CN104005229B - The preparation method of natural fiber is conducted electricity under a kind of water base high molecular chanza - Google Patents
The preparation method of natural fiber is conducted electricity under a kind of water base high molecular chanza Download PDFInfo
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- CN104005229B CN104005229B CN201410240726.2A CN201410240726A CN104005229B CN 104005229 B CN104005229 B CN 104005229B CN 201410240726 A CN201410240726 A CN 201410240726A CN 104005229 B CN104005229 B CN 104005229B
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- 239000000835 fiber Substances 0.000 title claims abstract description 140
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 230000005611 electricity Effects 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 53
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 46
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 32
- 229920005604 random copolymer Polymers 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000725 suspension Substances 0.000 claims description 32
- 239000006184 cosolvent Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 150000001768 cations Chemical class 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 14
- -1 acrylyl Chemical group 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 10
- 230000003292 diminished effect Effects 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical group [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 4
- TVXNKQRAZONMHJ-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=C(C=C)C=C1 TVXNKQRAZONMHJ-UHFFFAOYSA-M 0.000 claims description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- AIBUHXJSZPPYQC-UHFFFAOYSA-M dimethyl-(1-phenylethyl)-(2-prop-2-enoyloxyethyl)azanium chloride Chemical compound [Cl-].CC(C1=CC=CC=C1)[N+](C)(C)CCOC(C=C)=O AIBUHXJSZPPYQC-UHFFFAOYSA-M 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 9
- 238000004806 packaging method and process Methods 0.000 abstract description 7
- 125000002091 cationic group Chemical group 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002216 antistatic agent Substances 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000011065 in-situ storage Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 229920001940 conductive polymer Polymers 0.000 description 8
- 229920003043 Cellulose fiber Polymers 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000002322 conducting polymer Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WVILKCQOUPGWSM-UHFFFAOYSA-N benzyl(dimethyl)-$l^{3}-chlorane Chemical compound CCl(C)CC1=CC=CC=C1 WVILKCQOUPGWSM-UHFFFAOYSA-N 0.000 description 1
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical group [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses and under a kind of water base high molecular chanza, conduct electricity the preparation method of natural fiber.The present invention is first using a certain proportion of rigid vinyl monomer and soft vinyl monomer as oleophylic monomer, using cationic vinyl monomer and acrylamide monomers as hydrophilic monomer, it is prepared for serial water base cationic random copolymers surfactant by radical solution copolymerization method.Then with made water base copolymer as adulterant, with ferric trichloride as oxidant, it is successfully prepared polypyrrole/natural fiber composite conducting natural fiber by original position sorption chemical oxidative polymerization method.Product of the present invention directly can prepare series of conductive paper by traditional paper technology, and it all embodies tempting advantage and application prospect in the packaging etc. of numerous areas such as anti-static material, electromagnetic shielding, energy storage device, sensor and electronic equipment.Widely used electrostatic electromagnetic shielding plastic packaging on its most alternative current domestic and international market, alleviates the pressure that environment is caused by plastics.
Description
Technical field
The present invention relates to the preparation method of a kind of conductive fiber, particularly to a kind of water base high molecular
The preparation method of natural fiber is conducted electricity under chanza.
Background technology
Intrinsic conducting polymer (ICP)/fiber composite conductive material is prepared for template with fiber,
The stability excellent due to it and processability obtain close concern, but it is fine to focus primarily upon carbon
Inorganic and the researchs of polymer fiber such as dimension, graphite fibre, polyurethane and Fypro.With
Inorfil is compared with polymer fiber, and native cellulose fibre source is the simplest extensively, adds
The several functions such as its sustainable developability, environment friendly and biological degradability, and possess relatively
The strong market competitiveness；Can reduce the dependence that can exhaust petroleum resources simultaneously.And due to it
The characteristic of the functional groups such as porous and rich surface hydroxyl, is more beneficial for conducting polymer at it
The efficient absorption on surface and deposition.At present, the research to ICP modified natural fibers is the widest
General, mainly there is the absorption in situ of electrochemical plating, gas-phase polymerization and conducting polymer/paper pulp fiber
Polymerization.First two method is expensive, and obtained conducting polymer productivity is severely limited by
The area of electrode, and oxidant is difficult to reclaim, and there is the biggest application limitation；Absorption in situ
Polymerization technique is relatively easy.From the current study, researcher focus primarily upon employing little
Molecule and Middle molecule adulterant preparation conduction natural fiber, use big molecular dopant preparation conduction
The research of natural fiber have not been reported, particularly water-base cation polymer.
