CN1654515A - Method for preparing polymer/carbon nanotube composite gradient film - Google Patents
Method for preparing polymer/carbon nanotube composite gradient film Download PDFInfo
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- CN1654515A CN1654515A CN 200510016532 CN200510016532A CN1654515A CN 1654515 A CN1654515 A CN 1654515A CN 200510016532 CN200510016532 CN 200510016532 CN 200510016532 A CN200510016532 A CN 200510016532A CN 1654515 A CN1654515 A CN 1654515A
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Abstract
The present invention belongs to the field of interdisciplinary nanometer science and technology, and is the preparation process of nanometer composite gradient polymer/carbon film. The present invention compounds carbon nanotube with special engineering plastic with excellent performance, such as PES, PAEK, PAE, PEI or PI, via selecting one kind of proper solvent, such as DMF, with relatively high boiling point lower than the Tg of the polymer and less volatilization, so that under the action of the gravitational field, carbon nanotube is distributed gradiently and one kind of engineering plastic film with gradiently distributed carbon nanotube is obtained. The nanometer composite gradient polymer/carbon film has the excellent performance of engineering plastic maintained and new functional performance, such as electrical performance and optical performance.
Description
Technical field
The invention belongs to the emerging interdisciplinary high-tech sector that macromolecular material combines with nanotechnology, be nanometer science and technology, be specifically related to the preparation method of a kind of series of polymers material at the polymer/carbon nano-tube composite gradient film of preparation high-performance and many performances.
Background technology
Along with development of science and technology, a lot of fields are more and more higher to the requirement of material property, single macromolecular material can not satisfy the demand of its application purpose, therefore people carry out functionalization by the whole bag of tricks to existing high performance polymer material, under the prerequisite of not destroying the macromolecular material excellent properties, give that it is special functional.
Nanometer science and technology is an emerging interdisciplinary high-tech sector, especially carbon nanotube (CNTs), because it has unique texture and a lot of peculiar character, the existing focus that has become new quasi-one-dimensional nanometer material research, and its research is just progressing into the applied research stage.High molecular polymer/carbon nano tube compound material is to be matrix with the polymkeric substance, and the carbon nanotube of nanoscale is scattered in the novel high polymer matrix material in the matrix.Carbon nanotube itself has character such as excellent mechanics, electricity, optics, in addition, some macromolecular materials can embed carbon nanotube by the part and form in conjunction with fine and close, the unconspicuous matrix material in interface, make the polymer/carbon nano-tube matrix material on the basis of the mechanics that keeps the polymkeric substance excellence, thermostability etc., give full play to the specific performance of carbon nanotube, thereby make matrix material embody the character of aspects such as unique electricity, optics.
Based on the plurality of advantages of polyarylether series material, it is considered to integrate the special copolymer of high performance engineering plastics and functional polymer in matrix material, and itself and carbon nanotube is compound, and the performance of each side will reach optimization.
Therefore, the present invention has carried out relevant performance study by carbon nanotube with the functionally graded coatings of the compound preparation of special engineering plastics of excellent performance, on the basis of the every premium properties that does not change matrix polymer, given new functional, as electric property and optical property.
Summary of the invention
The objective of the invention is to prepare class carbon nanotube/special engineering plastics laminated film, and make carbon nanotube distribution gradient in series of polymers matrix polymer resin, thereby give many particular performances such as performances such as electricity, optics, and keep the original excellent performance of matrix polymer resin.
Characteristics of the present invention:
The polyarylether series material, as a kind of special engineering plastics, in molecular structure, contain polarity, stable on heating phenylene and flexibility, stable on heating oxygen-ether linkage or thioether bond, thereby show characteristics such as very high thermotolerance, excellent mechanical property, anti-solvent, radiation hardness, obtained using widely in fields such as transportation, Aeronautics and Astronautics, military affairs, electronics, information, nuclear energy.
