CN102102231B - Method for preparing conductive cellulose fibers - Google Patents
Method for preparing conductive cellulose fibers Download PDFInfo
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- CN102102231B CN102102231B CN 201010589210 CN201010589210A CN102102231B CN 102102231 B CN102102231 B CN 102102231B CN 201010589210 CN201010589210 CN 201010589210 CN 201010589210 A CN201010589210 A CN 201010589210A CN 102102231 B CN102102231 B CN 102102231B
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Abstract
The invention discloses a method for preparing conductive cellulose fibers, which comprises the following steps of: mixing nano carbon black and carbon nano tube in a certain ration, performing acid washing and purification, and then grinding and dispersing the mixture of carbon and ionic liquid under the condition of an infrared lamp; obtaining nano carbon/cellulose spinning solution containing 8 to 15 weight percent of carbon by using the carbon-containing ionic liquid as a cellulose solvent; and preparing carbon-containing cellulose composite fibers by using a dry-jet wet-spinning or wet-spinning process and using deionized water as a coagulation bath. The method can simply and feasibly realize uniform dispersion of the carbon nano tube and the carbon black in the cellulose fibers, and greatly improves the electric conductivity of the cellulose fibers; and the obtained carbon-containing cellulose composite fibers can be widely applied in the antistatic field of materials for clothes or industries. The solvent used for the process production is nontoxic and can be repeatedly reclaimed and used, and the whole process realizes green production.
Description
Technical field
The present invention relates to the preparation method of the conductive cellulose composite fibre in the chemical fibres industry.Form in the process that the present invention utilizes imidazole type ion liquid and nano carbon black and CNT to grind and interact, impel the nano-sized carbon material at the ionic liquid Uniform Dispersion, thereby overcome the after-processing technology difficulty that nano carbon black and CNT are reunited and caused, simple for process.In addition, utilize rational ratio between nanometer carbon black and the CNT, in cellulosic matrix, can build a large amount of energising networks, thereby greatly improve the electric conductivity of composite fibre.Conventional dry-jet wet-spinning or the technology of wet spinning are adopted in the production of composite fibre, and obtained cellulose composite fiber good conductivity is expected extensive use and takes with industry and use the field.
Background technology
Nanometer carbon black and CNT have good electric conductivity, are the focuses that people study always.Carbon black itself is semi-conducting material, and the nanometer carbon black particle diameter is little, and specific area is large and coarse, has lower resistivity, is used for different conduction or antistatic articles, such as antistatic or conductive rubber, plastic products, CABLE MATERIALS; The caliber of CNT generally in several nanometers to tens nanometers, and the length of CNT is typical monodimension nanometer material generally at several microns to several millimeters, the structure of CNT makes it have good electric conductivity.In addition, nano carbon black and CNT all have anti-strong acid, and highly basic and good heat endurance are the ideal fillers of polymer composites.CNT or nano carbon black have wide application potential as the polymer composites of filler preparation at aspects such as stealth material, high performance structures material, multifunctional materials.Simultaneously, nano carbon black and CNT be the rational proportion collocation in composite, can form synergy, improve the electric conductivity of composite, correlative study all has report in polypropylene film material and polyester material, according to different composite systems, the ratio of nano carbon black and CNT (carbon nano-tube) is different.In addition, because nano carbon black and CNT all belong to nanoscale, its surface energy is large, and it is serious to reunite each other, greatly reduces the materials'use performance.
Along with the day by day exhaustion of petroleum resources, the development and utilization natural macromolecular material more and more is subject to people's attention.Cellulose is the abundantest natural macromolecular material of a nature middle storage capacity, takes full advantage of cellulosic material and has very important realistic meaning.Imidazole type ion liquid [BMIM] Cl is cellulosic fine solvent, utilize this ion liquid dissolving and preparation cellulosic material to become in recent years the focus of research, its preparation process is according to related process cellulose pulp directly to be dissolved in to form cellulose solution in the ionic liquid, then by dry-wet spinning or wet spinning.Utilize ionic liquid for characteristics such as the cellulose fibre of solvent preparation have that mechanical property is good, even structure, dyeability are good, have higher prospects for commercial application.
