CN106587013B - A kind of switching mode Carbon nano-tube dispersant - Google Patents
A kind of switching mode Carbon nano-tube dispersant Download PDFInfo
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- CN106587013B CN106587013B CN201611110369.3A CN201611110369A CN106587013B CN 106587013 B CN106587013 B CN 106587013B CN 201611110369 A CN201611110369 A CN 201611110369A CN 106587013 B CN106587013 B CN 106587013B
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Abstract
A kind of switching mode Carbon nano-tube dispersant, the dispersing agent are decomposed after being passed through nitrogen, air or heating, generate the aminated compounds of not surface-active, which is passed through CO again2After become bicarbonate, become a kind of cationic surface active agent；The dispersing agent can dispersing Nano carbon tubes in aqueous solution, when needing clean carbon nanotube, the surfactant is decomposed after being passed through nitrogen, air or heating, and obtains the undispersed carbon nanotube of clean surface, after being passed through carbon dioxide, surfactant and energy dispersing Nano carbon tubes are re-formed.
Description
Technical field
The present invention relates to a kind of switching mode Carbon nano-tube dispersants, belong to Colloid and interface chemistry technical field.
Background technique
Carbon nanotube is because receiving people with unique structure and superior electricity, optics, chemically and thermally mechanical property due to
More and more concerns.But due to there is stronger Van der Waals force, leading to be easy to be wrapped in one between carbon nanotube
Rise or reunion bunchy, seriously constrain the application of carbon nanotube.The dispersibility for how improving carbon nanotube becomes urgent at present
Problem to be solved.Physical method and chemistry functional method are the methods of more commonly used dispersing Nano carbon tubes at present.Physical method
It is so that carbon nanotube is effectively scatter by the ultrasound and ultracentrifugation of high-energy, the ultrasound of high-energy can make in this method
Carbon nanotube fracture, shortens its length, reduces the draw ratio of carbon nanotube, certain damage is caused to carbon nanotube, influences it
Application value, and there is also disperse incomplete disadvantage for this method.Chemistry functional method can be divided into covalent functionalization
Two kinds of method and non-covalent functionalization method.Covalent functionalization method is to handle carbon nanotube by nitration mixture or other strong oxidizers, from
And the surface texture for changing carbon nanotube makes it introduce the various active groups such as carboxyl, hydroxyl, amino, improves point of its aqueous solution
Property is dissipated, but this method can damage the structurally and mechanically performance of carbon nanotube to a certain extent；Non-covalent functionalization method is
Carbon nanotube combines to obtain the functionalized carbon nano-tube of structural integrity with other compounds by π-π non-covalent bond effect, should
Kind of method can not only improve the dispersibility of carbon nanotube and also will not structure to carbon nanotube and electric property damage,
Belong to one of non-covalent functional method by surfactant-dispersed carbon nanotube.
However after conventional surfactants and carbon nanotube interaction, it is more difficult to by it under carbon nano tube surface removing
Come, the present invention attempts to invent a kind of switching mode Carbon nano-tube dispersant, the dispersing agent can in water dispersing Nano carbon tubes and
When needing clean carbon nanotube, the carbon nanotube of clean surface is obtained after being passed through nitrogen or air or heating.
Summary of the invention
The purpose of the present invention is to provide a kind of switching mode Carbon nano-tube dispersants, and on the one hand the dispersing agent can divide in water
Dissipate carbon nanotube；On the other hand, when needing clean carbon nanotube, the surface-active after being passed through nitrogen, air or heating
Agent is decomposed, and the undispersed carbon nanotube of clean surface is obtained.
Technical solution of the present invention
Technical solution of the present invention: a kind of switching mode Carbon nano-tube dispersant, the dispersing agent are passed through nitrogen, air or add
It decomposes after heat, generates the aminated compounds of not surface-active, which is passed through CO again2After become bicarbonate
Salt becomes a kind of cationic surface active agent；The dispersing agent can dispersing Nano carbon tubes in aqueous solution, needing clean carbon to receive
When mitron, the surfactant is decomposed after being passed through nitrogen, air or heating, and obtains the undispersed carbon nanometer of clean surface
Pipe after being passed through carbon dioxide, re-forms surfactant and energy dispersing Nano carbon tubes；Carbon nanotube is single wall or multi wall carbon
Nanotube or both mixture, the dispersant structure formula are as follows:
Wherein R1, R2, R3For C1~C18Linear chain or branched chain, saturation or unsaturation, the alkyl for containing or not contain aromatic rings.
