CN104005229A - Preparation method of water-based polymer-doped natural conductive fibers - Google Patents
Preparation method of water-based polymer-doped natural conductive fibers Download PDFInfo
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- CN104005229A CN104005229A CN201410240726.2A CN201410240726A CN104005229A CN 104005229 A CN104005229 A CN 104005229A CN 201410240726 A CN201410240726 A CN 201410240726A CN 104005229 A CN104005229 A CN 104005229A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000000835 fiber Substances 0.000 title abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 81
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 63
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 45
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 42
- 229920005604 random copolymer Polymers 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 27
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000004744 fabric Substances 0.000 claims description 130
- 239000000203 mixture Substances 0.000 claims description 45
- 239000000725 suspension Substances 0.000 claims description 40
- 150000001768 cations Chemical class 0.000 claims description 35
- 239000006184 cosolvent Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 230000005611 electricity Effects 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 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 compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229940089401 xylon Drugs 0.000 claims description 6
- UFAGAQUHRODLFO-UHFFFAOYSA-M [Cl-].CC=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 Chemical compound [Cl-].CC=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 UFAGAQUHRODLFO-UHFFFAOYSA-M 0.000 claims description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 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 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 compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 4
- -1 acrylyl Chemical group 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 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
- VGHRSPNHHSLNCP-UHFFFAOYSA-M ethyl-dimethyl-[phenyl(prop-2-enoyloxy)methyl]azanium;chloride Chemical compound [Cl-].C=CC(=O)OC([N+](C)(C)CC)C1=CC=CC=C1 VGHRSPNHHSLNCP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 239000002019 doping agent Substances 0.000 abstract description 5
- 239000002216 antistatic agent Substances 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 230000006353 environmental stress Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 229920001940 conductive polymer Polymers 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229920003043 Cellulose fiber Polymers 0.000 description 7
- 239000002322 conducting polymer Substances 0.000 description 6
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 229920002521 macromolecule Polymers 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
- 230000003068 static effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 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
- 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 a preparation method of water-based polymer-doped natural conductive fibers. The preparation method comprises the following steps: preparing a series of water-based cationic random copolymer surfactants by using a free radical solution copolymerization method by taking a hard vinyl monomer and a soft vinyl monomer in a certain ratio as oleophilic monomers and taking a cationic vinyl monomer and an acrylamide monomer as hydrophilic monomers; next, successfully preparing the polypyrrole/natural fiber composite natural conductive fibers by adopting an in-situ adsorption chemical-oxidization polymerization method by taking the prepared water-based copolymers as doping agents and taking ferric trichloride as an oxidizing agent. The water-based polymer-doped conductive natural fibers can be used for manufacturing a series of conductive paper by virtue of a traditional papermaking process, and has attractive advantages and application prospects in a plurality of fields such as antistatic materials, electromagnetic shielding, energy storage equipment, and packaging of sensors and electronic equipment. The water-based polymer-doped natural conductive fibers also can be used for replacing an electrostatic electromagnetic shielding plastic packaging material widely used in domestic and foreign markets at present, and therefore, the environment stress caused by plastics is relieved.
Description
Technical field
The present invention relates to a kind of preparation method of conductive fiber, particularly under a kind of water base high molecular chanza, conduct electricity the preparation method of natural fabric.
Background technology
Prepare intrinsic conducting polymer (ICP)/fiber composite conductive material taking fiber as template, because its good stability and processability obtain close concern, but mainly concentrate on the research of the inorganic and polymer fiber such as carbon fiber, graphite fibre, polyurethane and polyamide fiber.Compare with polymer fiber with inorfil, native cellulose fibre source is more simple extensive, the several functions such as its sustainable developability, environment friendly and biological degradability in addition, and possess the stronger market competitiveness; Can reduce the dependence to exhausting petroleum resources simultaneously.And due to the characteristic of the functional groups such as its porous and rich surface hydroxyl, be more conducive to conducting polymer in its surperficial efficient adsorption and deposition.At present, also increasingly extensive to the research of ICP modified natural fiber, mainly contain electrochemical plating, gas-phase polymerization and conducting polymer/paper pulp fiber original position adsorpting polymerization method.First two method is expensive, and obtained conducting polymer productive rate is seriously limited to the area of electrode, and oxidant is difficult to reclaim, and has very large application limitation; Original position adsorpting polymerization method technique is relatively simple.From the current study, researcher mainly concentrates on and adopts little molecule and middle molecular dopant preparation conduction natural fabric, adopts the research of large molecular dopant preparation conduction natural fabric have not been reported, particularly water-base cation polymer.