Summary of the invention
It is an object of the invention to provide and under a kind of water base high molecular chanza, conduct electricity natural fibre
The preparation method of dimension, obtained conductive cellulose fiber can be directly by traditional paper technology list
Solely or with fibrillation cellulose fiber compound and prepare series of conductive paper, and improve electric conductivity.
For achieving the above object, the technical solution used in the present invention is:
Polypyrrole/natural fiber composite conducting sky is prepared by original position sorption chemical oxidative polymerization method
So fiber, the detailed process of preparation is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 500～9900 parts of water,
Stir 10～40 minutes, prepare homodisperse natural fiber suspension；
2. in 600～10000 parts of homodisperse natural fiber suspension, 2.5～10 parts are added
Water-base cation random copolymer surfactant, stirs 10～60 minutes, obtains system A；
3. in system A, add 15～35 parts of catalyst and the mixed liquor of 30～60 parts of water, stir
Mix 10～30 minutes, obtain system B；
4. system B is placed in the ice-water bath that temperature is 0 DEG C, after constant temperature, in system B
Dripping 5～50 parts of pyrroles and the mixture of 5～30 portions of frozen water, time for adding is 10～30 minutes,
After dropping, at 0 DEG C, continue reaction 0.5～2 hour, prepare polypyrrole/natural fiber
Suspension；
5. by polypyrrole/natural fiber suspension through washing repeatedly and filtration under diminished pressure, prepare
Polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent press (10～30): (10～30): (5～50): (0～10):
(2～5): the mass ratio of (5～25) joins in reactor, is under agitation heated to
70～90 DEG C, then 0.05～2 part of initiator of dropping and the mixed liquor of 1～10 part of organic cosolvent,
Time for adding is 0.5～1 hour, then continues insulation reaction 3～4 hours under the conditions of 70～90 DEG C,
It is finally cooled to room temperature, prepares yellow translucent water-base cation random copolymer surface-active
Agent.
Described rigid vinyl monomer is one or both in methyl methacrylate, styrene
The arbitrarily mixture of proportioning.
Described soft vinyl monomer be the one in butyl acrylate, butyl methacrylate or
The mixture of two kinds of any proportionings.
Described cationic vinyl monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methyl
Acryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, propylene
Acyloxyethyl dimethyl benzyl ammonium chloride, p-vinylbenzyltrimethyl ammonium chloride, methyl-prop
One or two in olefin(e) acid dimethylamino ethyl ester benzyl chloride quaternary ammonium, diallyldimethylammonium chloride
Plant the mixture of any proportioning.
Described acrylamide monomers is the one in acrylamide, NMA or two
Plant the mixture of any proportioning.
Described organic cosolvent is one or both in acetone, N,N-dimethylformamide
The mixture of meaning proportioning.
Described initiator is in azodiisobutyronitrile, ABVN, dibenzoyl peroxide
One.
Described natural fiber is that one or both in cotton fiber, string, wood-fibred are any
The mixture of proportioning.
Described catalyst is the mixed of one or both any proportionings in ferric trichloride, ammonium persulfate
Compound.
Compared with prior art, the invention have the benefit that the present invention use water base sun from
Sub-macromolecule is as preparing the adulterant of polypyrrole/natural fiber composite conducting natural fiber, logical
Cross in situ chemical oxidative polymerization method preparation conduction natural fiber.The introducing of cation group such as amino
Can suitably suppress the generation of polypyrrole disordered chain；The wadding that simultaneously also can alleviate modified fibre gathers
Problem, additionally, big molecular dopant also can improve conduction and the heat endurance of conducting polymer.
