CN104559340B - Halobenzene functionalized and modified carbon nano tube and preparation method thereof - Google Patents
Halobenzene functionalized and modified carbon nano tube and preparation method thereof Download PDFInfo
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Abstract
The invention provides a halobenzene functionalized and modified carbon nano tube and a preparation method thereof. The halobenzene functionalized and modified carbon nano tube is characterized in that after carboxy groups on the surface of a carbon nano tube are acylated, the halobenzene functionalized carbon nano tube is prepared through Friedel-crafts reaction by using a Lewis acid as a catalyst and using halobenzene as a modifying agent. The dosage of an oxidizing agent and the processing time are controlled during oxidization, so that the adoption amount of carboxy groups is controlled, and further the number of halobenzene ketone structures grafted by the carbon nano tube is controlled; the types of halobenzene are changed so as to obtain multiple kinds of halobenzene functionalized carbon nano tubes. The obtained modified carbon nano tubes have good solubleness in organic solvents, such as NMP and DMF, the carbon nano tubes can be well dispersed in a resin matrix by an in-situ polymerization and in-situ compounding method, and the obtained modified carbon nano tubes can be used for preparing high-performance nano composite materials, high-strength film materials and high-performance fibers, and can also be used for preparing superfine fibers and non-woven fabrics through electrostatic spinning. Therefore, the surface-functionalized modified carbon nano tube prepared by the method disclosed by the invention can be applied to the fields of plastic and fiber modification, and electrostatic spinning.
Description
Technical field
The present invention relates to the method for modifying that a kind of carbon nano tube surface is modified, belong to Surface Modification of Nanosized Materials neck
Territory.
Background technology
CNT, because excellent mechanical property, heat conductivity, chemistry, energy storage and electric conductivity etc., is got over
Come the most enhancings being used as polymer or multi-functional packing material.CNT is as polymer filler
Only could effectively play in it is dispersed in polymeric matrix enhancing or heat-resisting wait act on.Due to carbon
Nanotube has higher specific surface area and easily reunites, and is difficult to preferably disperse, two in polymeric matrix
The interfacial interaction that person is formed is more weak, causes it to be difficult in the composite play Expected Results.Therefore,
How CNT is evenly dispersed in resin matrix, and makes CNT and matrix material fully tie
Close, farthest reduce the defect point that incompatibility causes, to reach the transmission of effective loading stress, to prevent
Only sliding between matrix and CNT and heat the subject matter becoming research such as effectively uniformly transfer.
Summary of the invention
Reunite greatly and easily to solve existing specific surface area of carbon nanotube, be difficult to preferably in polymeric matrix
Dispersion, the two formed interfacial interaction more weak, cause its in the composite be difficult to play expection effect
The technical problem of fruit, the present invention provides a kind of method of carbon nano tube surface functional modification..
The technical solution of the present invention is as follows:
The preparation method of a kind of halobenzene functional modification CNT, it is characterized in that this halobenzene function
Change modified carbon nano-tube preparation to comprise the following steps:
1] preparation of oxide/carbon nanometer tube
The mass ratio that CNT, strong oxidizer are pressed 3:5～32 adds in reaction vessel, at stirring condition
Under react, reaction temperature 50～90 DEG C, response time 2～12 hours；After having reacted, by reactant liquor
Dilution, vacuum filtration also repeatedly washs until filtrate is neutrality with deionized water, vacuum dried is dried
Oxide/carbon nanometer tube；
2] preparation of CNT it is acylated
Dry oxide/carbon nanometer tube, acylating agent, acid absorbent and solvent are joined anti-by certain mass ratio
Answering in container, carry out lucifuge reaction under agitation, reaction temperature is 30～80 DEG C, and the response time is 2.5～24
Hour；After completion of the reaction, to product vacuum filtration and use solvent cyclic washing, vacuum dried after,
Obtain the acylation CNT being dried,
3] preparation of halobenzene functionalized carbon nano-tube
Acylation CNT, halobenzene, catalyst and solvent are joined in reaction vessel by certain mass ratio,
Carrying out friedel-crafts acylation under agitation, reaction temperature is 40～80 DEG C, and the response time is 1～24 little
Time, halobenzene used is fluorobenzene or chlorobenzene；After completion of the reaction, by reactant liquor vacuum filtration and with solvent and going
Ionized water cyclic washing, vacuum dried after, obtain the halobenzene functionalized carbon nano-tube being dried.