Summary of the invention
The object of the present invention is to provide and under a kind of water base high molecular chanza, conduct electricity the preparation method of natural fabric, obtained conductive cellulose fiber can be directly by traditional paper technology separately or make serial conductive paper with fibrillation cellulose fiber is composite, and improved electric conductivity.
For achieving the above object, the technical solution used in the present invention is:
Adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 500～9900 parts of water, stir 10～40 minutes, make homodisperse natural fabric suspension;
2. in 600～10000 parts of homodisperse natural fabric suspension, add 2.5～10 parts of water-base cation random copolymer surfactants, stir 10～60 minutes, obtain system A;
3. to the mixed liquor that adds 15～35 parts of catalyst and 30～60 parts of water in system A, stir 10～30 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, after constant temperature, to the mixture that drips 5～50 parts of pyrroles and 5～30 portions of frozen water in system B, time for adding is 10～30 minutes, after dropwising, at 0 DEG C, continue reaction 0.5～2 hour, make polypyrrole/natural fabric suspension;
5. by polypyrrole/natural fabric suspension through washing and filtration under diminished pressure repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: by rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are pressed (10～30): (10～30): (5～50): (0～10): (2～5): the mass ratio of (5～25) joins in reactor, under agitation be heated to 70～90 DEG C, then drip the mixed liquor of 0.05～2 part of initator and 1～10 part of organic cosolvent, time for adding is 0.5～1 hour, under 70～90 DEG C of conditions, continue insulation reaction 3～4 hours again, finally be cooled to room temperature, make yellow translucent water-base cation random copolymer surfactant.
Described rigid vinyl monomer is the mixture of one or both any proportionings in methyl methacrylate, styrene.
Described soft vinyl monomer is the mixture of one or both any proportionings in butyl acrylate, butyl methacrylate.
Described cationic vinyl monomer is the mixture of one or both any proportionings in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, p-vinyl benzyl trimethyl ammonium chloride, Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium, diallyldimethylammonium chloride.
Described acrylamide monomers is the mixture of one or both any proportionings in acrylamide, n-methylolacrylamide.
Described organic cosolvent is the mixture of one or both any proportionings in acetone, DMF.
Described initator is the one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide.
Described natural fabric is the mixture of one or both any proportionings in cotton fiber, string, xylon.
Described catalyst is the mixture of one or both any proportionings in ferric trichloride, ammonium persulfate.