In the process that imidazole type ion liquid [BMIM] Cl and nano-sized carbon material grind, can interact between CATION and the carbon in the ionic liquid, reduce Van der Waals force between the nano-sized carbon, thereby the even carbon nanotube of agglomerated is disperseed.Coupled ion liquid can dissolve and prepare the characteristics of cellulose fibre as solvent, the nano-sized carbon material at first can be dispersed in the ionic liquid, then utilizes ionic liquid to be solvent, the preparation composite cellulose fiber.It is few to utilize at present natural polymer to prepare the research of conductive material, and patent ZL200410052885.6 receives quantitative nanometer carbon black by adding in cellulose spinning fluid, find that mechanical property, electric conductivity and the thermal property of fiber is improved to some extent.Patent CN200710036886.5 has significantly improved mechanical property and the conductance of cellulose fibre by add quantitative CNT in the cellulose fibre preparation process.More than two patents all relate to the modification of nano-sized carbon material, its complex disposal process, and the electric conductivity of the fiber of preparation promotes not obvious.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of conductive cellulose fiber preparation method.
Principle of the present invention is to utilize milled processed between CNT and the ionic liquid, makes to form between Nano carbon material and the ionic liquid to interact, and impels nano-sized carbon material Uniform Dispersion in ionic liquid.Utilize the mixture of ionic liquid and nano-sized carbon material to prepare cellulose spin dope for solvent, and prepare carbon/cellulose composite fiber through doing wet method or wet spinning.Utilize nano carbon black and CNT (carbon nano-tube) rational proportion, in the middle of cellulosic matrix, mutually build conductive network, thereby prepared the good cellulose fibre of electric conductivity.
One of purpose of the present invention is to provide a kind of cellulose base composite fibre that contains nano-sized carbon, and this composite fibre is prepared by following method:
1. nano carbon black and the CNT of addressing added the hot reflux certain hour in certain density acid solution, after cleaning, filtration, drying, obtain the nano-sized carbon material of purifying;
2. in the infrared lamp drier, the nano carbon black of purifying and the CNT mass ratio according to 1: 10～1: 20 is mixed, ionic liquid and nano-sized carbon substance weight are according to 765～1380: 1 mixes to put into and contains the agate mill and grind, grinding rate remains on 40r/min～70r/min, milling time remains on 1～4 hour, can obtain the ionic liquid solution of carbon containing;
3. be 300～1200 cellulose cotton pulp or wood pulp with the degree of polymerization, be ground into the particle of 2～5 μ m with food masher, 50～70 ℃ of lower vacuumizes 5～12 hours;
In the example liquid that contains the nano-sized carbon material and above-mentioned 3 with above-mentioned 2 gained dry resulting cellulose pulp particle with 10～16: the preparation of 1 weight ratio, join in the dissolver, under 90 ℃～110 ℃ through stirring, under vacuum environment, dissolved 2～6 hours, and namely obtained the spinning solution for the preparation of carbon/cellulose composite fiber of black.
5. the temperature with aforesaid spinning solution for the preparation of carbon/cellulose composite fiber is adjusted to 80～100 ℃, spray through spinnerets, air gap by 10～150mm is behind the air layer between spinning plate surface and the coagulating bath face, enter solidification forming in the deionized water solution, through washing, to obtain the carbon containing quality after the drying be carbon/cellulose composite fiber of 8%～15%.Perhaps the temperature of just aforesaid spinning solution for the preparation of carbon/cellulose composite fiber is adjusted to 80～100 ℃, spray through spinnerets, directly enter into deionized water solution by wet-spinning frame, through washing, can to obtain the carbon containing quality after the drying be carbon/cellulose composite fiber of 8%～15%.
The order of magnitude of prepared carbon/cellulose composite fiber conductance is 10
7～10
4Ω .cm.