Being more than the basic scheme of the present invention, based on this basic scheme, the present invention can also make following optimization.
Above-mentioned steps 1] used by CNT be arc discharge, template, catalytic pyrolysis method or laser evaporation
Single wall prepared by method or multi-walled carbon nano-tubes, strong oxidizer used is concentrated sulphuric acid, concentrated nitric acid, dense sulfur
Acid/concentrated nitric acid is arbitrarily arbitrary than the one in mixed acid than mixed acid and concentrated sulphuric acid/hydrogen peroxide.
Above-mentioned steps 2] used by acylating agent be thionyl chloride, Phosphorous chloride., phosphorus pentachloride, oxalyl chloride, three
One in phosphonium bromide, acid absorbent used is the one in pyridine, triethylamine, DMAP,
Solvent used be in dichloromethane, chloroform, oxolane, nitromethane any one and mutually it
Between the mixed solvent of arbitrary ratio.
Above-mentioned steps 3] in catalyst used be aluminum trichloride (anhydrous) or anhydrous ferric trichloride, solvent used
For a kind of and arbitrary ratio in petroleum ether, carbon tetrachloride, nitrobenzene ethane nitrile, 1,2-dichloroethanes
Mixed solvent.
Halobenzene functionalized carbon nano-tube prepared by above-mentioned method.
Present invention have the advantage that
Monomer the most used herein is the commercially available chemical products of high-volume, it is not necessary to prepares, purify monomer,
Cheap and easy to get.
2. the present invention uses friedel-crafts acylation to prepare halobenzene functionalized carbon nano-tube, can be aoxidized by control
During CNT, consumption and the oxidation treatment time of oxidant control the introducing of carboxyl on CNT
Amount, thus control on CNT, to be grafted the quantity to halobenzene ketone structure, by changing the kind of halobenzene monomer,
Obtaining the CNT of multiple halobenzene functionalization, process control is easier to.
3. the present invention uses friedel-crafts acylation to introduce on the carbon nanotubes halobenzene ketone structure, can use
" Grafted to " and the grafting method of " Grafted from ", by aromatic nucleophilic substitution reaction, be used for preparing carbon
Nanotube/polymer nanocomposites, CNT and polymer in nano composite material prepared by the method
Between covalent bond combine, and CNT presents in the polymer and is uniformly distributed.The method beneficially raising is received
Dispersibility between organic and inorganic phase and interface compatibility in nano composite material.
4. the modified carbon nano-tube prepared by the present invention has well in the organic solvents such as NMP, DMF
Dissolubility, makes CNT well be dispersed in resin matrix by the method for in-situ polymerization and In-situ reaction,
Can be used for preparing High performance nanometer composite material, high-strength membrane material and high-performance fiber；Owing to it has very
Good dissolubility, prepares superfine fibre and non-woven fabrics also by electrostatic spinning.Therefore the table that prepared by this invention
Surface function modified carbon nano-tube can be applicable to plastics, fibre modification and electrostatic spinning field.
5. the present invention uses Normal Pressure Stepwise to prepare halobenzene functionalized carbon nano-tube, its method is simple, low cost,
Process stabilizing, product yield are high, up to more than 90%.
Accompanying drawing explanation
Fig. 1 is the reaction equation preparing halobenzene functionalized carbon nano-tube.
Fig. 2 is the infrared spectrogram of fluorobenzene functionalized carbon nano-tube.
Fig. 3 is the thermogravimetic analysis (TGA) figure of fluorobenzene functionalized carbon nano-tube.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be the present embodiment
It is served only for the present invention is further described, it is impossible to be interpreted as the present invention is included the restriction of scope, this neck
The person skilled in the art in territory can make some nonessential improvement and adjustment according to the content of the invention described above,
Wherein said raw material number, in addition to specified otherwise, is parts by weight.
