least one ring, have the alkyl chain of 1-20 carbon to be used for mixing.
5. according to any one method in the claim 1 to 4, it is characterized in that by increasing mutual affinity between described porous fibre and the described conducting polymer forming aliphatic hydrocarbon structure adjacent one another are and aromatic hydrocarbon structure on the faying face between described fiber and the described conducting polymer.
6. according to the method for claim 5, it is with joint efforts plain to it is characterized in that increasing mutually combining of described porous fibre and described conducting polymer by the fiber of selecting its surface to be covered by lignin at least in part.
7. according to the method for claim 5, it is characterized in that by using the polyaniline that mixes as conducting polymer, increase the affinity that mutually combines of described porous fibre and described conducting polymer, wherein the equilibrium ion of the polyaniline of this doping comprises aromatic hydrocarbyl.
8. according to the method for claim 5, it is characterized in that by in containing the water-bearing media of porous fibre, carrying out the polymerisation of conducting polymer, so that the polymer that forms by polymerization is connected with porous fibre, increases the affinity that mutually combines of described porous fibre and described conducting polymer.
9. according to any one method in the claim 1 to 8, it is characterized in that using that soluble adulterant is used for described polymer is connected to the fiber that is made of chemical cellulose paper pulp in medium.
10. according to any one method in the claim 1 to 9, it is characterized in that producing a kind of fiber composition, wherein under 25 ℃ of temperature under the pH 7 ± 0.3, the conducting polymer that is connected with fiber of maximum 10 weight %, preferred maximum 5 weight % can be washed by water.
11. according to any one method in the claim 1 to 10, it is characterized in that described porous fibre comprises separates and loose fibres.
12., it is characterized in that and the polymer that forms can become in the presence of the organic balanced ion or adulterant of conduction form that the pH of water is 2-3 according to any one method in the claim 1 to 11.
13., it is characterized in that reclaiming described fibre blend and dry from aqueous phase according to any one method in the claim 1 to 12.
14. according to any one method in the claim 1 to 13, it is characterized in that described fibre blend be used to produce needn't in the middle of dry paper or cardboard.
15. according to any one method in the claim 1 to 14, it is characterized in that as follows polyaniline being connected with the fiber that is made of chemical cellulose paper pulp: the adulterant that at first will be selected from p-methyl benzenesulfonic acid, phenolsulfonic acid and camphorsulfonic acid is dissolved in aqueous phase, form fibrous suspension to wherein adding fiber then, aniline is mixed in the described fibrous suspension and forms the salt of aniline and described adulterant, and add polyalcohol catalyst and produce polyaniline with the temperature of rising suspension and it is connected with fiber.
16. according to any one method in the claim 1 to 15, it is characterized in that as follows polyaniline being connected with the fiber that is made of the plain wood pulp of mechanical fiber: at first will be distributed to aqueous phase as the DBSA of adulterant, form fibrous suspension to wherein adding fiber then, aniline joined in the described fibrous suspension and form the salt of aniline and described adulterant, the temperature that adds polyalcohol catalyst and the described suspension of rising is then produced polyaniline and it is connected with fiber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| FI20030490A FI20030490A (en) | 2003-04-01 | 2003-04-01 | Process for making fiber composition |
| FI20030490 | 2003-04-01 |
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| CN100393939C CN100393939C (en) | 2008-06-11 |
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| US (1) | US20060144543A1 (en) |
| EP (1) | EP1608809A1 (en) |
| JP (1) | JP2006522233A (en) |
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| CA (1) | CA2518565A1 (en) |
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| CA2825337A1 (en) * | 2011-01-25 | 2012-08-02 | Basf Se | Manufacturing a papery article |
| US20120186762A1 (en) * | 2011-01-25 | 2012-07-26 | Basf Se | Producing half-stuffs for the manufacture of papery articles |
| BR112013019042A2 (en) * | 2011-01-25 | 2018-07-10 | Basf Se | process to produce a semipaste for the production of paper products, and use of methanesulfonic acid. |
| US9384867B2 (en) * | 2011-03-29 | 2016-07-05 | Fpinnovations | Flexible, semiconducting nanocomposite materials based on nanocrystalline cellulose and polyaniline |
| JP5843463B2 (en) * | 2011-04-04 | 2016-01-13 | 花王株式会社 | Fibrous material |
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- 2004-04-01 EP EP04725077A patent/EP1608809A1/en not_active Withdrawn
- 2004-04-01 JP JP2006505628A patent/JP2006522233A/en not_active Withdrawn
- 2004-04-01 US US10/551,036 patent/US20060144543A1/en not_active Abandoned
- 2004-04-01 AU AU2004225736A patent/AU2004225736A1/en not_active Abandoned
- 2004-04-01 CA CA002518565A patent/CA2518565A1/en not_active Abandoned
- 2004-04-01 WO PCT/FI2004/000200 patent/WO2004088035A1/en active Application Filing
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| CN103965514A (en) * | 2014-04-29 | 2014-08-06 | 中原工学院 | Method for preparing polyaniline/cellulose diacetate compound conductive plastic |
| CN103965513A (en) * | 2014-04-29 | 2014-08-06 | 中原工学院 | Method for preparing polyaniline nanofiber/cellulose diacetate composite conductive material |
| CN103965513B (en) * | 2014-04-29 | 2016-04-27 | 中原工学院 | The preparation method of polyaniline nano fiber/Cellulose diacetate composite conducting material |
| CN103965514B (en) * | 2014-04-29 | 2017-01-18 | 中原工学院 | Method for preparing polyaniline/cellulose diacetate compound conductive plastic |
| CN113151971A (en) * | 2021-03-31 | 2021-07-23 | 海安启弘纺织科技有限公司 | Method for preparing warp-knitted super-soft velvet fabric by adopting radial superfine fibers and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1608809A1 (en) | 2005-12-28 |
| FI20030490A0 (en) | 2003-04-01 |
| FI20030490A (en) | 2004-10-02 |
| AU2004225736A1 (en) | 2004-10-14 |
| US20060144543A1 (en) | 2006-07-06 |
| JP2006522233A (en) | 2006-09-28 |
| CA2518565A1 (en) | 2004-10-14 |
| CN100393939C (en) | 2008-06-11 |
| WO2004088035A1 (en) | 2004-10-14 |
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