The preparation of above-mentioned dispersing agent mainly comprises the steps that
(1) hydroxyl protection: by the hydroxy-protecting agent of deoxycholic acid and 1~30 molar equivalent, 1 is reacted at 20~120 DEG C
Hydroxyl protection product is obtained after~30 hours, hydroxy-protecting agent is trimethylsilyl chloride, hexamethyldisilazane, formic acid, acetic acid
One or more of acid anhydride mixture；
(2) amidated products: by hydroxyl protection product and 1~10 molar equivalent thionyl chloride or oxalyl chloride in organic solvent
Middle reaction 1~72 hour, removes organic solvent and thionyl chloride or oxalyl chloride after reaction by 20~45 DEG C of reaction temperature, will
Intermediate product reacts 1~72 hour in organic solvent with alkyl diamine, and reaction temperature -10~40 DEG C obtain amidated products,
Wherein the alkyl in alkyl diamine is C1~C18Linear chain or branched chain, saturation or unsaturation, the alkyl for containing or not contain aromatic rings；
Organic solvent is one or more of mixed solvents such as methylene chloride, chloroform, ether；
(3) hydroxyl is deprotected: amidated products being reacted with alkali, obtain hydroxyl deprotection product, wherein alkali is hydroxide
The one or more mixture such as sodium, potassium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, saleratus；
(4) by reduzate and CO2Contact generates bicarbonate cationic surfactant.
Dispersing agent of the invention has excellent surface chemistry, has CO2/N2Response performance, the i.e. dispersing agent are passed through
It decomposes after nitrogen, air or heating, generates the aminated compounds of not surface-active, which is passed through again
CO2After become bicarbonate, become a kind of cationic surface active agent.
Beneficial effects of the present invention: the dispersing agent of the invention dispersing agent can dispersing Nano carbon tubes in aqueous solution, needing
When wanting clean carbon nanotube, the surfactant is decomposed after being passed through nitrogen, air or heating, and obtains not dispersing for clean surface
Carbon nanotube, after being passed through carbon dioxide, re-form surfactant and can dispersing Nano carbon tubes, therefore it is living with conventional surface
Property agent is compared, and dispersing agent of the invention can pass through CO2/N2The dispersion behavior for artificially controlling carbon nanotube, in chemical phase
Pass field, such as the multiple fields such as polymer, nano material, composite material, sensor and food, weaving, leather all have
Important application value.
Detailed description of the invention
Attached drawing 1 is aqueous dispersant N2/CO2Switch schematic diagram；
Attached drawing 2 is that carbon nanotube is added before and after dispersing agent and is passed through appearance diagram after nitrogen or air or heating.
Specific embodiment
Embodiment 1: the acetic anhydride of deoxycholic acid and 10 times of molar equivalents obtains hydroxyl guarantor after reacting 30 hours at 65 DEG C
Protect product；Hydroxyl protection product is reacted 24 hours at room temperature in methylene chloride with the thionyl chloride of 2 molar equivalents, reaction knot
Organic solvent and thionyl chloride are removed after beam, obtain chloride product, by chloride product and N, N- dimethyl-ethylenediamine is two
It is reacted 24 hours in chloromethanes, obtains amidated products, amidated products mixed with 2%NaOH (mass percent), room temperature
Stirring 24 hours obtains hydroxyl deprotection product, is passed through carbon dioxide into hydroxyl deprotection product aqueous solution, obtains deoxidation
Cholic acid amide groups ethylenediamine bicarbonate.
Embodiment 2: the hexamethyldisilazane of deoxycholic acid and 10 times of molar equivalents, after being reacted 30 hours at 65 DEG C
To hydroxyl protection product；Hydroxyl protection product and 2 molar equivalent oxalyl chlorides are reacted 24 hours at room temperature in methylene chloride, instead
Organic solvent and oxalyl chloride are removed after answering, and obtain chloride product, by chloride product and N, N- diamine dimethyl butyrate exists
It is reacted 24 hours in methylene chloride, obtains amidated products, amidated products mixed with 2%NaOH (mass percent), room
Temperature stirring 24 hours obtains hydroxyl deprotection product, is passed through carbon dioxide into hydroxyl deprotection product aqueous solution, is taken off
Oxycholic acid amide groups butanediamine bicarbonate.