This patent adopts a kind of novel method-solution evaporation method, selected a kind of suitable solvent as DMF (as described in below satisfying the solvent of condition can), its boiling point is higher, and below polymer Tg, volatilization is slower simultaneously, thereby make carbon nanotube under the effect of gravity field, utilize the difference of proportion, better reach Gradient distribution.The Gradient distribution model of carbon nanotube (tubulose or fibrous) in polymeric matrix as shown in Figure 1.
The preparation method of polymer/carbon nano-tube composite gradient film involved in the present invention is as follows:
(1) takes by weighing the polymer dissolution of 0.2～50 gram in 2～500 milliliters polar organic solvent, adding and polymer quality ratio are 0.0001～0.2: 1 carbon nanotube, after washing ultrasonic 1～30 hour, pour on the horizontal support flat board, adopt scraper control film thickness and planeness, place baking oven to transfer to level, under the vacuum respectively at 50 °～70 ℃, 80～100 ℃ temperature programmed controls 1～10 hour, half-dried polymer/carbon nano-tube composite membrane above obtaining;
(2) take by weighing the polymer dissolution of 0.2～50 gram in 2～500 milliliters polar organic solvent, this solution is coated on the top half-dried polymer/carbon nano-tube composite membrane, then respectively at 110～130 ℃, 140～160 ℃, 190～210 ℃, 240～260 ℃ temperature programmed controls 1～10 hour, heat-treat thoroughly to remove and desolvate, promptly get polymer/carbon nano-tube (CNTs) gradient composite membrane after peeling off.
Back up pad described in the aforesaid method can be the back up pad of any level, and as sheet glass, iron plate, steel plate, alloy sheets etc., the method with blade coating prepares film (scrape out with scraper, scraper is the instrument that a kind of commonly used being used for prepares film) thereon.Put into baking oven in 20 ℃～400 ℃ temperature programming processing under vacuum, thereby obtain carbon nano tube/polyamide 6 imines film.Temperature programming is to remove the solvent effective means in the preparation thin-film process, consider factors such as invention effect and production cost, the present invention determines above-mentioned comparatively ideal temperature programmed control processing parameter, is the process that is achieved in explanation the present invention, rather than is used to limit the present invention.
Polymkeric substance described in the aforesaid method is soluble engineering plastics such as polyethersulfone (PES), polyaryletherketone (PAEK), polyarylether (PAE), polyetherimide (PEI) or polyimide (PI).
Solvent described in the aforesaid method is N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP) or their mixed solvent.
Described carbon nanotube can be two kinds of many walls and Single Walled Carbon Nanotube, according to the number of plies difference that constitutes carbon nanotube tube wall carbon atom, can be divided into multi-walled carbon nano-tubes and Single Walled Carbon Nanotube, multi-walled carbon nano-tubes is formed to the dozens of carbon atomic layer by two, and the Single Walled Carbon Nanotube tube wall is made up of the monolayer carbon atom.Carbon nanotube is produced by nanometer port, Shenzhen.
As preferred implementation of the present invention, the solid content of polymkeric substance is 0.01～0.2g/ml in the polar organic solvent, and carbon nanotube is 0.01～0.2: 1 with the polymer quality ratio.
As further again preferred implementation of the present invention, the solid content of polymkeric substance is 0.05～0.1g/ml in the polar organic solvent, and carbon nanotube is 0.1～0.1: 1 with the polymer quality ratio.