Preparation technology of the present invention is simple, and obtained conductive cellulose fiber can be directly by traditional papermaking
Technique individually or compounds with fibrillation cellulose fiber and prepares series of conductive (packaging) paper, and it is many
The packaging of field such as anti-static material, electromagnetic shielding, energy storage device, sensor and electronic equipment
Embody in prominent advantage and application prospect, and alternative current domestic and international market wide Deng all
The electrostatic electromagnetic shielding plastic packaging of general use, alleviates the pressure that environment is caused by plastics.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 900 parts of water, stirring
20 minutes, prepare homodisperse natural fiber suspension；
2. in 1000 parts of homodisperse natural fiber suspension systems, addition 4.5 parts is water base
Cationic random copolymers surfactant, stirs 30 minutes, obtains system A；
3. in system A, add 20 parts of catalyst and the mixed liquor of 40 parts of water, stir 10～30
Minute, obtain system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 12 parts of pyrroles and the mixture of 15 portions of frozen water in B, time for adding is 20 minutes,
After dropping, at 0 DEG C, continue reaction 1 hour, prepare polypyrrole/natural fiber and suspend
Liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent are joined by the mass ratio of 20:20:30:4:3:10
In reactor, under agitation it is heated to 80 DEG C.Then in system, drip 1 part of initiation
Agent and the mixed liquor of 3 parts of organic cosolvents, time for adding is 0.5 hour, then at 70 DEG C
Under the conditions of continue insulation reaction 3 hours.Finally system is cooled to room temperature, prepares yellow semi-transparent
Bright water-base cation random copolymer surfactant.
Described natural fiber is string；Described catalyst is ferric trichloride；
Described rigid vinyl monomer is methyl methacrylate；Described soft vinyl monomer is
The mixture of one or both any proportionings in butyl acrylate, butyl methacrylate.Institute
Stating cationic vinyl monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；Described acryloyl
Amine monomers is acrylamide；Described organic cosolvent is acetone；Described initiator is azo two
Isobutyronitrile.
The conductive paper that conduction natural fiber obtained by the present invention is prepared by traditional paper-making process
Surface resistivity be 43 Ω cm.
Embodiment 2
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 566 parts of water, stirring
30 minutes, prepare homodisperse natural fiber suspension；
2. in 666 parts of homodisperse natural fiber suspension systems, add 4.5 parts of water base sun
Ion random copolymer surfactant, stirs 40 minutes, obtains system A；
3. in system A, add 26 parts of catalyst and the mixed liquor of 45 parts of water, stir 30 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 15 parts of pyrroles and the mixture of 26 portions of frozen water in B, time for adding is 20 minutes,
After dropping, at 0 DEG C, continue reaction 1.5 hours, prepare polypyrrole/natural fiber and hang
Supernatant liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent are joined by the mass ratio of 18:22:35:3:3:10
In reactor, under agitation it is heated to 75 DEG C.Then in system, drip 1.5 parts to draw
Sending out agent and the mixed liquor of 3 parts of organic cosolvents, time for adding is 0.5 hour, then at 75 DEG C
Under the conditions of continue insulation reaction 4 hours.Finally system is cooled to room temperature, prepares yellow semi-transparent
Bright water-base cation random copolymer surfactant.
Described natural fiber is wood-fibred；Described catalyst is ferric trichloride；
Described rigid vinyl monomer is methyl methacrylate；Described soft vinyl monomer is
Butyl methacrylate；Described cationic vinyl monomer is methylacryoyloxyethyl dimethyl
Benzyl ammonium chloride；Described acrylamide monomers is NMA；Described organic co-solvent
Agent is N,N-dimethylformamide；Described initiator is azodiisobutyronitrile.
The conductive paper that conduction natural fiber obtained by invention case is prepared by traditional paper-making process
Surface resistivity be 32 Ω cm.