Embodiment 1,
(1) preparation of oxidation multi-walled carbon nano-tubes:
By multi-walled carbon nano-tubes 30 parts, concentrated sulphuric acid 320 parts, join with agitator, the reaction of thermometer
In device, react 2 hours temperature 90 DEG C；Reactant liquor is poured slowly in 1000 parts of deionized waters, vacuum
Sucking filtration also repeatedly washs with deionized water, until the aobvious neutrality of filtered solution.The oxidation multi-walled carbon nano-tubes that will obtain,
It is placed in 120 DEG C of vacuum drying ovens the oxidation multi-walled carbon nano-tubes obtaining being dried after being dried 24 hours.
(2) preparation of acylation multi-walled carbon nano-tubes:
By dry oxidation multi-walled carbon nano-tubes 30 parts, thionyl chloride 100 parts, pyridine 4 parts, anhydrous nitro
160 parts of methane, joins in the reactor with agitator, thermometer and condensing tube, keeps away temperature 80 DEG C
Photoreaction 2.5 hours；Vacuum filtration with anhydrous nitromethane cyclic washing, dry in 70 DEG C of vacuum drying ovens
Within dry 10 hours, obtain the acylation multi-walled carbon nano-tubes being dried.
(3) preparation of halobenzene functionalization multi-walled carbon nano-tubes:
Multi-walled carbon nano-tubes 30 parts, fluorobenzene 20 parts, aluminum trichloride (anhydrous) 40 parts, dry oil will be acylated
300 parts of ether, joins in the reactor with agitator, thermometer and condensing tube, in temperature 80 DEG C reaction
1 hour；By reactant liquor vacuum filtration and with petroleum ether and deionized water cyclic washing, at 100 DEG C of vacuum drying ovens
In be dried and within 20 hours, obtain the fluorobenzene functionalization multi-walled carbon nano-tubes that is dried.
Embodiment 2,
(1) preparation of oxidation SWCN:
By SWCN 30 parts, concentrated nitric acid 160 parts, join with agitator, the reaction of thermometer
In device, react 12 hours at temperature 50 C；Reactant liquor is poured slowly in 400 parts of deionized waters, vacuum
Sucking filtration also repeatedly washs with deionized water, until the aobvious neutrality of filtered solution.The oxidation SWCN that will obtain,
It is placed in 120 DEG C of vacuum drying ovens the oxidation SWCN obtaining being dried after being dried 24 hours.
(2) preparation of acylation SWCN:
By dry oxidation SWCN 30 parts, phosphorus pentachloride 20 parts, triethylamine 1 part, anhydrous two
Chloromethanes 40 parts, joins in the reactor with agitator, thermometer and condensing tube, temperature 30 DEG C
Lucifuge is reacted 24 hours；Vacuum filtration also uses anhydrous methylene chloride cyclic washing, dry in 70 DEG C of vacuum drying ovens
Within dry 10 hours, obtain the acylation SWCN being dried.
(3) preparation of halobenzene functionalization SWCN:
SWCN 30 parts, chlorobenzene 5 parts, anhydrous ferric trichloride 10 parts, anhydrous two sulfur will be acylated
Change 100 parts of carbon, join in the reactor with agitator, thermometer and condensing tube, anti-temperature 40 DEG C
Answer 24 hours；By reactant liquor vacuum filtration and with Carbon bisulfide and deionized water cyclic washing, true at 100 DEG C
Empty baking oven is dried the chlorobenzene functionalization SWCN obtaining for 20 hours being dried.
Embodiment 3,
(1) preparation of oxidation SWCN:
By SWCN 30 parts, concentrated sulphuric acid 90 parts, concentrated nitric acid 30 parts joins with agitator, temperature
In the reactor of degree meter, react 5 hours at temperature 60 C；Reactant liquor is poured slowly into 300 parts of deionized waters
In, vacuum filtration also repeatedly washs with deionized water, until the aobvious neutrality of filtered solution.The oxidation single wall that will obtain
CNT, is placed in 120 DEG C of vacuum drying ovens the oxidation SWCN obtaining being dried after being dried 24 hours.
