CN113797767B - Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet - Google Patents
Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet Download PDFInfo
- Publication number
- CN113797767B CN113797767B CN202010534978.1A CN202010534978A CN113797767B CN 113797767 B CN113797767 B CN 113797767B CN 202010534978 A CN202010534978 A CN 202010534978A CN 113797767 B CN113797767 B CN 113797767B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- carbon nanotube
- cellulose
- composite sheet
- carbon nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
Abstract
The invention discloses a preparation method of a carbon nano tube-ionic liquid-derived cellulose composite membrane and a composite sheet. The carbon nano tube is a single-wall or multi-wall carbon nano tube, the ionic liquid mainly comprises functionalized imidazole and benzothiazole ionic liquid, and derivative cellulose including ethyl cellulose is used as a film forming agent/diluent. The invention adopts a natural molding or tabletting method to respectively prepare the carbon nano tube, the ionic liquid and the derivative cellulose mixture into a composite film or a composite sheet; the preparation process is simple, mild in condition, easy to popularize and suitable for large-scale preparation. The obtained composite film or composite sheet has the functions of ionic liquid and carbon nano tubes. The surface of the composite film or the composite sheet has strong hydrophobicity and is not easy to disintegrate in a water environment; the ionic liquid and the carbon nano tube are combined stably and cannot be lost in the continuous contact process with water. The composite film and the composite sheet have ideal environmental friendliness and recycling property.
Description
Technical Field
The invention belongs to the technical field of separation and catalysis, and particularly relates to a composite material related to ionic liquid and carbon nano tubes, which is applied to the field of separation and catalysis; it relates to a method for preparing composite film and composite sheet mainly using carbon nano tube and ionic liquid as functional components.
Background
As a special nano material, carbon nanotubes have been studied for the past 30 years to show excellent electrical, mechanical, thermal, chemical and mechanical properties. It can be classified into single-walled carbon nanotubes and multi-walled carbon nanotubes according to the classification of the number of graphite sheets. The single-walled carbon nanotube is formed by coiling single-walled flake graphite, and the single-walled carbon nanotubes with different diameters are sleeved by multi-walled carbon nanotubes, and the distance between layers is about 0.34nm. Due to the unique and stable hollow tube cavity structure, the larger length-diameter ratio and the flexible and changeable functional mode, the composite material can be widely applied to gas separation, catalytic degradation and adsorption of water quality organic pollutants (such as dioxin, chlorobenzene, antibiotics and the like), heavy metal ions from different sources and other environment harmful residues in the technical field.
Ionic liquids are of particular interest for their environmentally friendly physical and chemical properties, such as low vapor pressure, high solvent capacity, chemical stability, good electrical conductivity, versatility, which make them a significant advantage over traditional organic solvents. At present, various functionalized ionic liquids are widely applied to the fields related to catalysis, separation, electrochemistry, nano materials, polymer science, biomass processing, lubricants and the like, wherein certain processes can be operated on an industrial scale. Ionic liquids are considered one of the potential green solvents in industry because their extremely low volatility prevents their emission into the environment. In addition, the ionic liquid is immobilized in different modes, so that the ionic liquid is recovered and recycled, and the consumption and the loss of the ionic liquid are further reduced.
Cellulose is one of polysaccharides with the highest global yield, belongs to natural degradable products, is harmless, and different derivative products of the cellulose are widely used as fine chemical auxiliary materials; among them, a series of derivatives represented by ethylcellulose have very excellent adhesiveness and film-forming property, and stable chemical properties and biocompatibility, and thus are increasingly used in the technical field.