Embodiment 3
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 1900 parts of water, stirring
20 minutes, prepare homodisperse natural fiber suspension；
2. in 2000 parts of homodisperse natural fiber suspension systems, add 6 parts of water base sun
Ion random copolymer surfactant, stirs 40 minutes, obtains system A；
3. in system A, add 28 parts of catalyst and the mixed liquor of 39 parts of water, stir 20 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 16 parts of pyrroles and the mixture of 22 portions of frozen water in B, time for adding is 20 minutes,
After dropping, at 0 DEG C, continue reaction 1.5 hours, prepare polypyrrole/natural fiber and hang
Supernatant liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent are joined by the mass ratio of 15:26:32:2:4:12
In reactor, under agitation it is heated to 80 DEG C.Then in system, drip 1.5 parts to draw
Sending out agent and the mixed liquor of 5 parts of organic cosolvents, time for adding is 1 hour, then at 80 DEG C
Under the conditions of continue insulation reaction 4 hours.Finally system is cooled to room temperature, prepares yellow semi-transparent
Bright water-base cation random copolymer surfactant.
Described natural fiber is string；Described catalyst is ferric trichloride；
Described rigid vinyl monomer is methyl methacrylate；Described soft vinyl monomer is
Butyl acrylate；Described cationic vinyl monomer is acrylyl oxy-ethyl-trimethyl salmiac；
Described acrylamide monomers is acrylamide；Described organic cosolvent is N, N-dimethyl methyl
Acid amides；Described initiator is ABVN.
The conductive paper that conduction natural fiber obtained by the present invention is prepared by traditional paper-making process
Surface resistivity be 36 Ω cm.
Embodiment 4
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 500 parts of water, stirring
15 minutes, prepare homodisperse natural fiber suspension；
2. in 4000 parts of homodisperse natural fiber suspension systems, addition 2.5 parts is water base
Cationic random copolymers surfactant, stirs 50 minutes, obtains system A；
3. in system A, add 18 parts of catalyst and the mixed liquor of 35 parts of water, stir 15 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 5 parts of pyrroles and the mixture of 10 portions of frozen water in B, time for adding is 10 minutes,
After dropping, at 0 DEG C, continue reaction 0.5 hour, prepare polypyrrole/natural fiber and hang
Supernatant liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent join reactor by the mass ratio of 10:28:50:10:2.5:15
In, under agitation it is heated to 90 DEG C.Then in system, drip 1 part of initiator and 7
The mixed liquor of part organic cosolvent, time for adding is 0.5 hour, then under the conditions of 90 DEG C
Continue insulation reaction 3 hours.Finally system is cooled to room temperature, prepares the translucent water of yellow
Base cationic random copolymers surfactant.
Described natural fiber is cotton fiber；Described catalyst is ammonium persulfate；
Described rigid vinyl monomer is styrene；Described soft vinyl monomer is metering system
Acid butyl ester；Described cationic vinyl monomer is acryloxyethyldimethyl benzyl ammonium chloride；
Described acrylamide monomers is NMA；Described organic cosolvent is acetone；Institute
Stating initiator is dibenzoyl peroxide.
Embodiment 5
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 4000 parts of water, stirring
10 minutes, prepare homodisperse natural fiber suspension；
2. in 600 parts of homodisperse natural fiber suspension systems, add 7.5 parts of water base sun
Ion random copolymer surfactant, stirs 60 minutes, obtains system A；
3. in system A, add 30 parts of catalyst and the mixed liquor of 30 parts of water, stir 10 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 50 parts of pyrroles and the mixture of 18 portions of frozen water in B, time for adding is 25 minutes,
After dropping, at 0 DEG C, continue reaction 1.5 hours, prepare polypyrrole/natural fiber and hang
Supernatant liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent join in reactor by the mass ratio of 22:30:10:5:2:20,
Under agitation it is heated to 85 DEG C.Then in system, drip 0.05 part of initiator and 8 parts
The mixed liquor of organic cosolvent, time for adding is 1 hour, then continues under the conditions of 70 DEG C
Insulation reaction 4 hours.Finally system is cooled to room temperature, prepares the translucent water base sun of yellow
Ion random copolymer surfactant.