(2) preparation of acylation SWCN:
By dry oxidation SWCN 30 parts, Phosphorous chloride. 70 parts, DMAP 2.5 parts,
Anhydrous chloroform 100 parts, joins in the reactor with agitator, thermometer and condensing tube, in temperature
Spend 50 DEG C of lucifuges to react 14 hours；Vacuum filtration with anhydrous chloroform cyclic washing, in 70 DEG C of vacuum
Baking oven is dried the acylation SWCN obtaining for 10 hours being dried.
(3) preparation of halobenzene functionalization SWCN:
To and be acylated SWCN 30 parts, fluorobenzene 10 parts, aluminum trichloride (anhydrous) 30 parts, anhydrous 1,2-
Dichloromethane 120 parts, joins in the reactor with agitator, thermometer and condensing tube, temperature 65 DEG C
React 15 hours；By reactant liquor vacuum filtration and with 1,2-dichloromethane and deionized water cyclic washing,
100 DEG C of vacuum drying ovens are dried the fluorobenzene functionalization SWCN obtaining for 20 hours being dried.
Embodiment 4,
(1) preparation of oxidation multi-walled carbon nano-tubes:
By multi-walled carbon nano-tubes 30 parts, concentrated sulphuric acid 100 parts, hydrogen peroxide 40 parts join with agitator,
In the reactor of thermometer, react 4 hours temperature 80 DEG C；Reactant liquor is poured slowly into 460 parts of deionizations
In water, vacuum filtration also repeatedly washs with deionized water, until the aobvious neutrality of filtered solution.By many for the oxidation that obtains
Wall carbon nano tube, is placed in 120 DEG C of vacuum drying ovens the oxidation multi-wall carbon nano-tube obtaining being dried after being dried 24 hours
Pipe.
(2) preparation of acylation multi-walled carbon nano-tubes:
By dry oxidation multi-walled carbon nano-tubes 30 parts, oxalyl chloride 80 parts, pyridine 3 parts, anhydrous tetrahydrochysene furan
Mutter 120 parts, join in the reactor with agitator, thermometer and condensing tube, in temperature 60 C lucifuge
React 17 hours；Vacuum filtration also uses anhydrous tetrahydro furan cyclic washing, is dried in 70 DEG C of vacuum drying ovens
Within 10 hours, obtain the acylation multi-walled carbon nano-tubes being dried.
(3) preparation of halobenzene functionalization multi-walled carbon nano-tubes:
Multi-walled carbon nano-tubes 30 parts, fluorobenzene 12 parts, aluminum trichloride (anhydrous) 20 parts, anhydrous acetonitrile will be acylated
140 parts, join in the reactor with agitator, thermometer and condensing tube, react 15 temperature 75 DEG C
Hour；By reactant liquor vacuum filtration and with acetonitrile and deionized water cyclic washing, dry in 100 DEG C of vacuum drying ovens
Within dry 20 hours, obtain the fluorobenzene functionalization multi-walled carbon nano-tubes being dried.
Embodiment 5,
(1) preparation of oxidation SWCN:
By SWCN 30 parts, concentrated sulphuric acid 180 parts, join with agitator, the reaction of thermometer
In device, react 6 hours temperature 84 DEG C；Being poured slowly into by reactant liquor in 640 parts of deionized waters, vacuum is taken out
Filter is also repeatedly washed with deionized water, until the aobvious neutrality of filtered solution.The oxidation SWCN that will obtain,
It is placed in 120 DEG C of vacuum drying ovens the oxidation SWCN obtaining being dried after being dried 24 hours.
(2) preparation of acylation SWCN:
By dry oxidation SWCN 30 parts, phosphorus tribromide 40 parts, pyridine 1.5 parts, anhydrous trichlorine
75 parts of methane, joins in the reactor with agitator, thermometer and condensing tube, keeps away temperature 55 DEG C
Photoreaction 18.5 hours；Vacuum filtration with anhydrous chloroform cyclic washing, dry in 70 DEG C of vacuum drying ovens
Within dry 10 hours, obtain the acylation SWCN being dried.
