CN102839448A - Anti-static carbon-based fiber and preparation method and application thereof - Google Patents
Anti-static carbon-based fiber and preparation method and application thereof Download PDFInfo
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- CN102839448A CN102839448A CN2012103702187A CN201210370218A CN102839448A CN 102839448 A CN102839448 A CN 102839448A CN 2012103702187 A CN2012103702187 A CN 2012103702187A CN 201210370218 A CN201210370218 A CN 201210370218A CN 102839448 A CN102839448 A CN 102839448A
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- based fibers
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Abstract
The invention discloses an anti-static carbon-based fiber, which is prepared by using precursor fiber as a raw material and pre-oxidizing and carbonizing the raw material, wherein the precursor comprises the following components: more than or equal to 90 percent by weight of acrylonitrile, 0.1-10 percent by weight of amine itaconic acid, 0.1-2 percent by weight of ferrocene, and the balance of one of itaconic acid, crylic acid, methyl acrylate and methacrylic acid. In the anti-static carbon-based fiber, the resistivity is (1x10<3>-1.5x10<-2>) Omega/cm, the dielectric loss is less than 0.05, the anti-static carbon-based fiber has the characteristics of wide resistivity range and low dielectric loss, and serves as an anti-static additive to prepare an anti-static coating, the demand of the special field having different anti-static requirements can be met, the obtained anti-static coating has good impact resistance, abrasion resistance and corrosion resistance, and high requirement of special field such as airplane, guided missile, naval vessel, oil tank, electronic industry and the like on static protection is met.
Description
Technical field
The present invention relates to a kind of carbon based fibers with wide region resistivity and low-dielectric loss characteristic, its preparation method reaches in the antistatic Application for Field, belongs to field of new.
Background technology
Static is produced by phase mutual friction or the induction between object, like the conveying and the discharge of gas, the stirring of liquid and spraying; The pulverizing of solid and grinding, the mixing of dust and screening etc. all can produce static; Electrostatic defending has carelessness slightly; Just possibly cause fire, blast and the person to get an electric shock, then disturb ordinary production sometimes and influence product quality, therefore must take practicable safeguard procedures static.Often be employed in product or surface of the work spraying anti-static coatings in the commercial production and reach the purpose of eliminating electrostatic hazard.
In the existing anti-static coatings, the main additive that plays anti-static electrification is metal powder or graphite powder, though the two has good electrical conductivity; But metal powder is prone to oxidation; The graphite powder poor adhesive force, and in coating, all be difficult to form continuous conductive network, can not reach desirable anti-static effect; Particularly metal powder and graphite powder etc. are prone to reflection to radar wave, and dielectric loss is big, is not suitable as antistatic material and is used for key areas such as Aeronautics and Astronautics and military project.The final in addition anti-static coating that forms also should have performances such as good impact resistance, ABRASION RESISTANCE and corrosion resistance, and used anti-static coatings is difficult to satisfy fully these requirements.Publication number is the preparation method that the Chinese patent of CN1632002A discloses a kind of anti-static coatings, and mainly mixed with expanded graphite meterial and organic binder matter and solvent etc., its electric conductivity and impact resistance are relatively poor; Publication number is that the Chinese patent of CN1422919A discloses a kind of nano polyurethane antistatic coating and preparation method thereof, and mainly mixed as conductive agent and nano-polyurethane with mica, ABRASION RESISTANCE improves, but conductive effect is relatively poor; Publication number is the preparation method that the Chinese patent of CN1085927A discloses a kind of anti-static coatings, and mainly being that aluminium powder and polyurethane etc. are mixed gets, and performances such as its electric conductivity and ABRASION RESISTANCE are also undesirable.Carbon fiber has performances such as good electrical conductivity, corrosion resistance and ABRASION RESISTANCE; It is the additive of comparatively ideal anti-static coatings; Publication number is that the Chinese patent of CN1664034A discloses a kind of carbon fiber static-conducting coating and preparation method thereof; Graphited chopped carbon fiber and epoxy resin is mixed; Electric conductivity and corrosion resistance etc. are better, but because graphite fibre or high temperature cabonization fiber are the strong reflector of radar wave, the disclosed carbon fiber static-conducting coating of this patent can not satisfy the specific (special) requirements of fields such as aircraft and military project to the critical component electrostatic defending equally.Publication number is that the Chinese patent of CN101220535A discloses a kind of antistatic carbon fiber and preparation method thereof; Be that polyacrylonitrile fibre (being processed acrylonitrile and itaconic acid, acrylic acid, itaconic acid amine, methyl acrylate, methacrylic acid etc.) is prepared from through pre-oxidation, middle temperature carbonization, high temperature cabonization, its resistivity is 1 * 10
8~1.5 * 10
-3Ω cm, dielectric loss is high, can not satisfy the high request of special dimensions such as aircraft, guided missile, naval vessels, oil tank, electron trade to electrostatic defending.