Description of drawings
Fig. 1: the Gradient distribution model synoptic diagram of carbon nanotube (tubulose or fibrous) in polymeric matrix;
Fig. 2: (diameter is at 10～30nm) sem photograph for multi-walled carbon nano-tubes;
Fig. 2 (1) is 20000 times a sem photograph for magnification,
Fig. 2 (2) is 70000 times sem photograph for magnification;
Fig. 3: carbon nano tube-doped amount is 2% poly (arylene ether nitrile)/carbon nanotube gradient film side sem photograph;
Fig. 4: carbon nano tube-doped amount is the XPS spectrum figure of 1% poly (arylene ether nitrile)/carbon nanotube gradient film
Fig. 4 (1) is the XPS spectrum figure of gradient film air surface,
Fig. 4 (2) is the XPS spectrum figure of gradient film glass face;
Fig. 5: the two sides reflection ultraviolet-visible light spectrogram of poly (arylene ether nitrile)/carbon nanotube gradient film
Fig. 5 (1) is the film reflection ultraviolet-visible light spectrogram of not doped carbon nanometer pipe,
Fig. 5 (2) is the reflection ultraviolet-visible light spectrogram of 1% gradient film for doping;
Fig. 6: the poly (arylene ether nitrile)/carbon nanotube gradient film DSC scintigram of the different dopings of carbon nanotube;
Fig. 7: thermal weight loss (TGA) graphic representation of poly (arylene ether nitrile)/carbon nanotube gradient film under air,
Fig. 7 (1) is thermal weight loss (TGA) graphic representation of not doping,
Fig. 7 (2) is thermal weight loss (TGA) graphic representation of 1% gradient film for doping;
Table 1: the electrical properties of Gradient Film (the ZC25-3 type insulation resistance meter that adopts Hangzhou China ammeter factory to produce)
Content of carbon nanotubes air surface glass surface
(％) (MΩ) (MΩ)
1 ＞10
8 200
2 ＞10
8 0.075
5 ＞10
8 0.05
Table 2: the contact angle numerical value of Gradient Film (HARVEY, FT 200 types that MAIN﹠CO.LTD. produces)
The content of carbon nanotubes air surface (°) glass surface (°)
1％ 76±1 71±1
2％ 77±1 73±1
5％ 78±1 69±1
Table 3: the mechanical stretch test result of Gradient Film (the AG-I type almighty test machine that adopts Shimadzu company to produce)
CNT modulus fracture strength elongation at break
Content GPa MPa %
0％ 2.5 83 5
1％ 1.6 58 5
2％ 1.7 52 6
5％ 1.4 44 6
As shown in Figure 2, not surface treated carbon nanotube diameter is between 10～30nm.It is the tubulose winding arrangement.
Fig. 3 is that carbon nano tube-doped amount is 2% gradient film side sem photograph, can see carbon nanotube higher near sheet glass one side content, and lower at air one side content, has proved the content of carbon nanotubes difference on two sides.
Fig. 4 is the XPS spectrum figure on 1% gradient film two sides, and N1s is obviously different at the spectrum peak on two surfaces, proves the content difference of poly (arylene ether nitrile) on two surfaces.Wherein Fig. 4 (1) is the XPS spectrum figure of gradient film air surface, and Fig. 4 (2) is the XPS spectrum figure of gradient film glass face.
Shown in Fig. 5 (2), the ultraviolet-visible absorbance figure on 1% gradient film two sides is different, and (wherein solid line is the ultraviolet-visible absorbance figure of air surface, and dotted line is the ultraviolet-visible absorbance figure of glass surface.), can see that the two sides is obviously different.
Table 1 is the result of two surperficial electrical properties of different carbon nano tube-doped amount gradient films, and we can see that the resistance of each doping gradient film glass face is significantly less than the resistance of air surface, has proved that the content of carbon nanotubes on each doping gradient film two sides is obviously different.
Simultaneously can see that the content of carbon nanotube is increased at 2% o'clock by 1%, the resistance of gradient film glass face 3 orders of magnitude that descended, the content of carbon nanotube further is increased at 5% o'clock, has also embodied further obviously reducing of resistance.
Table 2 is the contact angle test result of gradient film, and we can see that two sides contact angle numerical value has significant difference, visible two sides difference.