(3) preparation of halobenzene functionalization SWCN:
SWCN 30 parts, chlorobenzene 14 parts, aluminum trichloride (anhydrous) 32 parts, anhydrous nitro will be acylated
Benzene 210 parts, joins in the reactor with agitator, thermometer and condensing tube, reacts at temperature 50 C
8 hours；By reactant liquor vacuum filtration and with Nitrobenzol and deionized water cyclic washing, at 100 DEG C of vacuum drying ovens
In be dried and within 20 hours, obtain the chlorobenzene functionalization SWCN that is dried.
Embodiment 6,
(1) preparation of oxidation multi-walled carbon nano-tubes:
By multi-walled carbon nano-tubes 30 parts, concentrated sulphuric acid 180 parts, concentrated nitric acid 40 parts join with agitator,
In the reactor of thermometer, react 5 hours temperature 65 DEG C；Reactant liquor is poured slowly into 700 parts of deionizations
In water, vacuum filtration also repeatedly washs with deionized water, until the aobvious neutrality of filtered solution.By many for the oxidation that obtains
Wall carbon nano tube, is placed in 120 DEG C of vacuum drying ovens the oxidation multi-wall carbon nano-tube obtaining being dried after being dried 24 hours
Pipe.
(2) preparation of acylation multi-walled carbon nano-tubes:
By dry oxidation multi-walled carbon nano-tubes 30 parts, thionyl chloride 60 parts, pyridine 3 parts, anhydrous tetrahydrochysene
160 parts of furan, joins in the reactor with agitator, thermometer and condensing tube, keeps away at temperature 50 C
Photoreaction 14.8 hours；Vacuum filtration also uses anhydrous tetrahydro furan cyclic washing, dry in 70 DEG C of vacuum drying ovens
Within dry 10 hours, obtain the acylation multi-walled carbon nano-tubes being dried.
(3) preparation of halobenzene functionalization multi-walled carbon nano-tubes:
To be acylated multi-walled carbon nano-tubes 30 parts, fluorobenzene 10.8 parts, aluminum trichloride (anhydrous) 24 parts, without water stone
120 parts of ether of oil, joins in the reactor with agitator, thermometer and condensing tube, anti-at temperature 70 C
Answer 15 hours；By reactant liquor vacuum filtration and with petroleum ether and deionized water cyclic washing, in 100 DEG C of vacuum
Baking oven is dried the fluorobenzene functionalization multi-walled carbon nano-tubes obtaining for 20 hours being dried.
CNT used by the inventive method first step is arc discharge, template, catalysis pyrolysis, laser
Single wall prepared by method of evaporating or multi-walled carbon nano-tubes.Strong oxidizer used include concentrated sulphuric acid, concentrated nitric acid,
Concentrated sulphuric acid/hydrogen peroxide is arbitrarily arbitrary than mixed acid and concentrated sulphuric acid/concentrated nitric acid compares mixed acid.
Acylating agent used in the inventive method second step is thionyl chloride, Phosphorous chloride., phosphorus pentachloride, grass
Acyl chlorides, phosphorus tribromide.Acid absorbent used is pyridine, triethylamine, DMAP.Used
Dissolving is that dichloromethane, chloroform, oxolane, nitromethane and arbitrary ratio mixing are molten
Agent.
Halobenzene used in the inventive method the 3rd step is fluorobenzene, chlorobenzene.Catalyst used is anhydrous trichlorine
Change aluminum, anhydrous ferric trichloride.Solvent used is petroleum ether, carbon tetrachloride, nitrobenzene ethane nitrile, 1,2-dichloro
Ethane and arbitrary compare mixed solvent.
