CN101338463A - Method for preparing PBO/single-wall carbon nanotube composite fiber - Google Patents
Method for preparing PBO/single-wall carbon nanotube composite fiber Download PDFInfo
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- CN101338463A CN101338463A CNA2008101368871A CN200810136887A CN101338463A CN 101338463 A CN101338463 A CN 101338463A CN A2008101368871 A CNA2008101368871 A CN A2008101368871A CN 200810136887 A CN200810136887 A CN 200810136887A CN 101338463 A CN101338463 A CN 101338463A
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- carbon nanotube
- walled carbon
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Abstract
A preparation method of the composite fiber of a PBO/single-walled carbon nano-tube relates to the preparation method of the composite fiber. The invention solves the problems existing in the prior art of poor thermal stability and low tensile-strength. The preparation method has procedures as follows: after undergoing the processes of heating and vacuum defoamation, the polymer of the PBO/single-walled carbon nano-tube settles for 12h to 72h under the protection of N2 and under the temperature of 160 DEG C to 200 DEG C to prepare spinning dope; the spinning dope is filtered by a filter screen and goes through a spinneret plate; obtained silk is drawn under the protection of N2 and under conditions that the length of an air-gap is 10cm to 15cm and draw ratio is 1 to 150; then the silk undergoes the processes of coagulation bath and water bath and the composite fiber is made. The tensile strength of the composite fiber of the PBO/single-walled carbon nano-tube prepared by the invention reaches the maximum of 5.4GPa when the addition of the carbon nano-tube is 7.5mass percent, thus increasing by 60 percent compared with PBO fiber. The test shows that the composite fiber of the PBO/single-walled carbon nano-tube prepared by the invention is better than the PBO fiber in high temperature resistance under air and argon atmosphere.
Description
Technical field
The present invention relates to a kind of preparation method of composite fibre.
Background technology
With 4,6-diamino resorcin hydrochlorate (DADHB) and terephthalic acid (TPA) (PTA) are polymerization single polymerization monomer, polycondensation can get liquid crystal PBO (Poly-p-phenylene-benzobisthiazole) polymer in polyphosphoric acids, adopt dried spray-wet spinning technology can make pbo fiber, structural formula is as follows:
Pbo fiber is the abbreviation of polyparaphenylene's benzo-dioxazole fiber (Poly-p-phenylene-benzobisthiazole), is to contain the most rising in the polyamide family of a heteroaromatic member, is the present the highest industrial fiber of intensity in the world.Its TENSILE STRENGTH reaches 5.8GPa, and stretch modulus is 280～380GPa, and heat decomposition temperature is up to 650 ℃, and density only is 1.56 * 10
3Kg/m
3
Single Walled Carbon Nanotube (Single-walled nanotubes, SWNT) thisly curl and the CNT that forms is the graphite that continues by graphite flake layer, diamond, the carbon of another simple substance form of finding after the fullerene, U.S. carbon nanotube technology company (Carbon Nanotechnologies Inc.C-NI) adds 10wt% Single Walled Carbon Nanotube (SWNT) and makes the PBO/SWNT composite fibre in PBO, through experimental study, this composite fibre is two times of pure PBO to the absorbent properties of energy, its TENSILE STRENGTH can reach more than the 8GPa, its combination property has surpassed pbo fiber, causes widely and pays close attention to.But pbo fiber of the prior art exists poor heat stability, problem that TENSILE STRENGTH is low.
Summary of the invention
The objective of the invention is provides a kind of preparation method of PBO/ Single Walled Carbon Nanotube composite fibre in order to solve the low problem of poor heat stability, TENSILE STRENGTH that pbo fiber of the prior art exists.