Disclosure of Invention
The invention aims to provide a preparation method of a composite membrane and a composite sheet which take ionic liquid and carbon nano tubes as functional components; the method has the advantages of simple process, mild conditions, convenient operation, easy popularization and no use of special equipment. The derivative cellulose is used for compounding the ionic liquid and the carbon nano tube in the form of a film or a sheet in simple steps, so that the defects of high cost, difficult recovery, difficult recycling and the like when the derivative cellulose and the carbon nano tube are used independently at present are overcome greatly, and the immobilization means and the application form of the conventional ionic liquid are expanded in a convenient, flexible and easily-amplified manner. The good physical and chemical properties of the carbon nano tube-ionic liquid-derivative cellulose composite membrane and the composite sheet show obvious combination advantages, and the overall properties, the functional integration and the mechanical strength of the carbon nano tube-ionic liquid-derivative cellulose composite membrane and the composite sheet are superior to those of the ionic liquid (or carbon nano tube) -derivative cellulose composite material prepared under the same conditions. The composite film has smooth appearance and good homogeneity, and is convenient to cut; the composite sheet has regular appearance and saves storage space in volume; both are easy to realize large-scale preparation and multiple use. The water-soluble organic silicon dioxide gel has the characteristics of strong hydrophobicity, no problems of disintegration and component loss in an aqueous solution, no pollution to environment and objects, environmental friendliness and good reusability.
The technical scheme is as follows: in order to realize the purpose, the preparation method of the composite membrane and the composite sheet which are composed of the ionic liquid, the carbon nano tube and the derivative cellulose is provided:
an ionic liquid and carbon nano tube-derived cellulose composite membrane is characterized in that carbon nano tubes and the ionic liquid are formed by simply physically combining, uniformly dispersing in a solvent together with a film forming agent and then recovering the solvent, and the preparation method comprises the following specific steps:
(1) Mixing the ionic liquid and the carbon nano tube according to the mass ratio (mg/mg) of 1/1-1/20 to ensure that the ionic liquid and the carbon nano tube are fully combined; adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 to dilute, finally adding the mixture of the three into ethanol with the mass volume ratio (g/ml) of 0.3/50-0.3/100, and ultrasonically oscillating at room temperature to uniformly disperse the system;
(2) Continuously evaporating the uniform mixed system formed in the step (1) under a vacuum condition to remove ethanol, and finally naturally forming the carbon nano tube-ionic liquid-derived cellulose composite membrane on a smooth and clean plane.
The ionic liquid-carbon nanotube-derivative cellulose composite sheet is characterized in that the carbon nanotube and the ionic liquid are prepared by simple physical combination and tabletting together with a diluent, and the preparation method comprises the following specific steps:
(1) Mixing the ionic liquid and the carbon nano tube according to the mass ratio (mg/mg) of 1/1-1/20 to ensure that the ionic liquid and the carbon nano tube are fully combined; then adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 to dilute, and finally fully grinding uniformly and sieving with a 200-mesh sieve;
(2) And (3) placing the sieved mixed powder into a stainless steel pressing die, and pressing and forming under the pressure of 5-20 MPa to obtain the carbon nanotube-ionic liquid-derived cellulose composite sheet.
The carbon nanotube-ionic liquid-derivatized cellulose composite membrane and composite sheet described above, the ionic liquid is mainly composed of imidazole and benzothiazole ionic liquids having different alkyl substituent chain lengths and anions, both of which include but are not limited to the structures shown in table 1.
Table 1 ionic liquid structures encompassed by the present patent
According to the preparation method of the carbon nanotube-ionic liquid-derivative cellulose composite membrane and the composite sheet, the carbon nanotube comprises a single-walled carbon nanotube or a multi-walled carbon nanotube.
The carbon nanotube-ionic liquid-derived cellulose composite membrane and the composite sheet are characterized in that: the film forming/diluent used is a derivatized cellulose including, but not limited to, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose.
According to the preparation method of the multi-walled carbon nanotube-ionic liquid-derived cellulose composite membrane and the composite sheet, the mass ratio (mg/mg) of the ionic liquid to the carbon nanotube is 1/1-1/20.
According to the preparation method of the carbon nanotube-ionic liquid-derived cellulose composite membrane and the composite sheet, the mass ratio (g/g) of the ionic liquid carbon nanotube mixture to the film forming agent is 0.05/0.25-0.15/0.15.