Carbon/the cellulose composite fiber of the method preparation has following advantage:
(1) under infrared lamp, after nano-sized carbon material and ionic liquid mixing, in the agate mill, can impel nano-sized carbon Uniform Dispersion in ionic liquid through after a while grinding, this is the key of preparation conductive cellulose composite fibre;
(2) rational proportion between nano carbon black and the CNT forms conductive channel in cellulosic matrix, can significantly improve the electric conductivity of cellulose composite fiber;
(3) ionic liquid is cellulosic fine solvent, and it is good to have a solubility property, rate of recovery high, environmentally safe;
(4) production of adopting conventional dried wet processing or wet spinning technology all can realize comparatively smoothly fiber, deionized water, technique simple possible are selected in coagulating bath;
(5) carbon/cellulose composite fiber of preparation has larger application prospect taking with the fabrics for industrial use field.
The specific embodiment
Below by example the present invention is specifically described.Following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention, and the person skilled in the art in this field can content make some nonessential improvement and adjustment to the present invention according to the present invention.
Embodiment 1:
1. with nano carbon black and the CNT mass ratio according to 1: 10, the nitric acid of putting into 3.0M added hot reflux 48 hours, after filtration, obtain nano carbon black and the carbon nano tube of purifying after the cleaning, drying;
2. be under the infrared lamp of 800w at power, with nano-sized carbon material and 354g ionic liquid mixed grinding in the agate mill of 2g purifying, grinding rate 60r/min, milling time 2 hours;
3. be 1000 cellulose cotton pulp with the degree of polymerization, with food masher pulp be ground into the particle that diameter is 2 μ m～5 μ m, these cotton pulp particles are placed on vacuum-10 * 10 with cotton bag parcel
4Dry 6 hours of the lower balance of Pa and 50 ℃;
4. getting the carbon containing ionic liquid that Cotton Pulp particle that 23g processes through super-dry and milled processed cross evenly mixes, place dissolver, under 90 ℃, through stirring, vacuum dissolving 5 hours, namely obtain the spinning solution for the preparation of carbon/cellulose composite fiber of black;
5. after the temperature of aforesaid spinning solution for the preparation of carbon/cellulose composite fiber being adjusted to 90～95 ℃, spinnerets ejection through 100 holes, aperture 0.15mm, be the air gap layer of 80mm by length, enter solidification forming in the deionized water, obtain carbon content and be carbon/cellulose composite fiber of 8% behind washing and drying, its electrical conductivity of fibres order of magnitude is 10
7Ω .cm.
Embodiment 2:
1. with nano carbon black and the CNT mass ratio according to 1: 15, put into concentration and be 95% sulfuric acid and added hot reflux 36 hours, after filtration, obtain nano carbon black and the carbon nano tube of purifying after the cleaning, drying;
2. be under the infrared lamp of 1000w at power, with nano-sized carbon material and 255g ionic liquid mixed grinding in the agate mill of 3g purifying, grinding rate 70r/min, milling time 1.5 hours;
3. be 800 cellulose cotton pulp with the degree of polymerization, with food masher pulp be ground into the particle that diameter is 2 μ m～5 μ m, these cotton pulp particles are placed on vacuum-10 * 10 with cotton bag parcel
4Dry 5 hours of the lower balance of Pa and 50 ℃;
4. getting the carbon containing ionic liquid that Cotton Pulp particle that 17g processes through super-dry and milled processed cross evenly mixes, place dissolver, under 105 ℃, through stirring, vacuum dissolving 6 hours, namely obtain the spinning solution for the preparation of carbon/cellulose composite fiber of black;
5. after the temperature of aforesaid spinning solution for the preparation of carbon/cellulose composite fiber being adjusted to 95～100 ℃, spinnerets ejection through 100 holes, aperture 0.2mm, be the air gap layer of 100mm by length, enter solidification forming in the deionized water, obtain carbon content and be carbon/cellulose composite fiber of 15% behind washing and drying, its electrical conductivity of fibres order of magnitude is 10
4Ω .cm.