The preparation method of PBO/ Single Walled Carbon Nanotube composite fibre of the present invention is as follows: one, the PBO/ single-wall carbon nanotube polymer is heated to 160 ℃～200 ℃, be vacuum defoamation 12h～72h under-0.08～-0.09 the condition at the vacuum meter reading then, again at 160 ℃～200 ℃, N
2Sedimentation 12h～72h makes spinning solution in the atmosphere; Two, spinning solution is 80～800 purpose filter screens by 5～10 layers of fineness at 160 ℃～200 ℃, pressure under less than the condition of 30MPa, and via hole diameter is the spinnerets spray silk of 0.15mm～0.8mm then; Three, at N
2Atmosphere, air-gap length are that 10cm～50cm, draw ratio are wire drawing under 1～150 the condition, and stretched silk is that 40 ℃～100 ℃ washing is bathed through excess temperature after 2～5 groups of coagulating baths again, promptly gets PBO/ Single Walled Carbon Nanotube composite fibre; Wherein coagulating bath is made of phosphate aqueous solution in the step 3, and phosphate aqueous solution concentration reduces successively, and temperature raises successively, and first coagulating bath concentration is that 60mass%, temperature are-20 ℃, and end coagulating bath concentration is that 0.1mass%, temperature are 40 ℃; Washing in the step 3 is bathed by the NaHCO of concentration less than 10mass%
3Or KHCO
3The aqueous solution constitutes.
Spinning pressure is by piston or N in the step 2 of the present invention
2Provide.
Find out that by Fig. 1 SWNT roughly arranges (being the fiber axial direction) along same direction.The formation of this structure makes PBO/ Single Walled Carbon Nanotube composite fibre than pbo fiber higher intensity and heat resisting temperature (see figure 3) be arranged.Find out that by Fig. 2 the TENSILE STRENGTH of pbo fiber is 3.2GPa, in Single Walled Carbon Nanotube content is 0～7.5mass% scope, the TENSILE STRENGTH of the PBO/ Single Walled Carbon Nanotube composite fibre of the present invention's preparation increases along with the increase of CNT addition, addition reaches maximum 5.4GPa during for 7.5mass%, has increased by 60% than pbo fiber.Find out that by Fig. 3 two kinds of fibers have all demonstrated good heat endurance.Pbo fiber is under air atmosphere, and pbo fiber weightlessness 5% when temperature is 590 ℃, reason may be end group or the oxidized decomposition of weak bond; When temperature reaches 750 ℃, pbo fiber remnants 4%.The PBO/ Single Walled Carbon Nanotube composite fibre of the present invention's preparation did not have tangible changes in weight under the air atmosphere before 600 ℃.When temperature reached 750 ℃, its weight maintained 15%.As seen the PBO/ Single Walled Carbon Nanotube composite fibre of the present invention's preparation is more high temperature resistant than pbo fiber under conditions of air.
Under argon gas atmosphere, the temperature of the thermal decomposition of two kinds of fibers has improved 100 ℃ than heat decomposition temperature under the air atmosphere.When temperature reached 750 ℃, the residual quantity of the PBO/ Single Walled Carbon Nanotube composite fibre of pbo fiber and the present invention's preparation was respectively 65%, 75%, and this shows that under argon gas atmosphere the PBO/ Single Walled Carbon Nanotube composite fibre of the present invention's preparation is more high temperature resistant than pbo fiber.
Description of drawings
Fig. 1 is a PBO/ Single Walled Carbon Nanotube composite fibre shape appearance figure.Fig. 2 is the TENSILE STRENGTH comparison diagram of PBO/ Single Walled Carbon Nanotube composite fibre and pbo fiber.Fig. 3 is PBO/ Single Walled Carbon Nanotube composite fibre and thermogravimetric (TG) the analytic curve figure of pbo fiber in air and argon gas, wherein a represents the thermogravimetric curve figure of airborne PBO/ Single Walled Carbon Nanotube composite fibre, b represents the thermogravimetric curve figure of airborne PBO/ Single Walled Carbon Nanotube composite fibre, c represents the thermogravimetric curve figure of the PBO/ Single Walled Carbon Nanotube composite fibre in the argon gas, and d represents the thermogravimetric curve figure of the PBO/ Single Walled Carbon Nanotube composite fibre in the argon gas.Fig. 4 is the flow chart of preparation PBO/ Single Walled Carbon Nanotube composite fibre.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre is as follows in the present embodiment:
One, the PBO/ single-wall carbon nanotube polymer being heated to 160 ℃～200 ℃, is vacuum defoamation 12h～72h under-0.08～-0.09 the condition at the vacuum meter reading, again at 160 ℃～200 ℃, N then
2Sedimentation 12h～72h makes spinning solution in the atmosphere; Two, spinning solution is 80～800 purpose filter screens by 5～10 layers of fineness at 160 ℃～200 ℃, pressure under less than the condition of 30MPa, and via hole diameter is the spinnerets spray silk of 0.15mm～0.8mm then; Three, at N
2Atmosphere, air-gap length are that 10cm～50cm, draw ratio are wire drawing under 1～150 the condition, and stretched silk is that 40 ℃～100 ℃ washing is bathed through excess temperature after 2～5 groups of coagulating baths again, promptly gets PBO/ Single Walled Carbon Nanotube composite fibre; Wherein coagulating bath is made of phosphate aqueous solution in the step 3, and phosphate aqueous solution concentration reduces successively, and temperature raises successively, and first coagulating bath concentration is that 60mass%, temperature are-20 ℃, and end coagulating bath concentration is that 0.1mass%, temperature are 40 ℃; Washing in the step 3 is bathed by the NaHCO of concentration less than 10mass%
3Or KHCO
3The aqueous solution constitutes.