In the preparation method of the carbon nanotube-ionic liquid-derivative cellulose composite membrane, the solvent is ethanol.
The carbon nanotube-ionic liquid-derivatized cellulose composite sheet prepared by the method has a pressing pressure range including, but not limited to, 5-20 MPa.
Drawings
FIG. 1 shows a carbon nanotube multi-walled carbon nanotube [ C ] having a thickness of 0.1mm 4 Bth][PF 6 ]The ubiquitous appearance of the ethylcellulose composite film (a: front view, b: side view)
FIG. 2 shows a multi-walled carbon nanotube [ C ] having a diameter of 13mm and a thickness of 2mm 4 Bth][PF 6 ]Appearance of ethylcellulose composite sheet
FIG. 3 (a) shows a multi-walled carbon nanotube- [ C ] 4 Bth][PF 6 ]Photograph of ethyl cellulose composite film in contact with water and (b) contact angle CA image (hydrophobic angle: 89.33) °
FIG. 4 shows a carbon nanotube-multiwalled carbon nanotube- [ C ] 4 Bth][PF 6 ]Scanning electron micrographs of ethylcellulose compacts (a: front view, b: cut view; carbon nanotubes are tubular, while the ethylcellulose surface appears nearly spherical); from the front and the section view, the ionic liquid, the multi-walled carbon nanotube and the ethyl cellulose can be seen to be uniformly mixed
FIG. 5 is a drawing of a multi-walled carbon nanotube- [ C ] 4 Bth][PF 6 ]Zeta potential result of composite ethylcellulose film and composite sheet (Zeta potential value of material surface 0 when pH is 3.20)
Examples
The following examples are given for the purpose of illustrating the invention in detail, but are not to be construed as limiting the scope of the invention. The endpoints of the ranges and any values stated herein are not to be limited to the precise range and value, and such ranges are to be understood as encompassing values close to the value of the ranges, and that insubstantial modifications and adaptations of those skilled in the art to which the invention pertains will still fall within the scope of the invention.
Example 1
0.05g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass 4 Bth][PF 6 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1 to fully combine the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.05/0.25, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, ultrasonic mixing at room temperature for 10min, and evaporating to remove solvent under vacuum conditionForming multi-walled carbon nanotubes- [ C ] on smooth clean planes 4 Bth][PF 6 ]-an ethylcellulose composite membrane.
Example 2
0.1g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass 4 Bth][PF 6 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.1/0.2, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane 4 Bth][PF 6 ]-an ethylcellulose composite membrane.
Example 3
0.15g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass 4 Bth][PF 6 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1 to fully combine the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane 4 Bth][PF 6 ]-an ethylcellulose composite membrane.
The contact angle test was performed on the composite film prepared in example 10, and the test conditions and results are shown in table 2.
TABLE 2 Multi-walled carbon nanotubes [ C ] 4 Bth][PF 6 ]-ethyl cellulose composite film contact angle test condition and result
The composite membrane prepared in example 10 was subjected to a material surface Zeta potential test, and the test conditions and results are shown in table 3.
TABLE 3 Multi-walled carbon nanotubes [ C ] 4 Bth][PF 6 ]Zeta potential test conditions and results for-ethyl cellulose composite membrane
Example 4
The total mass of 0.15g of benzothiazole tetrafluoroborate ionic liquid ([ HBth ]][BF 4 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1 to fully combine the two; mixing with hydroxypropyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming multi-walled carbon nanotube- [ HBth ] on smooth clean plane][BF 4 ]-hydroxypropyl cellulose composite membranes.
Example 5
Benzothiazole methanesulfonate ([ HBth ] in a total mass of 0.15g][CH 3 SO 3 ]) Mixing the single-walled carbon nanotube and the single-walled carbon nanotube in a mass ratio of 1/1, and fully combining the two; mixing with carboxymethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethanol, ultrasonic treating at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming single-walled carbon nanotube- [ HBth ] on smooth clean surface][CH 3 SO 3 ]-carboxymethyl cellulose composite membranes.