Compared with prior art, the beneficial effect that the present invention has: the present invention adopts water-base cation macromolecule as the adulterant of preparing polypyrrole/natural fabric composite conducting natural fabric, by the standby conduction of in situ chemical oxidative polymerization legal system natural fabric.Cation group can suitably suppress the generation of polypyrrole disordered chain as amino introducing; Also the poly-problem of wadding that can alleviate modified fibre, in addition, large molecular dopant also can be improved conduction and the heat endurance of conducting polymer simultaneously.Preparation technology of the present invention is simple, obtained conductive cellulose fiber can be directly by traditional paper technology separately or with composite series conduction (packaging) paper that makes of fibrillation cellulose fiber, it all embodies outstanding advantage and application prospect at numerous areas as the packaging of anti-static material, electromagnetic shielding, energy storage device, sensor and electronic equipment etc., and on alternative current domestic and international market, widely used static electromagnetic shielding plastic packaging, alleviates the pressure that plastics cause environment.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 900 parts of water, stir 20 minutes, make homodisperse natural fabric suspension;
2. in 1000 parts of homodisperse natural fabric suspension systems, add 4.5 parts of water-base cation random copolymer surfactants, stir 30 minutes, obtain system A;
3. to the mixed liquor that adds 20 parts of catalyst and 40 parts of water in system A, stir 10～30 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 12 parts of pyrroles and 15 portions of frozen water in system B, time for adding is 20 minutes, after dropwising, at 0 DEG C, continue reaction 1 hour, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 20:20:30:4:3:10, be under agitation heated to 80 DEG C.Then to the mixed liquor that drips 1 part of initator and 3 parts of organic cosolvents in system, time for adding is 0.5 hour, then under 70 DEG C of conditions, continues insulation reaction 3 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric 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.Described cationic vinyl monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride; Described acrylamide monomers is acrylamide; Described organic cosolvent is acetone; Described initator is azodiisobutyronitrile.
The surface resistivity of the conductive paper that obtained the present invention conduction natural fabric is made by traditional paper technology is 43 Ω cm.
Embodiment 2
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 566 parts of water, stir 30 minutes, make homodisperse natural fabric suspension;
2. in 666 parts of homodisperse natural fabric suspension systems, add 4.5 parts of water-base cation random copolymer surfactants, stir 40 minutes, obtain system A;
3. to the mixed liquor that adds 26 parts of catalyst and 45 parts of water in system A, stir 30 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 15 parts of pyrroles and 26 portions of frozen water in system B, time for adding is 20 minutes, after dropwising, at 0 DEG C, continue reaction 1.5 hours, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 18:22:35:3:3:10, be under agitation heated to 75 DEG C.Then to the mixed liquor that drips 1.5 parts of initators and 3 parts of organic cosolvents in system, time for adding is 0.5 hour, then under 75 DEG C of conditions, continues insulation reaction 4 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric is xylon; Described catalyst is ferric trichloride;
Described rigid vinyl monomer is methyl methacrylate; Described soft vinyl monomer is butyl methacrylate; Described cationic vinyl monomer is methylacryloxyethyldimethyl benzyl ammonium chloride; Described acrylamide monomers is n-methylolacrylamide; Described organic cosolvent is DMF; Described initator is azodiisobutyronitrile.
The surface resistivity of the conductive paper that obtained invention case conduction natural fabric is made by traditional paper technology is 32 Ω cm.
Embodiment 3
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 1900 parts of water, stir 20 minutes, make homodisperse natural fabric suspension;
2. in 2000 parts of homodisperse natural fabric suspension systems, add 6 parts of water-base cation random copolymer surfactants, stir 40 minutes, obtain system A;
3. to the mixed liquor that adds 28 parts of catalyst and 39 parts of water in system A, stir 20 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 16 parts of pyrroles and 22 portions of frozen water in system B, time for adding is 20 minutes, after dropwising, at 0 DEG C, continue reaction 1.5 hours, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 15:26:32:2:4:12, be under agitation heated to 80 DEG C.Then to the mixed liquor that drips 1.5 parts of initators and 5 parts of organic cosolvents in system, time for adding is 1 hour, then under 80 DEG C of conditions, continues insulation reaction 4 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric 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 DMF; Described initator is 2,2'-Azobis(2,4-dimethylvaleronitrile).
The surface resistivity of the conductive paper that obtained the present invention conduction natural fabric is made by traditional paper technology is 36 Ω cm.
