CN108301200A - Hold the TiO of fluorine-based dissaving polymer modification2The preparation method of intercalation graphene oxide - Google Patents
Hold the TiO of fluorine-based dissaving polymer modification2The preparation method of intercalation graphene oxide Download PDFInfo
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Abstract
The present invention provides a kind of TiO of the fluorine-based dissaving polymer modification in end2The preparation method of intercalation graphene oxide, including：TiO is prepared according to graphene oxide2Intercalation graphene oxide；According to TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide；It is modified TiO according to EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation graphene oxide；The TiO modified according to dissaving polymer2Intercalation graphene oxide prepares the TiO2 intercalation graphene oxides of the fluorine-based dissaving polymer modification in end.The TiO of the fluorine-based dissaving polymer modification in end obtained2Intercalation graphene oxide good water solubility has super hydrophobic effect, and integrates the functions such as catalysis, super-hydrophobic, antibacterial, and can effectively promote fastness between the substrates such as finish coating and fabric, raising wearability by the connection of chemical bond.
Description
Technical field
The present invention relates to a kind of TiO of the fluorine-based dissaving polymer modification in chemicals field more particularly to end2Intercalation oxygen
The preparation method of graphite alkene.
Background technology
Composite multifunction nano material not only has the special nature of nano material, and functional material can kept original
On the basis of Wuli-Shili-Renli system approach, the function that different materials are possessed organically is combined together, and this combination is not each group
Divide the simple addition of performance, but " learning from other's strong points to offset one's weaknesses " realizes different materials on the basis of holding each component original Wuli-Shili-Renli system approach
Performance between material is compound, complementary and optimization.
It is more about the related patents of graphene composite material at present, as " a kind of graphene oxide is negative for Chinese invention patent
The method for carrying golden platinum catalyst removal carbon monoxide "（CN 104923220A）In, disclose a kind of graphene oxide-loaded golden platinum
Graphite after graphene oxide is made in peroxidating, is then added to gold chloride and chloroplatinic acid by the preparation method of catalyst, this method
In solution, iron hydroxide, urea, nickel hydroxide, dispersant progress will be added in solution again after stirring, concussion or centrifugation
High temperature is dried, and a kind of catalyst of graphene oxide-loaded golden platinum is obtained after dry；As Chinese invention patent " a kind of graphene/
Optically catalytic TiO 2 composite material and preparation method "（CN 104084186B）In, disclose a kind of graphene/titanium dioxide
The preparation method of titanium optic catalytic composite material, this method by macropore graphene and mesoporous TiO 2 by macropore and it is mesoporous mutually
Connection so that titanium dioxide nanoparticle is filled in the macropore of graphene, and it is multiple that graphene/optically catalytic TiO 2 is prepared
Condensation material；Such as Chinese invention patent " a kind of super-hydrophobic redox graphene/sponge composite material and preparation method "（CN
105754144A）In, a kind of preparation method of super-hydrophobic redox graphene/sponge composite material is disclosed, this method is adopted
Graphene oxide is reduced into redox graphene, and in hole etc. using ethylenediamine as reducing agent with microwave-ultrasonic method
Redox graphene is disperseed under sound wave effect and is attached on commodity sponge, to obtain the oxygen reduction fossil of super-hydrophobicity
Black alkene/sponge composite material.Its common deficiency is that the graphene composite material prepared has a single function, and is not carried out multi-functional
Change.
Invention content
Present invention aims at provide a kind of TiO of the fluorine-based dissaving polymer modification in end2The system of intercalation graphene oxide
Preparation Method has super hydrophobic effect to prepare with good water solubility, and collect catalysis, super-hydrophobic, antibacterial etc. it is multi-functional in
The TiO of the fluorine-based dissaving polymer modification in end of one2Intercalation graphene oxide.
For achieving the above object, the present invention provides a kind of TiO of the fluorine-based dissaving polymer modification in end2Intercalation oxygen
The preparation method of graphite alkene, including：
（1）TiO is prepared according to graphene oxide2Intercalation graphene oxide；
（2）According to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide；
（3）It is modified TiO according to the EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation aoxidizes stone
Black alkene；
（4）The TiO modified according to the dissaving polymer2Intercalation graphene oxide prepares the fluorine-based dissaving polymer modification in end
TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the step（1）It specifically includes：
Graphene oxide is put into hydrothermal reaction kettle, the first preset time is reacted under the first preset temperature, ultrasound second is pre-
If after the time, anhydrous state being dried under the second preset temperature and obtains dewatered graphene oxide；
By the hydrochloric acid, butyl titanate, sodium hydroxide solution of the dewatered graphene oxide and the first preset ratio close
It closes in container after ultrasonic third preset time, acquisition TiO2Intercalation graphene oxide solution；
According to the TiO2Intercalation graphene oxide solution obtains TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, first preset temperature is 110 DEG C -130 DEG C, and described first is default
Time is 3-4 hours, and second preset time is 30-50 minutes, and second preset temperature is 40-50 DEG C, the oxidation
First preset ratio of graphene and the quality of hydrochloric acid, butyl titanate, sodium hydroxide is 1:3:50:3, when the third is preset
Between be 3-4 hours.