Example 6
The benzothiazole triflate ([ HBth ] in a total mass of 0.15g][CF 3 SO 3 ]) Mixing the single-walled carbon nanotube and the single-walled carbon nanotube in a mass ratio of 1/1, and fully combining the two; mixing with hydroxypropyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming single-walled carbon nanotube- [ HBth ] on smooth clean plane][CF 3 SO 3 ]-hydroxypropyl cellulose composite membranes.
Example 7
Mixing benzothiazole tosyloxy salt ([ HBth ] [ PTSA ]) with the total mass of 0.15g and the single-wall carbon nanotube in the mass ratio of 1/1 to combine the two fully; then evenly mixing the mixture with ethyl cellulose according to the mass ratio (g/g) of 0.15/0.15, adding the mixture of the three into a 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, carrying out ultrasonic treatment at room temperature for 10min to evenly disperse the system, evaporating the solvent under the vacuum condition, and forming the single-walled carbon nanotube- [ HBth ] [ PTSA ] -ethyl cellulose composite membrane on a smooth clean plane.
Example 8
1-butyl-3-methylimidazolium hexafluorophosphate ([ C ] in a total mass of 0.15g 4 mim][PF 6 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1 to fully combine the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane 4 mim][PF 6 ]-an ethylcellulose composite membrane.
Example 9
1-Ethyl-3-methylimidazolium tetrafluoroborate ([ C ]) in a total mass of 0.15g 2 mim][BF 4 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1 to fully combine the two; mixing with carboxymethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane 2 mim][BF 4 ]-carboxymethyl cellulose composite membranes.
Example 10
The total mass of 0.15g of 1-hexyl-3-methylimidazolium methanesulfonate ([ Hmim)][CH 3 SO 3 ]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1 to fully combine the two; mixing with hydroxypropyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round bottom flask, adding 50ml anhydrous ethanol, and performing ultrasonic treatment at room temperature for 10min to disperse the systemAfter homogenization, the solvent was evaporated under vacuum to form multi-walled carbon nanotubes- [ Hmim ] on smooth clean surfaces][CH 3 SO 3 ]-hydroxypropyl cellulose composite membranes.
Example 11
0.05g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass 4 Bth][PF 6 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with ethyl cellulose in a mortar in a mass ratio (g/g) of 0.05/0.25, grinding uniformly, and sieving with a 200-mesh sieve; putting the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nano-tube- [ C ] 4 Bth][PF 6 ]-an ethylcellulose compact.
Example 12
1-butylbenzothiazolium hexafluorophosphate ionic liquid ([ C ] with the total mass of 0.1g 4 Bth][PF 6 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with ethyl cellulose in a mortar in a mass ratio (g/g) of 0.1/0.2, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nanotube- [ C ] 4 Bth][PF 6 ]-an ethylcellulose compact.
Example 13
0.15g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass 4 Bth][PF 6 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with ethyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; putting the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nano-tube- [ C ] 4 Bth][PF 6 ]-an ethylcellulose compact.
Example 14
The total mass of 0.15g of benzothiazole tetrafluoroborate ionic liquid ([ HBth ]][BF 4 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with hydroxypropyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a containerPressing and molding in a stainless steel pressing mold under the pressure of 15MPa to obtain the multi-walled carbon nano tube- [ HBth [ ]][BF 4 ]-a hydroxypropyl cellulose compact.
Example 15
Benzothiazole methanesulfonate ([ HBth ] in a total mass of 0.15g][CH 3 SO 3 ]) Mixing with single-walled carbon nanotubes in a mass ratio of 1/1, then mixing with carboxymethyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; putting the mixture powder into a stainless steel pressing sheet die, and pressing and molding under the pressure of 20MPa to obtain the single-walled carbon nanotube- [ HBth ]][CH 3 SO 3 ]-a carboxymethyl cellulose composite sheet.