Embodiment 4
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 500 parts of water, stir 15 minutes, make homodisperse natural fabric suspension;
2. in 4000 parts of homodisperse natural fabric suspension systems, add 2.5 parts of water-base cation random copolymer surfactants, stir 50 minutes, obtain system A;
3. to the mixed liquor that adds 18 parts of catalyst and 35 parts of water in system A, stir 15 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 5 parts of pyrroles and 10 portions of frozen water in system B, time for adding is 10 minutes, after dropwising, at 0 DEG C, continue reaction 0.5 hour, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 10:28:50:10:2.5:15, be under agitation heated to 90 DEG C.Then to the mixed liquor that drips 1 part of initator and 7 parts of organic cosolvents in system, time for adding is 0.5 hour, then under 90 DEG C of conditions, continues insulation reaction 3 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric is cotton fiber; Described catalyst is ammonium persulfate;
Described rigid vinyl monomer is styrene; Described soft vinyl monomer is butyl methacrylate; Described cationic vinyl monomer is acrylyl oxy-ethyl dimethyl benzyl ammonium chloride; Described acrylamide monomers is n-methylolacrylamide; Described organic cosolvent is acetone; Described initator is dibenzoyl peroxide.
Embodiment 5
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 4000 parts of water, stir 10 minutes, make homodisperse natural fabric suspension;
2. in 600 parts of homodisperse natural fabric suspension systems, add 7.5 parts of water-base cation random copolymer surfactants, stir 60 minutes, obtain system A;
3. to the mixed liquor that adds 30 parts of catalyst and 30 parts of water in system A, stir 10 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 50 parts of pyrroles and 18 portions of frozen water in system B, time for adding is 25 minutes, after dropwising, at 0 DEG C, continue reaction 1.5 hours, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 22:30:10:5:2:20, be under agitation heated to 85 DEG C.Then to the mixed liquor that drips 0.05 part of initator and 8 parts of organic cosolvents in system, time for adding is 1 hour, then under 70 DEG C of conditions, continues insulation reaction 4 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric is the mixture of string and cotton fiber arbitrary proportion; Described catalyst is the mixture of ferric trichloride and ammonium persulfate arbitrary proportion;
Described rigid vinyl monomer is the mixture of methyl methacrylate and styrene arbitrary proportion; Described soft vinyl monomer is the mixture of butyl acrylate and butyl methacrylate arbitrary proportion; Described cationic vinyl monomer is the mixture of p-vinyl benzyl trimethyl ammonium chloride and Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium arbitrary proportion; Described acrylamide monomers is the mixture of acrylamide and n-methylolacrylamide arbitrary proportion; Described organic cosolvent is the mixture of acetone and DMF arbitrary proportion; Described initator is dibenzoyl peroxide.
Embodiment 6
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 9900 parts of water, stir 25 minutes, make homodisperse natural fabric suspension;
2. in 8000 parts of homodisperse natural fabric suspension systems, add 8.5 parts of water-base cation random copolymer surfactants, stir 20 minutes, obtain system A;
3. to the mixed liquor that adds 15 parts of catalyst and 55 parts of water in system A, stir 35 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 20 parts of pyrroles and 30 portions of frozen water in system B, time for adding is 15 minutes, after dropwising, at 0 DEG C, continue reaction 2 hours, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 30:16:20:7:5:23, be under agitation heated to 70 DEG C.Then to the mixed liquor that drips 1.8 parts of initators and 9 parts of organic cosolvents in system, time for adding is 0.5 hour, then under 70 DEG C of conditions, continues insulation reaction 3.5 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric is the mixture of string and xylon arbitrary proportion; Described catalyst is the mixture of ferric trichloride and ammonium persulfate arbitrary proportion;
Described rigid vinyl monomer is the mixture of methyl methacrylate and styrene arbitrary proportion; Described soft vinyl monomer is the mixture of butyl acrylate and butyl methacrylate arbitrary proportion; Described cationic vinyl monomer is the mixture of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and diallyldimethylammonium chloride arbitrary proportion; Described acrylamide monomers is the mixture of acrylamide and n-methylolacrylamide arbitrary proportion; Described organic cosolvent is the mixture of acetone and DMF arbitrary proportion; Described initator is azodiisobutyronitrile.