The preparation method of PBO/ single-wall carbon nanotube polymer is as follows in the present embodiment: what one, will be used for the PBO polymerization contains the single wall carbon nano-tube monomer compound (applying date: on May 21st, 2008, application number; 200810064550.4 patent name is " preparation method who contains the single wall carbon nano-tube monomer compound who is used for the PBO polymerization ") mix according to 1: 3.2～4.5 mass ratio with polyphosphoric acids, be 1 ℃～80 ℃, N in temperature then
2Stir 12h～72h under the condition of protection and obtain mixed solution; Two, with temperature be 100～120 ℃ P
2O
5Join in the mixed solution of step 1 preparation, then at N
2Be warming up to 140 ℃～160 ℃ reaction 2h～10h under the condition of gas shiled; Three, the product that obtains of step 2 is extruded 1～10 time repeatedly with double screw extruder, promptly gets the PBO/ single-wall carbon nanotube polymer; P in the step 1 polyphosphoric acids wherein
2O
5Content be 82mass%～84.5mass%; P in the step 2
2O
5In 24h, join in the mixed solution of step 1 preparation; P in the step 2
2O
5With the mass ratio of the mixed solution of step 1 preparation be 1.2～1.5: 1; In the step 3 initial temperature of each section of double screw extruder screw rod be 180 ℃, by temperature be 210 ℃, reaction mass time of staying in screw rod is 5min～60min.
Present embodiment is as follows in conjunction with the preparation method of Fig. 4 (flow chart of preparation PBO/ Single Walled Carbon Nanotube composite fibre) PBO/ Single Walled Carbon Nanotube composite fibre: one, the PBO/ single-wall carbon nanotube polymer is heated to 160 ℃～200 ℃, be vacuum defoamation 12h～72h under-0.08～-0.09 the condition at the vacuum meter reading then, again at 160 ℃～200 ℃, N
2Sedimentation 12h～72h in the atmosphere makes spinning solution and then spinning solution is put into storage tank 1; Two, spinning solution is 80～800 purpose filter screens by 5～10 layers of fineness at 160 ℃～200 ℃, pressure under less than the condition of 30MPa, and via hole diameter is the spinnerets 2 spray silks of 0.15mm～0.8mm then; Three, at N
2Atmosphere, air-gap length are that 10cm～50cm, draw ratio are wire drawing under 1～150 the condition, stretched silk is 40 ℃～100 ℃ washing bath 4 again through excess temperature after 2～5 groups of coagulating baths 3, promptly get PBO/ Single Walled Carbon Nanotube composite fibre 5, the PBO/ Single Walled Carbon Nanotube composite fibre 5 that obtains is wound on the up-coiler 6 gets final product.
Fig. 1 is the PBO/ Single Walled Carbon Nanotube composite fibre shape appearance figure of present embodiment preparation, finds out that by Fig. 1 SWNT roughly arranges (being the fiber axial direction) along same direction.The formation of this structure makes PBO/ Single Walled Carbon Nanotube composite fibre than pbo fiber higher intensity and heat resisting temperature (see figure 3) be arranged.