Example 16
The total mass of 0.15g of benzothiazole trifluoromethanesulfonate ([ HBth ]][F 3 CSO 3 ]) Mixing with single-walled carbon nanotubes in a mass ratio of 1/1, then mixing with hydroxypropyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; putting the mixture powder into a stainless steel pressing sheet die, and pressing and molding under the pressure of 20MPa to obtain the single-walled carbon nanotube- [ HBth ]][F 3 CSO 3 ]-a hydroxypropyl cellulose compact.
Example 17
Mixing benzothiazole tosyloxy salt ([ HBth ] [ PTSA ]) with the total mass of 0.15g and single-walled carbon nano tubes according to the mass ratio of 1/1, then mixing the mixture with ethyl cellulose according to the mass ratio (g/g) of 0.15/0.15 in a mortar, grinding the mixture evenly, and sieving the mixture with a 200-mesh sieve; and (3) placing the mixture powder into a stainless steel pressing die, and pressing and molding under the pressure of 18MPa to obtain the single-walled carbon nanotube- [ HBth ] [ PTSA ] -ethyl cellulose composite sheet.
Example 18
1-butyl-3-methylimidazolium hexafluorophosphate ([ C ] in a total mass of 0.15g 4 mim][PF 6 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with ethyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; putting the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 20MPa to obtain the multi-walled carbon nano-tube- [ C ] 4 mim][PF 6 ]-an ethylcellulose compact.
Example 19
1-Ethyl-3-methylimidazolium tetrafluoroborate ([ C ]) in a total mass of 0.05g 2 mim][BF 4 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with carboxymethyl cellulose in a mortar in a mass ratio (g/g) of 0.05/0.25, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 10MPa to obtain the multi-walled carbon nanotube- [ C ] 2 mim][BF 4 ]-a carboxymethyl cellulose composite sheet.
Example 20
The total mass of 0.05g of 1-hexyl-3-methylimidazolium methanesulfonate ([ Hmim)][CH 3 SO 3 ]) Mixing with multi-wall carbon nano-tubes in a mass ratio of 1/1, then mixing with hydroxypropyl cellulose in a mortar in a mass ratio (g/g) of 0.05/0.25, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 12MPa to obtain the multi-walled carbon nanotube- [ Hmim [ ]][CH 3 SO 3 ]-a hydroxypropyl cellulose compact.
Claims (9)
1. A carbon nanotube-ionic liquid-derived cellulose composite membrane is characterized in that the carbon nanotube, the ionic liquid and the derived cellulose used as a film forming agent are compounded by a simple physical mixing method, and the carbon nanotube-ionic liquid-derived cellulose composite membrane comprises the following specific steps:
(1) Mixing the ionic liquid and the carbon nano tube according to the mass ratio (mg/mg) of 1/1-1/20 to ensure that the ionic liquid and the carbon nano tube are fully combined; adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 to dilute, finally adding the mixture of the three into ethanol with the mass volume ratio (g/ml) of 0.3/50-0.3/100, and ultrasonically oscillating at room temperature to uniformly disperse the system;
(2) Continuously evaporating the uniform mixed system formed in the step (1) under a vacuum condition to remove ethanol, and finally naturally forming the carbon nano tube-ionic liquid-derived cellulose composite membrane on a smooth and clean plane.
2. A carbon nanotube-ionic liquid-derived cellulose composite sheet is characterized in that the carbon nanotube, the ionic liquid and the derived cellulose used as a diluent are pressed into sheets by a simple physical mixing method, and the carbon nanotube-ionic liquid-derived cellulose composite sheet comprises the following specific steps:
(1) Mixing the ionic liquid and the carbon nano tube according to the mass ratio (mg/mg) of 1/1-1/20 to ensure that the ionic liquid and the carbon nano tube are fully combined; then adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 to dilute, and finally fully grinding uniformly and sieving with a 200-mesh sieve;
(2) And placing the sieved mixture powder into a stainless steel pressing die, and pressing and forming under the pressure of 5-20 MPa to obtain the carbon nano tube-ionic liquid-derived cellulose composite sheet.