Described natural fiber is string and the mixture of cotton fiber arbitrary proportion；Described catalysis
Agent is ferric trichloride and the mixture of ammonium persulfate arbitrary proportion；
Described rigid vinyl monomer is the mixed of methyl methacrylate and styrene arbitrary proportion
Compound；Described soft vinyl monomer is butyl acrylate and butyl methacrylate arbitrary proportion
Mixture；Described cationic vinyl monomer be p-vinylbenzyltrimethyl ammonium chloride and
The mixture of Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium arbitrary proportion；Described acryloyl
Amine monomers is acrylamide and the mixture of NMA arbitrary proportion；Described organic
Cosolvent is acetone and the mixture of N,N-dimethylformamide arbitrary proportion；Described initiator
For dibenzoyl peroxide.
Embodiment 6
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 9900 parts of water, stirring
25 minutes, prepare homodisperse natural fiber suspension；
2. in 8000 parts of homodisperse natural fiber suspension systems, addition 8.5 parts is water base
Cationic random copolymers surfactant, stirs 20 minutes, obtains system A；
3. in system A, add 15 parts of catalyst and the mixed liquor of 55 parts of water, stir 35 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 20 parts of pyrroles and the mixture of 30 portions of frozen water in B, time for adding is 15 minutes,
After dropping, at 0 DEG C, continue reaction 2 hours, prepare polypyrrole/natural fiber and suspend
Liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent join in reactor by the mass ratio of 30:16:20:7:5:23,
Under agitation it is heated to 70 DEG C.Then in system, drip 1.8 parts of initiators and 9 parts have
The mixed liquor of co-solvent content, time for adding is 0.5 hour, then continues under the conditions of 70 DEG C
Insulation reaction 3.5 hours.Finally system is cooled to room temperature, prepares yellow translucent water base
Cationic random copolymers surfactant.
Described natural fiber is string and the mixture of wood-fibred arbitrary proportion；Described catalysis
Agent is ferric trichloride and the mixture of ammonium persulfate arbitrary proportion；
Described rigid vinyl monomer is the mixed of methyl methacrylate and styrene arbitrary proportion
Compound；Described soft vinyl monomer is butyl acrylate and butyl methacrylate arbitrary proportion
Mixture；Described cationic vinyl monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride
Mixture with diallyldimethylammonium chloride arbitrary proportion；Described acrylamide monomers is
Acrylamide and the mixture of NMA arbitrary proportion；Described organic cosolvent is third
Ketone and the mixture of N,N-dimethylformamide arbitrary proportion；Described initiator is that azo two is different
Butyronitrile.
Embodiment 7
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 6200 parts of water, stirring
40 minutes, prepare homodisperse natural fiber suspension；
2. in 6000 parts of homodisperse natural fiber suspension systems, add 10 parts of water base sun
Ion random copolymer surfactant, stirs 10 minutes, obtains system A；
3. in system A, add 35 parts of catalyst and the mixed liquor of 50 parts of water, stir 25 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 30 parts of pyrroles and the mixture of 5 portions of frozen water in B, time for adding is 30 minutes,
After dropping, at 0 DEG C, continue reaction 1 hour, prepare polypyrrole/natural fiber and suspend
Liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, glacial acetic acid and organic
Cosolvent joins in reactor by the mass ratio of 25:10:40:3.5:25, under agitation heats liter
Temperature is to 90 DEG C.Then in system, drip 2 parts of initiators and the mixing of 1 part of organic cosolvent
Liquid, time for adding is 1 hour, then continues insulation reaction 4 hours under the conditions of 85 DEG C.
Finally system is cooled to room temperature, prepares yellow translucent water-base cation random copolymer table
Face activating agent.
Described natural fiber is wood-fibred；Described catalyst is ferric trichloride；
Described rigid vinyl monomer is methyl methacrylate；Described soft vinyl monomer is
Butyl acrylate.Described cationic vinyl monomer is methylacryoyloxyethyl dimethyl benzyl
Ammonium chloride；Described organic cosolvent is acetone；Described initiator is ABVN.
Embodiment 8
The preparation method of natural fiber is conducted electricity: by adsorbing in situ under water base high molecular chanza
Chemical oxidative polymerization prepares polypyrrole/natural fiber composite conducting natural fiber, the tool of preparation
Body process is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 8500 parts of water, stirring
35 minutes, prepare homodisperse natural fiber suspension；
2. in 10000 parts of homodisperse natural fiber suspension systems, add 3 parts of water base sun
Ion random copolymer surfactant, stirs 25 minutes, obtains system A；
3. in system A, add 33 parts of catalyst and the mixed liquor of 60 parts of water, stir 30 points
Clock, obtains system B；
4. system B being placed in the ice-water bath that temperature is 0 DEG C, constant temperature is after 5 minutes, Xiang Ti
Being to drip 40 parts of pyrroles and the mixture of 28 portions of frozen water in B, time for adding is 10 minutes,
After dropping, at 0 DEG C, continue reaction 2 hours, prepare polypyrrole/natural fiber and suspend
Liquid；
5. by polypyrrole/natural fiber suspension by washing repeatedly for three times and filtration under diminished pressure,
Prepare polypyrrole/natural fiber composite conducting natural fiber.
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, glacial acetic acid and organic
Cosolvent joins in reactor by the mass ratio of 27:13:5:4.5:5, under agitation heat temperature raising
To 80 DEG C.Then in system, drip 0.07 part of initiator and the mixing of 10 parts of organic cosolvents
Liquid, time for adding is 1 hour, then continues insulation reaction 3 hours under the conditions of 75 DEG C.
Finally system is cooled to room temperature, prepares yellow translucent water-base cation random copolymer table
Face activating agent.
Described natural fiber is wood-fibred and the mixture of string arbitrary proportion；Described catalysis
Agent is ferric trichloride and the mixture of ammonium persulfate arbitrary proportion；
Described rigid vinyl monomer is the mixed of methyl methacrylate and styrene arbitrary proportion
Compound；Described soft vinyl monomer is butyl acrylate and butyl methacrylate arbitrary proportion
Mixture.Described cationic vinyl monomer is methylacryoyloxyethyl dimethyl benzyl chlorine
Change ammonium and the mixture of acrylyl oxy-ethyl-trimethyl salmiac arbitrary proportion；Described organic co-solvent
Agent is acetone and the mixture of N,N-dimethylformamide arbitrary proportion；Described initiator is even
Nitrogen bis-isobutyronitrile.
The present invention it is critical only that employing water-base cation macromolecule is as preparing polypyrrole/natural
The adulterant of the fiber composite natural fibre of conduction, the introducing of cation group such as amino can suitably press down
The generation of polypyrrole disordered chain processed；Also can alleviate the poly-problem of wadding of modified fibre simultaneously.Additionally,
Big molecular dopant also can improve conduction and the heat endurance of conducting polymer.Product of the present invention is adopted
Preparing by situ chemical oxidative polymerization method, technique is simple, and obtained conductive cellulose fiber can
Directly individually or compounded with fibrillation cellulose fiber by traditional paper technology and prepare series of conductive
(packaging) paper, it is in numerous areas such as anti-static material, electromagnetic shielding, energy storage device, biography
The packaging etc. of sensor and electronic equipment all embodies tempting advantage and application prospect.It also can replace
Pack for widely used electrostatic electromagnetic shielding plastic on current domestic and international market, alleviate plastics pair
The pressure that environment causes.