The PBO/ Single Walled Carbon Nanotube composite fibre of present embodiment preparation and the TENSILE STRENGTH comparison diagram of pbo fiber are Fig. 2, find out that by Fig. 2 the TENSILE STRENGTH of pbo fiber is 3.2GPa, in Single Walled Carbon Nanotube content is 0～7.5mass% scope, the TENSILE STRENGTH of the PBO/ Single Walled Carbon Nanotube composite fibre of present embodiment preparation increases along with the increase of CNT addition, addition reaches maximum 5.4GPa during for 7.5mass%, has increased by 60% than pbo fiber.
The PBO/ Single Walled Carbon Nanotube composite fibre of present embodiment preparation and the thermogravimetric in air and argon gas (TG) the analytic curve figure of pbo fiber are Fig. 3, find out that by Fig. 3 two kinds of fibers have all demonstrated good heat endurance.Pbo fiber is under air atmosphere, and pbo fiber weightlessness 5% when temperature is 590 ℃, reason may be end group or the oxidized decomposition of weak bond; When temperature reaches 750 ℃, pbo fiber remnants 4%.The PBO/ Single Walled Carbon Nanotube composite fibre of present embodiment preparation did not have tangible changes in weight under the air atmosphere before 600 ℃.When temperature reached 750 ℃, its weight maintained 15%.As seen the PBO/ Single Walled Carbon Nanotube composite fibre of present embodiment preparation is more high temperature resistant than pbo fiber under conditions of air.
Under argon gas atmosphere, the temperature of the thermal decomposition of two kinds of fibers has improved 100 ℃ than heat decomposition temperature under the air atmosphere.When temperature reached 750 ℃, the residual quantity of the PBO/ Single Walled Carbon Nanotube composite fibre of pbo fiber and present embodiment preparation was respectively 65%, 75%; And during EOT, two kinds of fiber residual quantities are all more than 50%.This shows that under argon gas atmosphere the PBO/ Single Walled Carbon Nanotube composite fibre of present embodiment preparation is more high temperature resistant than pbo fiber.
The specific embodiment two: what present embodiment and the specific embodiment one were different is in the step 1 PBO/ single-wall carbon nanotube polymer to be heated to 161 ℃～180 ℃.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is in the step 1 PBO/ single-wall carbon nanotube polymer to be heated to 170 ℃.Other is identical with the specific embodiment one.
The specific embodiment four: what present embodiment and the specific embodiment one were different is in the step 1 PBO/ single-wall carbon nanotube polymer to be heated to 181 ℃～199 ℃.Other is identical with the specific embodiment one.
The specific embodiment five: what present embodiment and the specific embodiment one were different is in the step 1 PBO/ single-wall carbon nanotube polymer to be heated to 190 ℃.Other is identical with the specific embodiment one.
The specific embodiment six: present embodiment and the specific embodiment one are different be in the step 1 deaeration time be 12.2h～32h.Other is identical with the specific embodiment one.
The specific embodiment seven: present embodiment and the specific embodiment one are different be in the step step 1 deaeration time be 32.5h～71h.Other is identical with the specific embodiment one.
The specific embodiment eight: present embodiment and the specific embodiment one are different be in the step 2 spinning pressure by piston or N
2Provide.Other is identical with the specific embodiment one.
The specific embodiment nine: present embodiment and the specific embodiment one are different is to be spray silk under 161 ℃～180 ℃ the condition in temperature in the step 2.Other is identical with the specific embodiment one.
The specific embodiment ten: present embodiment and the specific embodiment one are different is to be spray silk under 170 ℃ the condition in temperature in the step 2.Other is identical with the specific embodiment one.
The specific embodiment 11: present embodiment and the specific embodiment one are different is to be spray silk under 181 ℃～199 ℃ the condition in temperature in the step 2.Other is identical with the specific embodiment one.
The specific embodiment 12: present embodiment and the specific embodiment one are different is to be spray silk under 190 ℃ the condition in temperature in the step 2.Other is identical with the specific embodiment one.
The specific embodiment 13: present embodiment and the specific embodiment one are different be in the step 2 spinning pressure by N
2Be less than 12MPa when providing.Other is identical with the specific embodiment one.