Embodiment 3:
1. with nano carbon black and the CNT mass ratio according to 1: 18, put into chloroazotic acid and added hot reflux 24 hours, after filtration, obtain nano carbon black and the carbon nano tube of purifying after the cleaning, drying;
2. be under the infrared lamp of 500w at power, with nano-sized carbon material and 517.5g ionic liquid mixed grinding in the agate mill of 5g purifying, grinding rate 70r/min, milling time 4 hours;
3. be 900 cellulose wood pulp with the degree of polymerization, with food masher pulp be ground into the particle that diameter is 2 μ m～5 μ m, these cotton pulp particles are placed on vacuum-10 * 10 with cotton bag parcel
4Dry 5 hours of the lower balance of Pa and 60 ℃;
4. getting the carbon containing ionic liquid that Cotton Pulp particle that 45g processes through super-dry and milled processed cross evenly mixes, place dissolver, under 100 ℃, through stirring, vacuum dissolving 6 hours, namely obtain the spinning solution for the preparation of carbon/cellulose composite fiber of black;
5. after the temperature of aforesaid spinning solution for the preparation of carbon/cellulose composite fiber being adjusted to 90～95 ℃, spinnerets ejection through 100 holes, aperture 0.15mm, enter solidification forming in the deionized water, obtain carbon content and be carbon/cellulose composite fiber of 10% behind washing and drying, its electrical conductivity of fibres order of magnitude is 10
5Ω .cm.
Claims (6)
1. the preparation method of the cellulose fibre of a carbon containing is characterized in that may further comprise the steps:
(1) nano carbon black and CNT are according to 1: 10～1: 20 quality proportioning and carry out purification process;
(2) will under infrared light, grind after the mixing of nano-sized carbon material and ionic liquid behind the purifying, the infrared lamp power selection is 500w～1200w, nano-sized carbon material and ionic liquid grind in the agate mill, and grinding rate is 40r/min～70r/min, and milling time is 1～4 hour;
(3) utilize ground carbon containing ionic liquid to be solvent, prepare certain density cellulose spinning fluid;
(4) cellulose spinning fluid for preparing is adopted dry-jet wet spinning process or wet spinning process, adopting deionized water is that solvent can obtain fiber of the present invention.
2. preparation method according to claim 1 is characterized in that nano carbon black and CNT gross weight are 8～15% of cellulose gross weight.
3. preparation method according to claim 1 is characterized in that, the purification process of nano carbon black and CNT comprises the steps:
The nano-sized carbon material be impregnated in the acid solution, and acid solution refluxes at a certain temperature, and then the impurity of carbon nano tube surface obtain the nano-sized carbon material of purifying via the oxidation removal of acid solution after washed with de-ionized water, filtration, drying.
4. preparation method according to claim 3 is characterized in that, acid solution comprises chloroazotic acid, nitric acid, sulfuric acid.
5. preparation method according to claim 1 is characterized in that:
(1) with the degree of polymerization is 300～1200 cellulose cotton pulp or wood pulp, is ground into the particle of 2-5 μ m with food masher, 50～70 ℃ of lower vacuumizes 5～12 hours;
(2) carbon containing ion liquid solvent and the dry cellulose grain weight ratio with 16: 1～10: 1 is joined in the dissolver, under 90 ℃～110 ℃ through stirring, dissolving is 2-6 hour under the condition that vacuumizes, and namely obtains the spinning solution for the preparation of carbon/cellulose composite fiber.
6. preparation method according to claim 5, it is characterized in that the temperature of aforementioned spinning solution for the preparation of carbon/cellulose composite fiber is adjusted to 80～100 ℃, spray through spinnerets, air gap by 10～150mm is behind the air layer between spinning plate surface and the coagulating bath face, enter the deionized water solidification forming, through washing, obtain nano-sized carbon substance weight content after the drying and be carbon/cellulose composite fiber of 8%～15%, perhaps adopt the mode of wet spinning, spinning solution sprays through spinnerets, enter solidification forming in the deionized water, through washing, obtain nano-sized carbon substance weight content after the drying and be carbon/cellulose composite fiber of 8%～15%.