3. The carbon nanotube-ionic liquid-derivatized cellulose composite membrane or composite sheet according to claim 1 or 2, wherein the carbon nanotube and the ionic liquid are physically combined and mixed uniformly with a film-forming agent or a diluent to form the composite membrane or composite sheet, and the ionic liquid comprises imidazole or benzothiazole ionic liquids having different alkyl substituted chain lengths and anions.
4. The method for preparing a carbon nanotube-ionic liquid-cellulose composite membrane or composite sheet according to claim 1 or 2, wherein the carbon nanotube comprises a single-walled carbon nanotube or a multi-walled carbon nanotube.
5. The carbon nanotube-ionic liquid-derivatized cellulose composite film or composite sheet according to claim 1 or 2, wherein the film-forming agent or diluent is derivatized cellulose, including ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose.
6. The method for preparing the carbon nanotube-ionic liquid-derivatized cellulose composite membrane or sheet according to claim 1 or 2, wherein the mass ratio (mg/mg) of the ionic liquid to the carbon nanotube is 1/1 to 1/20.
7. A method for preparing a carbon nanotube-ionic liquid-derived cellulose composite membrane or composite sheet according to claim 1 or 2, wherein the mass ratio (g/g) of the ionic liquid-carbon nanotube mixture to the film forming agent or diluent is 0.05/0.25-0.15/0.15.
8. The method for preparing the carbon nanotube-ionic liquid-derivatized cellulose composite membrane according to claim 1, wherein ethanol is used as a solvent.
9. The method of preparing a carbon nanotube-ionic liquid-derivatized cellulose composite sheet according to claim 2, wherein the pressure is in the range of 5 to 20MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010534978.1A CN113797767B (en) | 2020-06-12 | 2020-06-12 | Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010534978.1A CN113797767B (en) | 2020-06-12 | 2020-06-12 | Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113797767A CN113797767A (en) | 2021-12-17 |
| CN113797767B true CN113797767B (en) | 2022-10-28 |
Family
ID=78944057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010534978.1A Active CN113797767B (en) | 2020-06-12 | 2020-06-12 | Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113797767B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177261A (en) * | 2007-11-08 | 2008-05-14 | 上海交通大学 | Method for preparing biocompatible cellulose functionalized carbon nano tube |
| WO2011026104A2 (en) * | 2009-08-31 | 2011-03-03 | The Regents Of The University Of Michigan | Preparation of layer-by-layer materials and coatings from ionic liquids |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005014332A (en) * | 2003-06-25 | 2005-01-20 | Toray Ind Inc | Laminate and its manufacturing method |
| US7713448B1 (en) * | 2007-08-21 | 2010-05-11 | Oceanit Laboratories, Inc. | Carbon nanomaterial dispersion and stabilization |
| US8974862B2 (en) * | 2009-11-03 | 2015-03-10 | Jong-Sam Yu | Method of manufacturing composite carbon sheet using expanded graphite sheet and mixed dispersion solution |
| WO2013081563A2 (en) * | 2011-10-24 | 2013-06-06 | Mahmut Bilgic | Stable tablet formulations |
| CN102677546B (en) * | 2012-05-02 | 2014-07-23 | 清华大学 | Ionic liquid coated paper of thin-walled carbon nanotube and preparation method of ionic liquid coated paper |
| CN102800846A (en) * | 2012-08-30 | 2012-11-28 | 上海锦众信息科技有限公司 | Preparation method for positive electrode of power battery |
| CN104064375B (en) * | 2014-07-08 | 2017-04-12 | 黑龙江大学 | Method for compounding ternary composite membrane of cellulose, graphene oxide and carbon nano tube in ionic liquid |
| CN104815695B (en) * | 2015-05-18 | 2017-03-08 | 浙江海洋学院 | A kind of method that carbon nanotube loaded ionic-liquid catalyst catalysis prepares diisobutylene |