The specific embodiment 14: what present embodiment and the specific embodiment one were different is to constitute one group of coagulating bath, the wherein H of coagulating bath 1 by 2 coagulating baths in the step 3
3PO
4Concentration is 60mass%～30mass%, and temperature is-20 ℃～10 ℃; The H of coagulating bath 2
3PO
4Concentration is 30mass%～0mass%, and temperature is 10 ℃～40 ℃.Other is identical with the specific embodiment one.
The specific embodiment 15: what present embodiment and the specific embodiment one were different is to constitute one group of coagulating bath, the wherein H of coagulating bath 1 by 3 coagulating baths in the step 3
3PO
4Concentration is 60mass%～40mass%, and temperature is-20 ℃～0 ℃; The H of coagulating bath 2
3PO
4Concentration is 40mass%～20mass%, and temperature is 0 ℃～20 ℃; The H of coagulating bath 3
3PO
4Concentration is less than 20mass%, and temperature is 20 ℃～40 ℃.Other is identical with the specific embodiment one.
The specific embodiment 16: what present embodiment and the specific embodiment one were different is to constitute one group of coagulating bath, the wherein H of coagulating bath 1 by 4 coagulating baths in the step 3
3PO
4Concentration is 60mass%～45mass%, and temperature is-20 ℃～-5 ℃; The H of coagulating bath 2
3PO
4Concentration is 45mass%～30mass%, and temperature is-5 ℃～10 ℃; The H of coagulating bath 3
3PO
4Concentration is 30mass%～15mass%, and temperature is 10 ℃～25 ℃; The H of coagulating bath 4
3PO
4Concentration is less than 15mass%, and temperature is 25 ℃～40 ℃.Other is identical with the specific embodiment one.
The specific embodiment 17: present embodiment and the specific embodiment one are different is that the number of the coagulating bath in the step 3 is decided by the quality of the PBO/ Single Walled Carbon Nanotube composite fibre that finally makes.Other is identical with the specific embodiment one.
The specific embodiment 18: present embodiment and the specific embodiment one are different is that draw ratio in the step 3 is 2～50.Other is identical with the specific embodiment one.
The specific embodiment 19: present embodiment and the specific embodiment one are different is that draw ratio in the step 3 is 51～100.Other is identical with the specific embodiment one.
The specific embodiment 20: present embodiment and the specific embodiment one are different is that draw ratio in the step 3 is 101～149.Other is identical with the specific embodiment one.
The specific embodiment 21: present embodiment and the specific embodiment one are different is that draw ratio in the step 3 is 25.Other is identical with the specific embodiment one.
The specific embodiment 22: present embodiment and the specific embodiment one are different is that draw ratio in the step 3 is 75.Other is identical with the specific embodiment one.
The specific embodiment 23: present embodiment and the specific embodiment one are different is that draw ratio in the step 3 is 115.Other is identical with the specific embodiment one.
The specific embodiment 24: present embodiment and the specific embodiment one are different is that temperature in the step 3 is 41 ℃～50 ℃.Other is identical with the specific embodiment one.
The specific embodiment 25: present embodiment and the specific embodiment one are different is that temperature in the step 3 is 51 ℃～70 ℃.Other is identical with the specific embodiment one.
The specific embodiment 26: present embodiment and the specific embodiment one are different is that temperature in the step 3 is 71 ℃～99 ℃.Other is identical with the specific embodiment one.
The specific embodiment 27: present embodiment and the specific embodiment one are different is that temperature in the step 3 is 80 ℃.Other is identical with the specific embodiment one.
Claims (10)
1, a kind of preparation method of PBO/ Single Walled Carbon Nanotube composite fibre, the preparation method who it is characterized in that PBO/ Single Walled Carbon Nanotube composite fibre is as follows: one, the PBO/ single-wall carbon nanotube polymer is heated to 160 ℃～200 ℃, be vacuum defoamation 12h～72h under-0.08～-0.09 the condition at the vacuum meter reading then, again at 160 ℃～200 ℃, N
2Sedimentation 12h～72h makes spinning solution in the atmosphere; Two, spinning solution is 80～800 purpose filter screens by 5～10 layers of fineness at 160 ℃～200 ℃, pressure under less than the condition of 30MPa, and via hole diameter is the spinnerets spray silk of 0.15mm～0.8mm then; Three, at N
2Atmosphere, air-gap length are that 10cm～50cm, draw ratio are wire drawing under 1～150 the condition, and stretched silk is that 40 ℃～100 ℃ washing is bathed through excess temperature after 2～5 groups of coagulating baths again, promptly gets PBO/ Single Walled Carbon Nanotube composite fibre; Wherein coagulating bath is made of phosphate aqueous solution in the step 3, and phosphate aqueous solution concentration reduces successively, and temperature raises successively, and first coagulating bath concentration is that 60mass%, temperature are-20 ℃, and end coagulating bath concentration is that 0.1mass%, temperature are 40 ℃; Washing in the step 3 is bathed by the NaHCO of concentration less than 10mass%
3Or KHCO
3The aqueous solution constitutes.
2, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that in the step 1 PBO/ single-wall carbon nanotube polymer being heated to 161 ℃～180 ℃.
3, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that in the step 1 PBO/ single-wall carbon nanotube polymer being heated to 181 ℃～199 ℃.
4, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that spinning pressure is by piston or N in the step 2
2Provide.
5, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that spinning pressure is 12MPa in the step 2.
6, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that in the step 2 that in temperature be spray silk under 161 ℃～180 ℃ the condition.
7, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that in the step 2 that in temperature be spray silk under 170 ℃ the condition.
8, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that in the step 2 that in temperature be spray silk under 181 ℃～199 ℃ the condition.
9, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that the draw ratio in the step 3 is 75.
10, the preparation method of PBO/ Single Walled Carbon Nanotube composite fibre according to claim 1 is characterized in that the temperature in the step 3 is 80 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014901A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO (Poly-P-Phenylene Benzobisoxazazole) composite fiber |
| CN103254433A (en) * | 2013-05-21 | 2013-08-21 | 华东理工大学 | Preparation method of in-situ grafted composite material containing barium titanate-modified carbon nanotubes and benzoxazole ring polymer |
| CN104593901A (en) * | 2014-12-25 | 2015-05-06 | 东华大学 | Preparation method of polyamide grafted carbon nanotube (CNT) composite fiber |
| CN104894679A (en) * | 2015-06-04 | 2015-09-09 | 苏州市湘园特种精细化工有限公司 | Preparation method of carbon nanotube enhanced PBO composite fibers |
| CN111439744A (en) * | 2020-04-01 | 2020-07-24 | 福建滤冠新型材料科技有限公司 | Preparation method of graphene nanofiber membrane |
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| CN1226326C (en) * | 2003-07-18 | 2005-11-09 | 哈尔滨工业大学 | Synthesis method of PBO/carbon nanometer pipe composite material |
| US7425368B2 (en) * | 2004-08-20 | 2008-09-16 | Massachusetts Institute Of Technology | Filler-enhanced polymeric fibers with improved mechanical properties and method for making |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014901A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO (Poly-P-Phenylene Benzobisoxazazole) composite fiber |
| CN103014901B (en) * | 2012-12-12 | 2014-12-24 | 哈尔滨工业大学 | Preparation method of graphene/PBO (Poly-P-Phenylene Benzobisoxazazole) composite fiber |
| CN103254433A (en) * | 2013-05-21 | 2013-08-21 | 华东理工大学 | Preparation method of in-situ grafted composite material containing barium titanate-modified carbon nanotubes and benzoxazole ring polymer |
| CN103254433B (en) * | 2013-05-21 | 2015-04-15 | 华东理工大学 | Preparation method of in-situ grafted composite material containing barium titanate-modified carbon nanotubes and benzoxazole ring polymer |
| CN104593901A (en) * | 2014-12-25 | 2015-05-06 | 东华大学 | Preparation method of polyamide grafted carbon nanotube (CNT) composite fiber |
| CN104894679A (en) * | 2015-06-04 | 2015-09-09 | 苏州市湘园特种精细化工有限公司 | Preparation method of carbon nanotube enhanced PBO composite fibers |
| CN111439744A (en) * | 2020-04-01 | 2020-07-24 | 福建滤冠新型材料科技有限公司 | Preparation method of graphene nanofiber membrane |
| CN111439744B (en) * | 2020-04-01 | 2022-07-29 | 福建滤冠新型材料科技有限公司 | Preparation method of graphene nanofiber membrane |
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|---|---|
| CN101338463B (en) | 2010-06-02 |
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