1% (mass percent) dispersing agent deoxycholic acid amide groups ethylenediamine bicarbonate aqueous solution of embodiment 3:10mL
Middle addition 10mg multi-walled carbon nanotube, after being dispersed with ultrasonic disperse machine, the multi-walled carbon nanotube aqueous solution dispersed, this is water-soluble
When liquid is passed through nitrogen or heating, dispersing agent is decomposed, the multi-walled carbon nanotube aqueous solution reunited；When being passed through CO again2And surpass
After sound dispersion, the multi-walled carbon nanotube aqueous solution of dispersion is retrieved.
1% (mass percent) dispersing agent deoxycholic acid amide groups butanediamine bicarbonate aqueous solution of embodiment 4:10mL
Middle addition 10mg single-walled carbon nanotube, after being dispersed with ultrasonic disperse machine, the single-walled carbon nanotube aqueous solution dispersed, this is water-soluble
When liquid is passed through nitrogen or heating, dispersing agent is decomposed, the single-walled carbon nanotube aqueous solution reunited；When being passed through CO again2And surpass
After sound dispersion, the single-walled carbon nanotube aqueous solution of dispersion is retrieved.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on above description specific embodiment.To those skilled in the art, the equivalent modifications and replace that any couple of present invention carries out
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and repair
Change, all covers within the scope of the present invention.
Claims (3)
1. a kind of switching mode Carbon nano-tube dispersant, it is characterized in that its can dispersing Nano carbon tubes in aqueous solution, needing cleaning
When carbon nanotube, the dispersing agent is decomposed after being passed through nitrogen, air or heating, and generates the aminated compounds of not surface-active,
The undispersed carbon nanotube of clean surface is obtained, the aminated compounds after decomposition is passed through CO again2After become bicarbonate surface
Activating agent, again become can dispersing Nano carbon tubes dispersing agent, the dispersing agent be using deoxycholic acid as raw material, through hydroxyl protection,
Amidation, hydroxyl deprotection are passed through a kind of bicarbonate cationic surface active agent obtained after carbon dioxide, chemistry knot
Structure formula are as follows:
Wherein R1, R2, R3For C1~C18Linear chain or branched chain, saturation or unsaturation, the alkyl for containing or not contain aromatic rings.
2. switching mode Carbon nano-tube dispersant according to claim 1, it is characterised in that synthesis step are as follows:
(1) by the hydroxy-protecting agent of deoxycholic acid and 1~30 molar equivalent, 1~30 hydroxyl protection: is reacted at 20~120 DEG C
Hydroxyl protection product is obtained after hour, hydroxy-protecting agent is trimethylsilyl chloride, in hexamethyldisilazane, formic acid, acetic anhydride
One or more of mixtures；
(2) amidated products: hydroxyl protection product and 1~10 molar equivalent thionyl chloride or oxalyl chloride is anti-in organic solvent
It answers 1~72 hour, 20~45 DEG C of reaction temperature, removes organic solvent and thionyl chloride or oxalyl chloride after reaction, it will be intermediate
Product reacts 1~72 hour in organic solvent with alkyl diamine, and reaction temperature -10~40 DEG C obtain amidated products, wherein
Alkyl in alkyl diamine is C1~C18Linear chain or branched chain, saturation or unsaturation, the alkyl for containing or not contain aromatic rings；It is organic
Solvent is methylene chloride, chloroform, ether one or more mixed solvent；
(3) hydroxyl is deprotected: amidated products being reacted with alkali, obtain hydroxyl deprotection product, wherein alkali is sodium hydroxide, hydrogen
Potassium oxide, ammonium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, saleratus one or more mixture；
(4) by reduzate and CO2Contact generates bicarbonate cationic surfactant.
3. switching mode Carbon nano-tube dispersant according to claim 1, it is characterised in that carbon nanotube be single wall or
Multi-walled carbon nanotube or both mixture.
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| CN201611110369.3A CN106587013B (en) | 2016-12-06 | 2016-12-06 | A kind of switching mode Carbon nano-tube dispersant |
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| CN1246218C (en) * | 2003-11-27 | 2006-03-22 | 上海交通大学 | Carbon nanometer tube with initiating group on surface and its preparation method |
| CN101327415B (en) * | 2008-07-24 | 2012-10-03 | 中国科学院上海硅酸盐研究所 | Dispersing method of polyalcohol dispersing agent of one-dimensional carbon nano material |
| CN102794133A (en) * | 2012-05-08 | 2012-11-28 | 内蒙古大学 | Cationic surfactant and preparation method thereof |
| CN105597617B (en) * | 2015-11-04 | 2018-04-13 | 江南大学 | A kind of cumarin base light CO2/N2Double stimuli responsive type surfactant and preparation method thereof |
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