To sum up, by scanning electron microscope, XPS, the reflection ultraviolet-as seen, contact angle and electricity are measured five kinds of characterization methods, have proved target product---and polymer/carbon nano-tube composite gradient film two sides moiety, content and nature difference thereof are obvious.
As shown in Figure 6, it is the DSC scintigram of poly (arylene ether nitrile)/carbon nanotube gradient film, by this figure we as can be seen the second-order transition temperature (Tg) of the gradient film of different dopings do not have obvious variation, proved that this gradient film has kept the good thermal characteristics of poly (arylene ether nitrile), has higher use temperature.
Wherein solid line is represented the not DSC scintigram of doping, and the some broken string is the DSC scintigram of 1% gradient film, and point is represented the DSC scintigram of 2% gradient film, and broken string is the DSC scintigram of 5% gradient film.
Fig. 7 is the hot weightless picture of poly (arylene ether nitrile)/carbon nanotube gradient film under air, shown in Fig. 7 (1) and Fig. 7 (2), be respectively the TGA graphic representation of 0% and 1% gradient film under air, as seen the 5% thermal weight loss temperature of 1% gradient film under air can reach about 487 ℃, and this has shown that this material has excellent thermostability and thermo-oxidative stability.
Table 3 is the mechanics tensile property test result of poly (arylene ether nitrile)/carbon nanotube gradient film, can see that this gradient film has kept polyarylether body material good mechanical performance.
To sum up, by DSC, TGA and three kinds of characterization methods of mechanics Elongation test, proved that target product-polyarylether/carbon nanotube gradient film has kept good thermal characteristics and mechanical property.
In sum, by the gradient film being carried out the test of performance, prove that our prepared polyarylether/carbon nanotube gradient film is better dispersed, double-sided anisotropic is obvious, the mechanics thermal property is fine, the of paramount importance considerable influence that is carbon nano tube-doped to gradient film glass face electrical properties, have good application may with prospect.
Concrete embodiment
Embodiment 1:
Taking by weighing poly (arylene ether nitrile) 2.11g is dissolved in the 20ml dimethyl formamide (DMF), suction filtration, add multi-walled carbon nano-tubes 0.04212g (2%, wt), wash ultrasonic 1h after, pour on the horizontal support sheet glass, adopt scraper control film thickness 100 microns and planeness, place baking oven to transfer to level, 60 ℃, 90 ℃ each 1h of temperature programmed control make above the film half-dried; And then take by weighing poly (arylene ether nitrile) 2.11g and be dissolved in the 20ml dimethyl formamide (DMF), this solution is coated on the top half-dried film, adopt scraper control thickness at 300 microns, temperature programming: 120 ℃/1 hour, 150 ℃/1 hour, 200 ℃/1 hour, 250 ℃/1 hour, thoroughly remove and desolvate, after peeling off thickness at 30 microns poly (arylene ether nitrile)/carbon nanotube gradient composite membrane.
Prove that after tested this new membrane material gradient is better dispersed, the film double-sided anisotropic that obtains is obvious, and mechanics and thermal property are fine, have broad application prospects, and as seen the film that obtains under this processing condition is better.
The poly (arylene ether nitrile) structural formula is as follows:
Embodiment 2:
Method such as embodiment 1, with the amount of carbon nanotube be increased to 0.02106g (1%, wt).The back up pad one side electric conductivity of this film has reduced by 1 order of magnitude.
Embodiment 3:
Method such as embodiment 1, with the amount of carbon nanotube be increased to 0.1053g (5%, wt).The back up pad one side electric conductivity of this film has improved 4 orders of magnitude.
Embodiment 4:
Method such as embodiment 1, with the amount of carbon nanotube be increased to 0.2106g (10%, wt).The back up pad one side electric conductivity of this film has improved 5 orders of magnitude.
Embodiment 5:
Method such as embodiment 1 replace multi-walled carbon nano-tubes with Single Walled Carbon Nanotube.The back up pad one side electric conductivity of this film increases.(because the diameter of Single Walled Carbon Nanotube is less, can better be distributed in the polymkeric substance, thereby the network structure that forms being better)
Embodiment 6:
Method such as embodiment 1, (2.11g) replace poly (arylene ether nitrile) (PEN) with polyethersulfone (PES), obtain carbon nano tube-doped amount and be polyethersulfone/carbon nanotube gradient film of 1%, the thermotolerance of this film has improved 50 degree (5% heat decomposition temperature of poly (arylene ether nitrile)/carbon nanotube is 488 ℃).
The structure of polyethersulfone is as follows:
Embodiment 7:
Method such as embodiment 1 (2.11g) replace poly (arylene ether nitrile) (PEN) with soluble poly aromatic ether ketone (PAEK), obtain carbon nano tube-doped amount and be 1% polyarylether ketone/carbon nanotube gradient film, and the toughness of this film improves greatly.
The structure of soluble poly aromatic ether ketone is as follows:
Embodiment 8:
Method such as embodiment 1, (2.11g) replace poly (arylene ether nitrile) (PEN) with polyimide (PI), obtain carbon nano tube-doped amount and be polyimide/carbon nanotube gradient film of 1%, the thermotolerance of this film has improved 100 degree above (5% heat decomposition temperature of poly (arylene ether nitrile)/carbon nanotube is 488 ℃).
The structure of polyimide is as follows:
Embodiment 9:
Method such as embodiment 1 replace N with N,N-dimethylacetamide (DMAc), dinethylformamide (DMF), and the character of the film that obtains does not have considerable change.
Embodiment 10:
Method such as embodiment 1 replace N with N-Methyl pyrrolidone (NMP), dinethylformamide (DMF), and the character of the film that obtains does not have considerable change.
Embodiment 11:
Method such as embodiment 1, with N-Methyl pyrrolidone and N, the mixed solvent of dinethylformamide, volume respectively account for 50%, and the character of the film that obtains does not have considerable change.
Embodiment 12:
Method such as embodiment 1, with N,N-dimethylacetamide and N, the mixed solvent of dinethylformamide, volume respectively account for 50%, and the character of the film that obtains does not have considerable change.
Embodiment 13:
Method such as embodiment 1 are increased to 5 hours with 60 degree and 90 heat treatment times of spending, and the character of the film that obtains does not have considerable change.
Claims (8)
1, the preparation method of polymer/carbon nano-tube composite gradient film comprises the steps:
(1) takes by weighing the polymer dissolution of 0.2～50 gram in 2～500 milliliters polar organic solvent, adding and polymer quality ratio are 0.0001～0.2: 1 carbon nanotube, after washing ultrasonic 1～30 hour, pour on the horizontal support flat board, adopt scraper control film thickness and planeness, place baking oven to transfer to level, under the vacuum respectively at 50 °～70 ℃, 80～100 ℃ temperature programmed controls 1～10 hour, half-dried polymer/carbon nano-tube composite membrane above obtaining;
(2) take by weighing the polymer dissolution of 0.2～50 gram in 2～500 milliliters polar organic solvent, this solution is coated on the top half-dried polymer/carbon nano-tube composite membrane, then respectively at 110～130 ℃, 140～160 ℃, 190～210 ℃, 240～260 ℃ temperature programmed controls 1～10 hour, heat-treat thoroughly to remove and desolvate, promptly get polymer/carbon nano-tube (CNTs) gradient composite membrane after peeling off.
2, the preparation method of polymer/carbon nano-tube composite gradient film as claimed in claim 1 is characterized in that: back up pad is sheet glass, iron plate, steel plate or the alloy sheets of any level.
3, the preparation method of polymer/carbon nano-tube composite gradient film as claimed in claim 1 is characterized in that: polymkeric substance is soluble engineering plastics polyethersulfone (PES), polyaryletherketone (PAEK), polyarylether (PAE), polyetherimide (PEI) or polyimide (PI).