Embodiment 7
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 6200 parts of water, stir 40 minutes, make homodisperse natural fabric suspension;
2. in 6000 parts of homodisperse natural fabric suspension systems, add 10 parts of water-base cation random copolymer surfactants, stir 10 minutes, obtain system A;
3. to the mixed liquor that adds 35 parts of catalyst and 50 parts of water in system A, stir 25 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 30 parts of pyrroles and 5 portions of frozen water in system B, time for adding is 30 minutes, after dropwising, at 0 DEG C, continue reaction 1 hour, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 25:10:40:3.5:25, be under agitation heated to 90 DEG C.Then to the mixed liquor that drips 2 parts of initators and 1 part of organic cosolvent in system, time for adding is 1 hour, then under 85 DEG C of conditions, continues insulation reaction 4 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric is xylon; Described catalyst is ferric trichloride;
Described rigid vinyl monomer is methyl methacrylate; Described soft vinyl monomer is butyl acrylate.Described cationic vinyl monomer is methylacryloxyethyldimethyl benzyl ammonium chloride; Described organic cosolvent is acetone; Described initator is 2,2'-Azobis(2,4-dimethylvaleronitrile).
Embodiment 8
Under water base high molecular chanza, conduct electricity the preparation method of natural fabric: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 8500 parts of water, stir 35 minutes, make homodisperse natural fabric suspension;
2. in 10000 parts of homodisperse natural fabric suspension systems, add 3 parts of water-base cation random copolymer surfactants, stir 25 minutes, obtain system A;
3. to the mixed liquor that adds 33 parts of catalyst and 60 parts of water in system A, stir 30 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, constant temperature is after 5 minutes, to the mixture that drips 40 parts of pyrroles and 28 portions of frozen water in system B, time for adding is 10 minutes, after dropwising, at 0 DEG C, continue reaction 2 hours, make polypyrrole/natural fabric suspension;
5. polypyrrole/natural fabric suspension is passed through to washing and the filtration under diminished pressure of three times repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
The concrete preparation process of described water-base cation random copolymer surfactant is: rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, glacial acetic acid and organic cosolvent are joined in reactor by the mass ratio of 27:13:5:4.5:5, be under agitation heated to 80 DEG C.Then to the mixed liquor that drips 0.07 part of initator and 10 parts of organic cosolvents in system, time for adding is 1 hour, then under 75 DEG C of conditions, continues insulation reaction 3 hours.Finally system is cooled to room temperature, makes yellow translucent water-base cation random copolymer surfactant.
Described natural fabric is the mixture of xylon and string arbitrary proportion; Described catalyst is the mixture of ferric trichloride and ammonium persulfate arbitrary proportion;
Described rigid vinyl monomer is the mixture of methyl methacrylate and styrene arbitrary proportion; Described soft vinyl monomer is the mixture of butyl acrylate and butyl methacrylate arbitrary proportion.Described cationic vinyl monomer is the mixture of methylacryloxyethyldimethyl benzyl ammonium chloride and acrylyl oxy-ethyl-trimethyl salmiac arbitrary proportion; Described organic cosolvent is the mixture of acetone and DMF arbitrary proportion; Described initator is azodiisobutyronitrile.
Key of the present invention is to adopt water-base cation macromolecule as the adulterant of preparing the natural fibre of polypyrrole/natural fabric composite conducting, and cation group can suitably suppress the generation of polypyrrole disordered chain as amino introducing; Also can alleviate the poly-problem of wadding of modified fibre simultaneously.In addition, large molecular dopant also can be improved conduction and the heat endurance of conducting polymer.Product of the present invention adopts the preparation of in situ chemical oxidative polymerization method, technique is simple, obtained conductive cellulose fiber can be directly by traditional paper technology separately or with composite series conduction (packaging) paper that makes of fibrillation cellulose fiber, it all embodies tempting advantage and application prospect at numerous areas as the packaging of anti-static material, electromagnetic shielding, energy storage device, sensor and electronic equipment etc.It is widely used static electromagnetic shielding plastic packaging on alternative current domestic and international market also, alleviates the pressure that plastics cause environment.