Summary of the invention
To above-mentioned prior art; The invention provides a kind of antistatic carbon based fibers with wide electrical resistivity range and low-dielectric loss characteristic; And preparation method thereof; Utilize carbon based fibers of the present invention not only to have good impact resistance, ABRASION RESISTANCE and corrosion resistance, and have the good anti-static performance, thereby satisfy the high request of special dimensions such as aircraft, guided missile, naval vessels, oil tank, electron trade electrostatic defending as the antistatic networking coating that antistatic additive forms.
The present invention realizes through following technical scheme:
A kind of antistatic carbon based fibers is that somatic nerve fiber was a raw material in the past, prepares through following method:
(1) pre-oxidation: the precursor fiber is kept tensioning state, in air dielectric, heat-treat in 190~280 ℃, degree of draft is 0~10%, and be 45~65min heat time heating time;
(2) carbonization: after the above-mentioned pre-oxidation, heat-treat in 300~1200 ℃ under inert gas shielding or in the vacuum state, degree of draft is 0~5%, and be 5~20min heat time heating time, promptly gets the antistatic carbon based fibers.
The composition of said precursor fiber consists of: acrylonitrile content is more than or equal to 90wt%, itaconic acid amine 0.1~10wt%, and ferrocene 0.1~2wt%, surplus is a kind of in itaconic acid, acrylic acid, methyl acrylate, the methacrylic acid.
Said precursor fiber prepares through following method: acrylonitrile and other monomers are carried out combined polymerization, obtain spinning solution, make the precursor fiber through wet spinning or dry-jet wet-spinning.
The preparation method of said antistatic carbon based fibers, the same.
Antistatic carbon based fibers of the present invention, carbon content be greater than 68%, fibre diameter 1~10um, and resistivity is 1 * 10
3~1.5 * 10
-2Ω cm; Dielectric loss is less than 0.05; Have wide electrical resistivity range and low-dielectric loss characteristic; Prepare anti-static coating as antistatic additive, can satisfy the needs of the special dimension of different preventing static requirement, and the anti-static coating that obtains has good impact resistance, ABRASION RESISTANCE and corrosion resistance simultaneously.
Concrete application mode is: antistatic carbon based fibers weak point of the present invention is cut to 3~6mm, by volume the antistatic carbon based fibers: polyurethane coating: solvent cyclohexanone=0.005: (0.8~1.2): the ratio of (3~5) is prepared burden and conventional method prepares anti-static coating.Preferred ratio is: antistatic carbon based fibers: polyurethane coating: solvent cyclohexanone=0.005:1:4.
The present invention has prepared the precursor fiber through acrylonitrile, itaconic acid amine and the ferrocene etc. of specific proportion relation; And through specific pre-oxidation and carburising step, technological parameter; Prepared antistatic carbon based fibers with wide electrical resistivity range and low-dielectric loss characteristic; It prepares anti-static coating as antistatic additive; Can satisfy the needs of the special dimension of different preventing static requirement, and the anti-static coating that obtains has good impact resistance, ABRASION RESISTANCE and corrosion resistance simultaneously, thereby satisfy the high request of special dimensions such as aircraft, guided missile, naval vessels, oil tank, electron trade electrostatic defending.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1 preparation antistatic carbon based fibers
Step is following:
(1) proportion relation by acrylonitrile 97wt%, itaconic acid amine 2wt%, ferrocene 0.1wt% and itaconic acid 0.9wt% takes by weighing each monomer, and carries out combined polymerization, and wet spinning makes the precursor fiber.
(2) the precursor fiber carries out pre-oxidation under 270 ℃, degree of draft 5%, heat time heating time 45min, then in vacuum condition, 700 ℃ of following carbonizations, degree of draft 5%, heat time heating time, 10min promptly got the antistatic carbon based fibers, its diameter is 7um, resistivity is 1.5~5 * 10
-2Ω cm, carbon content is greater than 90%.
This carbon based fibers weak point is cut to 3~6mm; In carbon based fibers: polyurethane coating: the ratio of solvent cyclohexanone=0.005:1:4 (volume ratio) is prepared burden and is obtained anti-static coating; Recording insulating resistance value is 1.1~9.5M Ω; Dielectric loss 0.046 less than 0.05, can satisfy the specific (special) requirements to electrostatic defending such as aircraft.
Embodiment 2 preparation antistatic carbon based fibers
Step is following:
(1) proportion relation by acrylonitrile 92wt%, itaconic acid amine 0.1wt%, ferrocene 2wt% and methyl acrylate 5.9wt% takes by weighing each monomer, and carries out combined polymerization, and wet spinning makes the precursor fiber.