| RU2018139875A (en) * | 2016-04-27 | 2020-05-27 | Торэй Индастриз, Инк. | LIQUID DISPERSION OF CARBON NANOTUBES, METHOD FOR ITS PRODUCTION AND ELECTRIC CONDUCTING FORMED BODY |
| CN109763210B (en) * | 2019-01-15 | 2021-06-18 | 中国科学院过程工程研究所 | Method for preparing cellulose-based carbon fiber or carbon film by ionic liquid |
-
2020
- 2020-06-12 CN CN202010534978.1A patent/CN113797767B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177261A (en) * | 2007-11-08 | 2008-05-14 | 上海交通大学 | Method for preparing biocompatible cellulose functionalized carbon nano tube |
| WO2011026104A2 (en) * | 2009-08-31 | 2011-03-03 | The Regents Of The University Of Michigan | Preparation of layer-by-layer materials and coatings from ionic liquids |
Non-Patent Citations (2)
| Title |
|---|
| "Doping metal organic frameworks with ionic liquids for adsorption of tetracyclines from water samples";Shun Yao等;《The Second International Conference on Materials Chemistry and Environmental Protection(2018)》;20181231;第69-72页 * |
| "Preparation of cellulose/multi-walled carbon nanotube composite membranes with enhanced conductive property regulated by ionic liquids";Wang Wenjun等;《Fibers and Polymers》;20170901;第18卷(第9期);第1780-1789页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113797767A (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Recent progress in bio-based aerogel absorbents for oil/water separation | |
| CN104495780B (en) | Hydrophilic graphene-carbon nano-tube composite super-light elastic aerogel and preparation method thereof | |
| Ding et al. | Nitrogen-enriched carbon nanofiber aerogels derived from marine chitin for energy storage and environmental remediation | |
| CN101993056B (en) | Graphene-based porous macroscopic carbon material and preparation method thereof | |
| Chen et al. | Fast microwave-assisted purification, functionalization and dispersion of multi-walled carbon nanotubes | |
| CN105642233B (en) | A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons | |
| Huang et al. | Large-scale preparation of electrically conducting cellulose nanofiber/carbon nanotube aerogels: Ambient-dried, recyclable, and 3D-Printable | |
| JPWO2007004652A1 (en) | Method for producing carbon nanotube dispersion | |
| KR101627016B1 (en) | Highly dispersible carbon nano structures and method for preparation thereof, and polymer composite comprising the carbon nano structures | |
| CN106276844B (en) | High Strength Carbon Nanotubes film, preparation method and application | |
| KR101610890B1 (en) | Carbon nanotube composite and method of matufacturing the same | |
| JP2006063307A (en) | Carbon nanotube-containing solution, film, and fiber | |
| CN106390952A (en) | Novel carbon nanotube composite hydrogel and preparation method thereof | |
| CN107081127A (en) | A kind of preparation method of graphene/activated carbon composite porous microspheres | |
| CN113797767B (en) | Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet | |
| CN114477151B (en) | Preparation method of graphene material, graphene material and application of graphene material | |
| CN107032323A (en) | A kind of preparation method of flake porous nano material | |
| CN104693474A (en) | Preparation method for three-dimensional porous material | |
| CN101177261B (en) | Method for preparing biocompatible cellulose functionalized carbon nano tube | |
| CN113527753A (en) | Bio-based foam material prepared under normal pressure and preparation method and application thereof | |
| Porwal et al. | An overview on carbon nanotubes | |
| Feng et al. | Interaction of water soluble chitosan with multiwalled carbon nanotubes | |
| CN105086300A (en) | Light, conducting and shielding composite material and preparation method thereof | |
| He et al. | Preparation and characterization of cellulose nanocrystals from spent edible fungus substrate | |
| Wang et al. | TEMPO-Oxidized Cellulose Beads for Cationic Dye Adsorption. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |