CN108329679A - A kind of preparation method of solvent-free graphene electric-heating thin film - Google Patents
A kind of preparation method of solvent-free graphene electric-heating thin film Download PDFInfo
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- CN108329679A CN108329679A CN201810108267.0A CN201810108267A CN108329679A CN 108329679 A CN108329679 A CN 108329679A CN 201810108267 A CN201810108267 A CN 201810108267A CN 108329679 A CN108329679 A CN 108329679A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The invention discloses a kind of preparation methods of solvent-free graphene electric-heating thin film, include the following steps：（1）, using Physical remove graphene microchip, modified graphene is obtained by corona treatment mode；（2）, modified graphene is blended with silane coupling agent, dispersant, TPU particles in high-temperature blending equipment；（3）, graphene/TPU of uniform molten will be blended by screw machine T-type lamination head lamination on release carrier, it is cooling to remove after release carrier up to solvent-free graphene electric-heating thin film.Graphene electric-heating thin film initial bonding strength prepared by present invention solventless method is relatively low, and after overcuring is fully cured, interlaminar strength and heat seal strength are fine, and the electric-heating thin film moisture-proof moisture resistance of this technique productions is all fine.
Description
Technical field
The present invention relates to a kind of preparation methods of solvent-free graphene electric-heating thin film, belong to grapheme material technical field.
Background technology
Graphene electric-heating thin film is the film of the heating that can be powered prepared with certain technical method.Usually there are two types of shapes
State：First, the transparent electric heating film that CVD method grows out, another is grey black opaque film prepared by powder.At present
The common technology for preparing graphene electric-heating thin film has silk-screen printing, CVD method growth, suction method etc., silk-screen thickness to be difficult to accurately control
System, CVD method is of high cost, and suction method is not suitable for large-scale production.Coating and silk-screen can be inexpensive, continuously, large-scale industrialization
Production, but coat and the electric heating slurry used of silk-screen contains organic solvent, in drying process, organic solvent volatilization causes ring
Border is polluted, and another aspect environment temperature has an impact the volatilization of organic solvent, and the resistance for being easy to cause Electric radiant Heating Film is unstable.
Invention content
To solve the above-mentioned problems, the present invention proposes a kind of preparation method of solvent-free graphene electric-heating thin film, prepares
Organic solvent is not added in the process, thus in process of production, is volatilized without solvent, and pollution will not be generated to environment, is conducive to
Cleanly production.On the other hand, solventless method prepares electric-heating thin film, and product quality stability is high, resistance stabilization.
Technical scheme is as follows：
A kind of preparation method of solvent-free graphene electric-heating thin film, includes the following steps：
（1）, using Physical remove graphene microchip, modified graphene is obtained by corona treatment mode；
（2）, modified graphene is blended with silane coupling agent, dispersant, TPU particles in high-temperature blending equipment；
（3）, graphene/TPU of uniform molten will be blended by screw machine T-type lamination head lamination on release carrier, it is cooling
It removes after release carrier up to solvent-free graphene electric-heating thin film.
Above-mentioned steps（1）Middle plasma treatment mode it is as follows：
（a）, graphene microchip is evenly laid out on surface plate, be put into corona treatment instrument；
（b）, first open vacuum pump, so that vacuum degree is reached 5 pa or less；
（c）, be passed through gas again, adjusting flow makes vacuum degree reach the pa of 10pa~50；
（d）, adjust discharge power, open high frequency electric source carry out glow discharge, after reaching preset processing time, close high frequency
Power supply takes out graphene microchip, obtains modified graphene.
Above-mentioned steps（c）In gas be ammonia, carbon dioxide, sulfur dioxide, ozone, one kind in air.
Above-mentioned steps（2）The proportioning of middle modified graphene and silane coupling agent, dispersant, TPU particles is：10~20：1~
5：5~10：50~70, said ratio is mass ratio.
Above-mentioned steps（2）Temperature in high temperature blending equipment is controlled at 120~170 degree.
Above-mentioned steps（3）Middle lamination temperature control is at 70~140 degree.
Above-mentioned steps（3）In release carrier be release paper or release film.
The advantageous effect that the present invention is reached：
Graphene electric-heating thin film initial bonding strength prepared by present invention solventless method is relatively low, after overcuring is fully cured, interlayer stripping
Fine from intensity and heat seal strength, the electric-heating thin film moisture-proof moisture resistance of this technique productions is all fine.
Description of the drawings
Fig. 1 is plasma treatment mode flow chart；
Fig. 2 is corona treatment instrument structural schematic diagram.
Fig. 3 is the graphene microchip of ozone treatment and the infrared comparison diagram of unmodified graphene microchip.
Fig. 4 is that the modified graphene microchip of different functional groups is disperseed in deionized water with unmodified graphene microchip
The comparison diagram of property.
Specific implementation mode
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention
Technical solution, and not intended to limit the protection scope of the present invention.
A kind of preparation method of solvent-free graphene electric-heating thin film, includes the following steps：
（1）, using Physical remove graphene microchip, modified graphene is obtained by corona treatment mode；Plasma
Processing time is 10-30 minutes.
As shown in Figure 1 and Figure 2, above-mentioned steps（1）Middle plasma treatment mode it is as follows：
（a）, graphene microchip is evenly laid out on surface plate, be put into corona treatment instrument；
（b）, first open vacuum pump, so that vacuum degree is reached 5 pa or less；
（c）, be passed through gas again, adjusting flow makes vacuum degree reach 10pa~50pa；Gas be ammonia, carbon dioxide, sulfur dioxide,
One kind in ozone, air.
（d）, adjust discharge power, open high frequency electric source carry out glow discharge, after reaching preset processing time, close
High frequency electric source takes out graphene microchip, obtains modified graphene.
（2）, modified graphene is blended with silane coupling agent, dispersant, TPU particles in high-temperature blending equipment；
Temperature in high-temperature blending equipment is controlled at 120~170 degree.
The proportioning of modified graphene and silane coupling agent, dispersant, TPU particles is：10~20：1~5：5~10：50~
70, said ratio is mass ratio.
（3）, graphene/TPU of uniform molten will be blended by screw machine T-type lamination head lamination on release carrier,
Lamination temperature is controlled in 70-140 degree.Up to solvent-free graphene electric-heating thin film after the cooling release carrier of stripping.Release carrier is
Release paper or release film.
Embodiment 1：
A kind of preparation method of solvent-free graphene electric-heating thin film, includes the following steps：
Step 1：It is 15 by quality proportioning：2：8：Graphene microchip and the silane coupling agent of 75 Physical stripping, dispersant,
TPU particles are blended in high-temperature blending equipment, and temperature is 150 degree.
Step 2：By the graphene TPU of the molten after blending a period of time by screw machine T-type lamination head lamination in release
On carrier, lamination temperature is at 120 degree to get solvent-free graphene electric-heating thin film.
Embodiment 2：
A kind of preparation method of solvent-free graphene electric-heating thin film, includes the following steps：
Step 1：The graphene microchip removed using Physical, is changed after about 30 minutes are handled under ammonia plasmas atmosphere
Property amido graphene；
Step 2：It is 15 by quality proportioning：2：8：75 modified amine base graphene exists with silane coupling agent, dispersant, TPU particles
It is blended in high-temperature blending equipment, temperature is 150 degree.
Step 3：By the graphene TPU of the molten after blending a period of time by screw machine T-type lamination head lamination in release
On carrier, lamination temperature is at 120 degree to get solvent-free graphene electric-heating thin film.
Embodiment 3：
A kind of preparation method of solvent-free graphene electric-heating thin film, includes the following steps：
Step 1：The graphene microchip removed using Physical, after being handled under carbon dioxide plasma atmosphere about 30 minutes
To modified carboxyl graphene；
Step 2：It is 15 by quality proportioning：2：8：75 modification amido carboxyl graphene and silane coupling agent, dispersant, TPU
Grain is blended in high-temperature blending equipment, and temperature is 150 degree.
Step 3：By the graphene TPU of the molten after blending a period of time by screw machine T-type lamination head lamination in release
On carrier, lamination temperature removes release carrier at 120 degree, after cooling can obtain solvent-free graphene electric-heating thin film.
Embodiment 4：
A kind of preparation method of solvent-free graphene electric-heating thin film, includes the following steps：
Step 1：The graphene microchip removed using Physical, is changed after about 30 minutes are handled under ozone plasma atmosphere
Property graphene oxide；
Step 2：It is 15 by quality proportioning：2：8：75 modified graphene oxide exists with silane coupling agent, dispersant, TPU particles
It is blended in high-temperature blending equipment, temperature is 150 degree.
Step 3：By the graphene TPU of the molten after blending a period of time by screw machine T-type lamination head lamination in release
On carrier, lamination temperature removes release carrier at 120 degree, after cooling can obtain solvent-free graphene electric-heating thin film.
The IR figures PE companies of the ozone modified graphene microplate and unmodified graphene microchip of the present invention
1000 type infrared spectrometers of Paragon are measured, and test sample is powder.
Fig. 3 be under ozone plasma before modified with modified infrared absorption spectrum.At ozone plasma
After reason, there are three apparent peaks, respectively in 3500 cm-1Place, 1633 cm-1With in 1378 cm-1Place.3500 cm-1Place
Wider peak corresponds to the hydroxyl in the hydrone of the hydroxyl peak in graphene and absorption, and data are shown by plasma
After processing, hydroxyl peak becomes apparent from, graphene microchip crystal grain refinement, the hydrone being easier in transfer process in absorption air,
The graphene microchip that oleophylic is not hydrophilic originally is set to increase hydrophily.1633 cm-1The peak at place is that the stretching vibration of C=O keys is drawn
It rises, 1378 cm-1The peak at place is caused by c h bond stretching vibration, the two peaks all do not have in untreated graphene microchip
Have, it follows that under the action of odor at low temperature plasma, graphene part C-C keys disconnect, then form hydrophily
The better sp such as C=O keys and C-OH keys3The hybrid bond of type.
As shown in figure 4, the microplate of the graphene after embodiment 2-4 corona treatments, in deionized water
Dispersibility is significantly better than 1 unmodified graphene microchip of embodiment.Subsequently graphene electric-heating thin film is being prepared with solventless method
In the process, modified graphene microchip and the compatibility of TPU can be more preferable, and the electric-heating thin film stability prepared is more preferable, the service life
It is longer.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of solvent-free graphene electric-heating thin film, it is characterised in that include the following steps：
（1）, using Physical remove graphene microchip, modified graphene is obtained by corona treatment mode；
（2）, modified graphene is blended with silane coupling agent, dispersant, TPU particles in high-temperature blending equipment；
（3）, graphene/TPU of uniform molten will be blended by screw machine T-type lamination head lamination on release carrier, it is cooling
It removes after release carrier up to solvent-free graphene electric-heating thin film.
2. a kind of preparation method of solvent-free graphene electric-heating thin film according to claim 1, it is characterised in that：The step
Suddenly（1）Middle plasma treatment mode it is as follows：
（a）, graphene microchip is evenly laid out on surface plate, be put into corona treatment instrument；
（b）, first open vacuum pump, so that vacuum degree is reached 5 pa or less；
（c）, be passed through gas again, adjusting flow makes vacuum degree reach 10pa~50pa；
（d）, adjust discharge power, open high frequency electric source carry out glow discharge, after reaching preset processing time, close high frequency
Power supply takes out graphene microchip, obtains modified graphene.
3. a kind of preparation method of solvent-free graphene electric-heating thin film according to claim 2, it is characterised in that：The step
Suddenly（c）In gas be ammonia, carbon dioxide, sulfur dioxide, ozone, one kind in air.
4. a kind of preparation method of solvent-free graphene electric-heating thin film according to claim 1, it is characterised in that：The step
Suddenly（2）The proportioning of middle modified graphene and silane coupling agent, dispersant, TPU particles is：10~20：1~5：5~10：50~
70, said ratio is mass ratio.
5. a kind of preparation method of solvent-free graphene electric-heating thin film according to claim 1, it is characterised in that：The step
Suddenly（2）Temperature in high temperature blending equipment is controlled at 120~170 degree.
6. a kind of preparation method of solvent-free graphene electric-heating thin film according to claim 1, it is characterised in that：The step
Suddenly（3）Middle lamination temperature control is at 70~140 degree.
7. a kind of preparation method of solvent-free graphene electric-heating thin film according to claim 1, it is characterised in that：The step
Suddenly（3）In release carrier be release paper or release film.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109774292A (en) * | 2019-03-19 | 2019-05-21 | 中金态和(武汉)石墨烯研究院有限公司 | A kind of preparation method of graphene composite heating film |
| CN109878165A (en) * | 2019-03-01 | 2019-06-14 | 中金态和(武汉)石墨烯研究院有限公司 | A kind of graphene composite heating film and its graphene composite heating film group |
| CN109927324A (en) * | 2019-03-01 | 2019-06-25 | 中金态和(武汉)石墨烯研究院有限公司 | A kind of three-layer co-extruded preparation method out of graphene composite heating film |
| CN110885548A (en) * | 2019-10-17 | 2020-03-17 | 江苏宏远新材料科技有限公司 | Antistatic modified thermoplastic polyurethane film and preparation method thereof |
| CN111995861A (en) * | 2020-08-27 | 2020-11-27 | 裕克施乐塑料制品（太仓）有限公司 | GO/TPU composite powder for selective laser sintering of heat-resistant workpieces and preparation method thereof |
| WO2022120587A1 (en) * | 2020-12-08 | 2022-06-16 | 中国科学院深圳先进技术研究院 | Preparation method for thermally conductive gaskets with high normal thermal conductivity and high elasticity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109878165A (en) * | 2019-03-01 | 2019-06-14 | 中金态和(武汉)石墨烯研究院有限公司 | A kind of graphene composite heating film and its graphene composite heating film group |
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| CN111995861A (en) * | 2020-08-27 | 2020-11-27 | 裕克施乐塑料制品（太仓）有限公司 | GO/TPU composite powder for selective laser sintering of heat-resistant workpieces and preparation method thereof |
| WO2022120587A1 (en) * | 2020-12-08 | 2022-06-16 | 中国科学院深圳先进技术研究院 | Preparation method for thermally conductive gaskets with high normal thermal conductivity and high elasticity |
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