(2) the precursor fiber carries out pre-oxidation under 190 ℃, degree of draft 8%, heat time heating time 65min; Then in inert gas shielding, 1200 ℃ of following carbonizations, degree of draft 2%, heat time heating time 20min; Promptly get the antistatic carbon based fibers, its diameter 7um, resistivity is 2.5~6.0 * 10
-1Ω cm, carbon content is greater than 74%.
This carbon based fibers weak point is cut to 3~6mm; In carbon based fibers: polyurethane coating: the ratio of solvent cyclohexanone=0.005:1:4 (volume ratio) is prepared burden and is obtained anti-static coating; Recording insulating resistance value is 0.1~5M Ω; Dielectric loss 0.048 less than 0.05, can satisfy the specific (special) requirements to electrostatic defending such as aircraft.
Embodiment 3 preparation antistatic carbon based fibers
Step is following:
(1) proportion relation by acrylonitrile 98wt%, itaconic acid amine 1wt%, ferrocene 0.2wt% and acrylic acid 0.8wt% takes by weighing each monomer, and carries out combined polymerization, and wet spinning makes the precursor fiber.
(2) the precursor fiber carries out pre-oxidation under 250 ℃, degree of draft 7%, and heat time heating time, 50min carried out carbonization then under vacuum condition, 900 ℃, degree of draft 3%, heat time heating time, 15min promptly got the antistatic carbon based fibers, its diameter 10um, resistivity is 5~9 * 10
-2Ω cm, carbon content is greater than 82%.
This carbon based fibers weak point is cut to 2~4mm; In carbon based fibers: polyurethane coating: the ratio of solvent cyclohexanone=0.005:1:4 (volume ratio) is prepared burden and is obtained anti-static coating; Recording insulating resistance value is 1~15M Ω; Dielectric loss 0.035 less than 0.05, can satisfy the specific (special) requirements to electrostatic defending such as aircraft.
Embodiment 4 preparation antistatic carbon based fibers
Step is following:
(1) proportion relation by acrylonitrile 90wt%, itaconic acid amine 3.8wt%, ferrocene 0.2wt% and methyl acrylate 6% takes by weighing each monomer, and carries out combined polymerization, and dry-wet spinning makes the precursor fiber.
(2) the precursor fiber carries out pre-oxidation under 230 ℃, degree of draft 10%, heat time heating time 55min; Then in inert gas shielding, 1000 ℃ of following carbonizations, degree of draft 3%, heat time heating time 15min; Promptly get the antistatic carbon based fibers, its diameter 6um, resistivity is 1~10 * 10
2Ω cm, carbon content is greater than 68%.
This carbon based fibers weak point is cut to 3~6mm; In carbon based fibers: polyurethane coating: the ratio of solvent cyclohexanone=0.005:1:4 (volume ratio) is prepared burden and is obtained anti-static coating; Recording insulating resistance value is 15~60M Ω; Dielectric loss 0.031 less than 0.05, can satisfy the specific (special) requirements to electrostatic defending such as aircraft.
Embodiment 5 preparation antistatic carbon based fibers
Step is following:
(1) proportion relation by acrylonitrile 96wt%, itaconic acid 4wt% takes by weighing each monomer, and carries out combined polymerization, and wet spinning makes the precursor fiber.
(2) the precursor fiber carries out pre-oxidation under 240 ℃, degree of draft 10%, and heat time heating time, 55min carried out high temperature cabonization then under inert gas shielding, 1000 ℃, promptly got the antistatic carbon based fibers, its diameter 7um, resistivity is 1.5~5 * 10
-3Ω cm, carbon content is greater than 94%.
This carbon based fibers weak point is cut to 3~6mm; In carbon based fibers: polyurethane coating: the ratio of solvent cyclohexanone=0.005:1:4 (volume ratio) is prepared burden and is obtained anti-static coating; Recording insulating resistance value is 0.001~0.1M Ω; Dielectric loss 0.163 greater than 0.15, can not satisfy the specific (special) requirements to electrostatic defending such as aircraft.
Claims (9)
1. antistatic carbon based fibers is characterized in that: somatic nerve fiber was a raw material before being, prepared through following method:
(1) pre-oxidation: the precursor fiber is kept tensioning state, in air dielectric, heat-treat in 190~280 ℃, degree of draft is 0~10%, and be 45~65min heat time heating time;
(2) carbonization: after the above-mentioned pre-oxidation, heat-treat in 300~1200 ℃ under inert gas shielding or in the vacuum state, degree of draft is 0~5%, and be 5~20min heat time heating time, promptly gets the antistatic carbon based fibers;
The composition of said precursor fiber consists of: acrylonitrile content is more than or equal to 90wt%, itaconic acid amine 0.1~10wt%, and ferrocene 0.1~2wt%, surplus is a kind of in itaconic acid, acrylic acid, methyl acrylate, the methacrylic acid.
2. a kind of antistatic carbon based fibers according to claim 1; It is characterized in that: said precursor fiber prepares through following method: acrylonitrile and other monomers are carried out combined polymerization; Obtain spinning solution, make the precursor fiber through wet spinning or dry-jet wet-spinning.
3. a kind of antistatic carbon based fibers according to claim 1, it is characterized in that: the composition of said precursor fiber consists of one of following combination:
1. acrylonitrile 97wt%, itaconic acid amine 2wt%, ferrocene 0.1wt% and itaconic acid 0.9wt%;
2. acrylonitrile 92wt%, itaconic acid amine 0.1wt%, ferrocene 2wt% and methyl acrylate 5.9wt%;
3. acrylonitrile 98wt%, itaconic acid amine 1wt%, ferrocene 0.2wt% and acrylic acid 0.8wt%;
4. acrylonitrile 90wt%, itaconic acid amine 3.8wt%, ferrocene 0.2wt% and methyl acrylate 6%.
4. the preparation method of each described a kind of antistatic carbon based fibers in the claim 1~3, it is characterized in that: step is following:
(1) pre-oxidation: the precursor fiber is kept tensioning state, in air dielectric, heat-treat in 190~280 ℃, degree of draft is 0~10%, and be 45~65min heat time heating time;
(2) carbonization: after the above-mentioned pre-oxidation, heat-treat in 300~1200 ℃ under inert gas shielding or in the vacuum state, degree of draft is 0~5%, and be 5~20min heat time heating time, promptly gets the antistatic carbon based fibers.
5. the application of each described a kind of antistatic carbon based fibers in the preparation anti-static coating in the claim 1~3.
6. application according to claim 5; It is characterized in that: application mode is: antistatic carbon based fibers weak point is cut to 3~6mm, by volume the antistatic carbon based fibers: polyurethane coating: solvent cyclohexanone=0.005: (0.8~1.2): the ratio of (3~5) is prepared burden and is prepared anti-static coating.
7. application according to claim 6 is characterized in that: said antistatic carbon based fibers: polyurethane coating: solvent cyclohexanone=0.005:1:4.
8. anti-static coating; It is characterized in that: prepared by following method: each described antistatic carbon based fibers weak point in the claim 1~3 is cut to 3~6mm, by volume the antistatic carbon based fibers: polyurethane coating: solvent cyclohexanone=0.005: (0.8~1.2): the ratio of (3~5) is prepared burden and is prepared anti-static coating.
9. anti-static coating according to claim 8 is characterized in that: said antistatic carbon based fibers: polyurethane coating: solvent cyclohexanone=0.005:1:4.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105623490A (en) * | 2016-03-23 | 2016-06-01 | 山东大学 | Wave-transparent antistatic coating, and preparation method and application thereof |
CN109276824A (en) * | 2018-09-27 | 2019-01-29 | 国网河南省电力公司内乡县供电公司 | A kind of electric power overhaul dedicated safety belt |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08311722A (en) * | 1995-05-16 | 1996-11-26 | Sgl Technik Gmbh | Method and apparatus for manufacturing polydimensional sheetstructure consisting of polyacrylonitrile fiber |
CN101220535A (en) * | 2008-01-23 | 2008-07-16 | 山东大学 | Antistatic carbon fiber and preparation thereof |
CN102465360A (en) * | 2010-11-16 | 2012-05-23 | 晓健科技(大连)有限公司 | Anti-static phosgene modified polyacrylonitrile carbon fiber |
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2012
- 2012-09-28 CN CN201210370218.7A patent/CN102839448B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08311722A (en) * | 1995-05-16 | 1996-11-26 | Sgl Technik Gmbh | Method and apparatus for manufacturing polydimensional sheetstructure consisting of polyacrylonitrile fiber |
CN101220535A (en) * | 2008-01-23 | 2008-07-16 | 山东大学 | Antistatic carbon fiber and preparation thereof |
CN102465360A (en) * | 2010-11-16 | 2012-05-23 | 晓健科技(大连)有限公司 | Anti-static phosgene modified polyacrylonitrile carbon fiber |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105623490A (en) * | 2016-03-23 | 2016-06-01 | 山东大学 | Wave-transparent antistatic coating, and preparation method and application thereof |
CN105623490B (en) * | 2016-03-23 | 2018-05-11 | 山东大学 | A kind of wave transparent antistatic coating and preparation method and application |
CN109276824A (en) * | 2018-09-27 | 2019-01-29 | 国网河南省电力公司内乡县供电公司 | A kind of electric power overhaul dedicated safety belt |
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