4, the preparation method of polymer/carbon nano-tube composite gradient film as claimed in claim 1, it is characterized in that: solvent is N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP) or their mixed solvent.
5, as the preparation method of any one described polymer/carbon nano-tube composite gradient film of claim 1-4, it is characterized in that: the solid content of polymkeric substance is 0.01～0.2g/ml in the organic solvent, and carbon nanotube is 0.01～0.2: 1 with the polymer quality ratio.
6, the preparation method of polymer/carbon nano-tube composite gradient film as claimed in claim 5 is characterized in that: the solid content of polymkeric substance is 0.05～0.1g/ml in the organic solvent, and carbon nanotube is 0.1～0.1: 1 with the polymer quality ratio.
7, as the preparation method of any one described polymer/carbon nano-tube composite gradient film of claim 1-4, it is characterized in that: carbon nanotube is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
8, the preparation method of polymer/carbon nano-tube composite gradient film as claimed in claim 6 is characterized in that: carbon nanotube is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
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| CN100348667C (en) * | 2006-05-11 | 2007-11-14 | 上海交通大学 | Process for preparing rare earth modified carbon nanotube/polyimide composite materials |
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| CN101792588A (en) * | 2010-02-10 | 2010-08-04 | 吉林大学 | Polyarylether ketone/carbon nanotube composite material with high dielectric property and preparation method thereof |
| CN101235193B (en) * | 2008-01-15 | 2010-12-08 | 北京科技大学 | Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material |
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| CN100410656C (en) * | 2006-03-21 | 2008-08-13 | 扬州大学 | Method for preparing carbon nano-tube/poly L-cysteine composite modified glassy carbon electrode |
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| CN101235193B (en) * | 2008-01-15 | 2010-12-08 | 北京科技大学 | Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material |
| CN101792588A (en) * | 2010-02-10 | 2010-08-04 | 吉林大学 | Polyarylether ketone/carbon nanotube composite material with high dielectric property and preparation method thereof |
| CN102702744A (en) * | 2012-05-29 | 2012-10-03 | 河北工业大学 | Method for preparing polyimide/carbon nanotube nanocomposite |
| CN102702744B (en) * | 2012-05-29 | 2013-09-04 | 河北工业大学 | Method for preparing polyimide/carbon nanotube nanocomposite |
| CN109244238A (en) * | 2018-09-04 | 2019-01-18 | 武汉华星光电半导体显示技术有限公司 | Flexible base board and preparation method thereof for display panel |
| CN110743389A (en) * | 2019-12-07 | 2020-02-04 | 中化泉州能源科技有限责任公司 | Carbon molecular sieve membrane and preparation method thereof |
| CN111470876A (en) * | 2020-03-16 | 2020-07-31 | 中山大学 | High-graphitization polyimide-based graphite thick film and preparation method thereof |
| CN113912884A (en) * | 2021-11-10 | 2022-01-11 | 贵州省材料产业技术研究院 | Preparation method of flexible electromagnetic shielding polyether sulfone membrane |
| CN113912884B (en) * | 2021-11-10 | 2022-04-15 | 贵州省材料产业技术研究院 | Preparation method of flexible electromagnetic shielding polyether sulfone membrane |
| CN114316637A (en) * | 2021-12-28 | 2022-04-12 | 南开大学 | Controllable preparation method of gradient composite membrane |
| CN114485244A (en) * | 2022-02-14 | 2022-05-13 | 中国电建集团华东勘测设计研究院有限公司 | Thermal diode, thermal rectifying coating, phase-change heat storage and supply device and heat monitoring method |
| CN114485244B (en) * | 2022-02-14 | 2023-10-13 | 中国电建集团华东勘测设计研究院有限公司 | Thermal diode, thermal rectification coating, phase-change heat storage and supply device and heat monitoring method |
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