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| CN 201010589210 CN102102231B (en) | 2010-12-15 | 2010-12-15 | Method for preparing conductive cellulose fibers |
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| CN 201010589210 CN102102231B (en) | 2010-12-15 | 2010-12-15 | Method for preparing conductive cellulose fibers |
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| CN102102231B true CN102102231B (en) | 2013-02-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3075227A1 (en) * | 2017-12-18 | 2019-06-21 | Association Pour Le Developpement De L'enseignement Et Des Recherches Aupres Des Universites, Des Centres De Recherche Et Des Entreprises D'aquitaine (Adera) | PROCESS FOR PRODUCING A CARBON FIBER FROM RECYCLED COTTON AND USING THE FIBER THUS OBTAINED FOR FORMING AN ARTICLE IN COMPOSITE MATERIAL |
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|---|---|---|---|---|
| CN103225173B (en) * | 2013-05-17 | 2015-11-25 | 天津工业大学 | A kind of preparation method of Cellulose/carbon nano tube composite nanofiber membrane |
| CN104086783B (en) * | 2014-07-08 | 2016-06-29 | 黑龙江大学 | A kind of method utilizing ionic liquid to prepare graphene oxide/CNT/cellulose pluralgel |
| CN104594077B (en) * | 2015-01-14 | 2017-06-13 | 中国科学院过程工程研究所 | The preparation method of ionic liquid carbon conductive nano solution and conductive fiber |
| CN105862156B (en) * | 2016-05-27 | 2018-05-08 | 北京林业大学 | A kind of cellulose/hydroxyl multi-walled carbon nano-tube/Fe3O4Nano-particles reinforcement fiber and preparation method thereof |
| CN106435797B (en) * | 2016-09-21 | 2018-11-23 | 东华大学 | A kind of preparation method of cellulose/carbon nano composite fibre |
| CN106435817B (en) * | 2016-09-21 | 2019-01-15 | 东华大学 | A kind of preparation method of functional regeneration cellulose fibre |
| CN106700329A (en) * | 2016-12-07 | 2017-05-24 | 西南交通大学 | Preparation method of antistatic ultra-flexible coal mine ventilating duct |
| CN109097870A (en) * | 2017-06-21 | 2018-12-28 | 中国科学院过程工程研究所 | Ionic liquid is the method that solvent wet spinning prepares Far-infrared carbon nano-conductive fiber |
| CN109930188A (en) * | 2019-01-31 | 2019-06-25 | 山东金宝电子股份有限公司 | A method of holey copper is prepared based on conductive fiber |
| JP7224256B2 (en) * | 2019-07-24 | 2023-02-17 | オーミケンシ株式会社 | Carbon nanotube-containing cellulose fiber and method for producing the same |
| CN115559011B (en) * | 2022-09-29 | 2024-01-26 | 武汉纺织大学 | Anisotropic organic-inorganic hybrid ionic liquid gel fiber and preparation method thereof |
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| CN1587457A (en) * | 2004-07-15 | 2005-03-02 | 东华大学 | Process for preparing precursor fiber of cellulose base carbon fiber |
| JP2005219964A (en) * | 2004-02-05 | 2005-08-18 | Teijin Ltd | Method for treating single-wall carbon nanotube, method for producing dispersion of single-wall carbon nanotube, obtained single-wall carbon nanotube, and dispersion of single-wall carbon nanotube |
| CN101016659A (en) * | 2007-01-26 | 2007-08-15 | 东华大学 | Method of preparing Lyocell fiber containing carbon nano tube |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005219964A (en) * | 2004-02-05 | 2005-08-18 | Teijin Ltd | Method for treating single-wall carbon nanotube, method for producing dispersion of single-wall carbon nanotube, obtained single-wall carbon nanotube, and dispersion of single-wall carbon nanotube |
| CN1587457A (en) * | 2004-07-15 | 2005-03-02 | 东华大学 | Process for preparing precursor fiber of cellulose base carbon fiber |
| CN101016659A (en) * | 2007-01-26 | 2007-08-15 | 东华大学 | Method of preparing Lyocell fiber containing carbon nano tube |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3075227A1 (en) * | 2017-12-18 | 2019-06-21 | Association Pour Le Developpement De L'enseignement Et Des Recherches Aupres Des Universites, Des Centres De Recherche Et Des Entreprises D'aquitaine (Adera) | PROCESS FOR PRODUCING A CARBON FIBER FROM RECYCLED COTTON AND USING THE FIBER THUS OBTAINED FOR FORMING AN ARTICLE IN COMPOSITE MATERIAL |
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