Claims (4)
1. conducting electricity the preparation method of natural fiber under water base high molecular chanza, it is special
Levy and be: prepare polypyrrole/natural fiber composite guide by original position sorption chemical oxidative polymerization method
Electricity natural fiber, the detailed process of preparation is as follows:
In reactor, the most at room temperature add 100 parts of natural fibers and 500～9900 parts of water,
Stir 10～40 minutes, prepare homodisperse natural fiber suspension；
2. in 600～10000 parts of homodisperse natural fiber suspension, 2.5～10 parts are added
Water-base cation random copolymer surfactant, stirs 10～60 minutes, obtains system A；
3. in system A, add 15～35 parts of catalyst and the mixed liquor of 30～60 parts of water, stir
Mix 10～30 minutes, obtain system B；
4. system B is placed in the ice-water bath that temperature is 0 DEG C, after constant temperature, in system B
Dripping 5～50 parts of pyrroles and the mixture of 5～30 portions of frozen water, time for adding is 10～30 minutes,
After dropping, at 0 DEG C, continue reaction 0.5～2 hour, prepare polypyrrole/natural fiber
Suspension；
5. by polypyrrole/natural fiber suspension through washing repeatedly and filtration under diminished pressure, prepare
Polypyrrole/natural fiber composite conducting natural fiber；
The concrete preparation process of described water-base cation random copolymer surfactant is: will be hard
Sex ethylene base monomer, soft vinyl monomer, cationic vinyl monomer, acrylic amide list
Body, glacial acetic acid and organic cosolvent press (10～30): (10～30): (5～50): (0～10):
(2～5): the mass ratio of (5～25) joins in reactor, is under agitation heated to
70～90 DEG C, then 0.05～2 part of initiator of dropping and the mixed liquor of 1～10 part of organic cosolvent,
Time for adding is 0.5～1 hour, then continues insulation reaction 3～4 hours under the conditions of 70～90 DEG C,
It is finally cooled to room temperature, prepares yellow translucent water-base cation random copolymer surface-active
Agent；
Described rigid vinyl monomer is methyl methacrylate；
Described soft vinyl monomer is butyl methacrylate；
Described cationic vinyl monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methyl
Acryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, propylene
Acyloxyethyl dimethyl benzyl ammonium chloride, p-vinylbenzyltrimethyl ammonium chloride, methyl-prop
One or two in olefin(e) acid dimethylamino ethyl ester benzyl chloride quaternary ammonium, diallyldimethylammonium chloride
Plant the mixture of any proportioning；
Described natural fiber is the mixing of one or both any proportionings in cotton fiber, wood-fibred
Thing；
Described catalyst is ammonium persulfate；
The method uses water-base cation macromolecule as preparing polypyrrole/natural fiber composite guide
The adulterant of electricity natural fiber, by situ chemical oxidative polymerization method preparation conduction natural fiber.
Conduct electricity natural under a kind of water base high molecular chanza the most according to claim 1
The preparation method of fiber, it is characterised in that: described acrylamide monomers is methylol acryloyl
Amine.
Conduct electricity natural under a kind of water base high molecular chanza the most according to claim 1
The preparation method of fiber, it is characterised in that: described organic cosolvent is acetone.
Conduct electricity natural under a kind of water base high molecular chanza the most according to claim 1
The preparation method of fiber, it is characterised in that: described initiator is ABVN, peroxidating
One in dibenzoyl.
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| CN101070672A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院化学研究所 | Super-hydrophobic conductive fiber, fabric and preparing method and use |
| CN102720066A (en) * | 2012-07-05 | 2012-10-10 | 苏州大学 | Method for preparing ultra-high molecular weight polyethylene/polyaniline composite conductive fibre |
| CN103290685A (en) * | 2012-02-22 | 2013-09-11 | 北京服装学院 | Method for preparing high-conductivity conductive fiber and fabric, prepared conductive fiber and fabric and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070672A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院化学研究所 | Super-hydrophobic conductive fiber, fabric and preparing method and use |
| CN103290685A (en) * | 2012-02-22 | 2013-09-11 | 北京服装学院 | Method for preparing high-conductivity conductive fiber and fabric, prepared conductive fiber and fabric and applications thereof |
| CN102720066A (en) * | 2012-07-05 | 2012-10-10 | 苏州大学 | Method for preparing ultra-high molecular weight polyethylene/polyaniline composite conductive fibre |
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| Title |
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| 无规共聚物表面活性剂的合成及其结构对导电纤维性能的影响;牟静;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20131015(第10期);第20-22，101-103页 * |
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