Claims (10)
1. under water base high molecular chanza, conduct electricity the preparation method of natural fabric, it is characterized in that: adsorb chemical oxidative polymerization by original position and prepare polypyrrole/natural fabric composite conducting natural fabric, the detailed process of preparation is as follows:
1. at room temperature in reactor, add 100 parts of natural fabrics and 500～9900 parts of water, stir 10～40 minutes, make homodisperse natural fabric suspension;
2. in 600～10000 parts of homodisperse natural fabric suspension, add 2.5～10 parts of water-base cation random copolymer surfactants, stir 10～60 minutes, obtain system A;
3. to the mixed liquor that adds 15～35 parts of catalyst and 30～60 parts of water in system A, stir 10～30 minutes, obtain system B;
4. system B is placed in to temperature and is the ice-water bath of 0 DEG C, after constant temperature, to the mixture that drips 5～50 parts of pyrroles and 5～30 portions of frozen water in system B, time for adding is 10～30 minutes, after dropwising, at 0 DEG C, continue reaction 0.5～2 hour, make polypyrrole/natural fabric suspension;
5. by polypyrrole/natural fabric suspension through washing and filtration under diminished pressure repeatedly, make polypyrrole/natural fabric composite conducting natural fabric.
2. under a kind of water base high molecular chanza according to claim 1, conduct electricity the preparation method of natural fabric, it is characterized in that: the concrete preparation process of described water-base cation random copolymer surfactant is: by rigid vinyl monomer, soft vinyl monomer, cationic vinyl monomer, acrylamide monomers, glacial acetic acid and organic cosolvent are pressed (10～30): (10～30): (5～50): (0～10): (2～5): the mass ratio of (5～25) joins in reactor, under agitation be heated to 70～90 DEG C, then drip the mixed liquor of 0.05～2 part of initator and 1～10 part of organic cosolvent, time for adding is 0.5～1 hour, under 70～90 DEG C of conditions, continue insulation reaction 3～4 hours again, finally be cooled to room temperature, make yellow translucent water-base cation random copolymer surfactant.
3. under a kind of water base high molecular chanza according to claim 2, conduct electricity the preparation method of natural fabric, it is characterized in that: described rigid vinyl monomer is the mixture of one or both any proportionings in methyl methacrylate, styrene.
4. under a kind of water base high molecular chanza according to claim 2, conduct electricity the preparation method of natural fabric, it is characterized in that: described soft vinyl monomer is the mixture of one or both any proportionings in butyl acrylate, butyl methacrylate.
5. under a kind of water base high molecular chanza according to claim 2, conduct electricity the preparation method of natural fabric, it is characterized in that: described cationic vinyl monomer is the mixture of one or both any proportionings in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, p-vinyl benzyl trimethyl ammonium chloride, Dimethylaminoethyl Methacrylate benzyl chloride quaternary ammonium, diallyldimethylammonium chloride.
6. under a kind of water base high molecular chanza according to claim 2, conduct electricity the preparation method of natural fabric, it is characterized in that: described acrylamide monomers is the mixture of one or both any proportionings in acrylamide, n-methylolacrylamide.
7. under a kind of water base high molecular chanza according to claim 2, conduct electricity the preparation method of natural fabric, it is characterized in that: described organic cosolvent is the mixture of one or both any proportionings in acetone, DMF.
8. under a kind of water base high molecular chanza according to claim 2, conduct electricity the preparation method of natural fabric, it is characterized in that: described initator is the one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide.
9. under a kind of water base high molecular chanza according to claim 1, conduct electricity the preparation method of natural fabric, it is characterized in that: described natural fabric is the mixture of one or both any proportionings in cotton fiber, string, xylon.
10. under a kind of water base high molecular chanza according to claim 1, conduct electricity the preparation method of natural fabric, it is characterized in that: described catalyst is the mixture of one or both any proportionings in ferric trichloride, ammonium persulfate.
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