Fig. 1 is the preparation process of halobenzene functionalized carbon nano-tube, wherein the fluorobenzene functionalized carbon prepared by embodiment 1
The structure of nanotube is confirmed through examination of infrared spectrum, as in figure 2 it is shown, result shows: compared to not making
The CNT (MWNTs) processed, carboxylic carbon nano-tube (MWNTs-COOH) and fluorobenzene function
Carbon nano tube (MWNTs-F) is at 1707cm-1There is the stretching vibration peak of C=O, and fluorobenzene function in place
Carbon nano tube 1440,1500 and 1580cm-1There is obvious phenyl ring absorption of vibrations at place, illustrates that carboxyl is
By fluorobenzene functionalization, fluorobenzene ketone structure is keyed on CNT.Fig. 3 is different in embodiment 1
Processing stage CNT thermogravimetric analysis, relative to the CNT without any process, carboxylated carbon is received
Mitron and fluorobenzene functionalized carbon nano-tube are along with the rising of heating-up temperature, and carbon left reduces substantially, and this explanation exists
After CNT is done chemical modification, a certain amount of little molecule of keyed jointing on the carbon nanotubes, in conjunction with infrared table
The result levied i.e. shows carboxyl and has been keyed to fluorobenzene ketone on CNT.
Claims (5)
1. the preparation method of a halobenzene functional modification CNT, it is characterised in that: this halobenzene function
Change modified carbon nano-tube preparation to comprise the following steps:
1] preparation of oxide/carbon nanometer tube
The mass ratio that CNT, strong oxidizer are pressed 3:5～32 adds in reaction vessel, at stirring condition
Under react, reaction temperature 50～90 DEG C, response time 2～12 hours；After having reacted, by reactant liquor
Dilution, vacuum filtration also repeatedly washs until filtrate is neutrality with deionized water, vacuum dried is dried
Oxide/carbon nanometer tube,
2] preparation of CNT it is acylated
Dry oxide/carbon nanometer tube, acylating agent, acid absorbent and solvent are joined anti-by certain mass ratio
Answering in container, carry out lucifuge reaction under agitation, reaction temperature is 30～80 DEG C, and the response time is 2.5～24
Hour；After completion of the reaction, to product vacuum filtration and use solvent cyclic washing, vacuum dried after,
Obtain the acylation CNT being dried,
3] preparation of halobenzene functionalized carbon nano-tube
Acylation CNT, halobenzene, catalyst and solvent are joined in reaction vessel by certain mass ratio,
Carrying out friedel-crafts acylation under agitation, reaction temperature is 40～80 DEG C, and the response time is 1～24 little
Time, halobenzene used is fluorobenzene or chlorobenzene；After completion of the reaction, by reactant liquor vacuum filtration and with solvent and going
Ionized water cyclic washing, vacuum dried after, obtain the halobenzene functionalized carbon nano-tube being dried.
2. according to the preparation method of the halobenzene functional modification CNT described in claim 1, its feature
It is:
Step 1] used by CNT be arc discharge, template, catalytic pyrolysis method or laser evaporation method
The single wall of preparation or multi-walled carbon nano-tubes, strong oxidizer used is concentrated sulphuric acid, concentrated nitric acid, concentrated sulphuric acid/dense
Nitric acid is arbitrarily arbitrary than the one in mixed acid than mixed acid and concentrated sulphuric acid/hydrogen peroxide.
3. according to the preparation method of the halobenzene functional modification CNT described in claim 1, its feature
It is:
Step 2] used by acylating agent be thionyl chloride, Phosphorous chloride., phosphorus pentachloride, oxalyl chloride, tribromide
One in phosphorus,
Acid absorbent used is the one in pyridine, triethylamine, DMAP,
Solvent used is any one and phase in dichloromethane, chloroform, oxolane, nitromethane
The mixed solvent of arbitrary ratio between Hu.
4., according to the preparation method of the halobenzene functional modification CNT described in claim 1, its feature exists
In:
Step 3] in catalyst used be aluminum trichloride (anhydrous) or anhydrous ferric trichloride,
Solvent used be the one in petroleum ether, carbon tetrachloride, nitrobenzene ethane nitrile, 1,2-dichloroethanes and
The mixed solvent of arbitrary ratio.
5. the halobenzene functionalized carbon nano-tube prepared according to the method one of Claims 1-4 Suo Shu.
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