Preferably, in above-mentioned preparation method, the step（2）It specifically includes：
By the TiO2Intercalation graphene oxide is dispersed in sub- containing ethylene modulators, dicyclohexyl carbon two by the second preset ratio
In the DMF solution of amine and 4- dimethyl-nitrine pyridine, after supersound process, it is heated to third preset temperature, reaction the 4th is pre-
If after the time, washing DMF by deionized water and centrifuging the acquisition EDA modifications TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the TiO2Intercalation graphene oxide and the quality of the DMF solution
Second preset ratio is 1:500, DMF with ethylene modulators, dicyclohexylcarbodiimide, 4- dimethyl-nitrine pyridine quality
Than being 1:0.2：0.02:0.004, the third preset temperature is 50-70 DEG C, and the 4th preset time is 9-12 hours.
Preferably, in above-mentioned preparation method, the step（3）It specifically includes：
The EDA is modified TiO2Intercalation graphene oxide be dispersed in containing dicyclohexylcarbodiimide by third preset ratio and
Dispersion is obtained in the nmp solution of 4- dimethyl-nitrine pyridine, pyridine and triphenyl phosphite；
The LiCl powder of 4th preset ratio and dissaving polymer are added in the dispersion simultaneously stirring and dissolving, mixed
Close object；
After the mixture is heated to the 4th preset temperature under magnetic stirring, it is added into the play of 10 times of mixture quality
In the methanol of strong stirring；
The 5th preset time of ultrasonic disperse, steams methanol under the 5th preset temperature, is washed and is centrifuged with DMF and is overspend
The TiO of fluidized polymer modification2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the TiO of EDA modifications2The quality of intercalation graphene oxide and nmp solution
The third preset ratio be 1:160, NMP with DMAP, pyridine, triphenyl phosphite mass ratio be 1:0.006:0.06:
0.1, the TiO that the EDA is modified2The described 4th of the quality of intercalation graphene oxide and LiCl powder, dissaving polymer is pre-
If ratio is 1:0.6:6, the 4th preset temperature be 80-90 DEG C, the 5th preset temperature be 70-80 DEG C, the described 5th
Preset time is 9-10 hours, and the dissaving polymer is Hyperbranched Polymer with Terminal Amido, Hyperbranched Polymer with Terminal Hydroxyl
And any one or more in end carboxyl super branched polymer.
Preferably, in above-mentioned preparation method, the step（4）It specifically includes：
The TiO that the dissaving polymer is modified2Intercalation graphene oxide is dispersed in the mixing of absolute ethyl alcohol and deionized water
In solution, it is ultrasonically treated the 6th preset time under the 6th preset temperature and obtains the TiO that dissaving polymer is modified2Intercalation aoxidizes
Graphene dispersion body；
The TiO of dissaving polymer modification is adjusted using acetic acid2The pH value of intercalation graphene oxide dispersion, is then stirred in machinery
The lower 1H by the 5th preset ratio, 1H, 2H are mixed, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer and repair
The TiO of decorations2In intercalation graphene oxide dispersion；
Mixture is stirred at reflux the 7th preset time under the 7th preset temperature, after reaction, it is fluorine-based hyperbranched to obtain the end
Polymer-modified TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the 6th preset temperature is room temperature, and the 6th preset time is 3-
4 hours, the TiO of the dissaving polymer modification2The mixed solution of intercalation graphene oxide and absolute ethyl alcohol and deionized water
（The ratio of ethyl alcohol and water is 8:1）The 5th preset ratio be 1:1.5, acetic acid adjusts the TiO of dissaving polymer modification2
The pH value of intercalation graphene oxide dispersion is 2.5-3, the TiO of dissaving polymer modification2Intercalation graphene oxide and 1H,
The mass ratio of 1H, 2H, 2H- perfluoro capryl triethoxysilane is 1:5, the 7th preset temperature be 80-90 DEG C, the described 7th
Preset time is 6-8 hours.
Preferably, in above-mentioned preparation method, the graphene oxide is prepared by following steps：
1）Under the conditions of ice-water bath, a certain amount of natural flake graphite is slowly added into a certain amount of concentrated sulfuric acid, machinery stirs
It mixes until being uniformly mixed；
2）Under the action of mechanical agitation, it is slowly added to a certain amount of K2MnO4Until reaction completely；
3）A certain amount of distilled water mechanical agitation is added, a certain amount of H is added after mixing2O2, solution becomes by dark-brown
Glassy yellow；
4）With cleaning solution under the conditions of hydrochloric acid and distilled water Centrifugal dispersion to neutrality, stable graphene oxide solution is obtained.
Preferably, in above-mentioned preparation method, which is characterized in that the quality of the natural flake graphite and the concentrated sulfuric acid
Than being 1:30-1:40, the natural flake graphite and K2MnO4Mass ratio be 1:1-1:6, the natural flake graphite with
H2O2Mass ratio be 1:3-1:10, the volume ratio of the hydrochloric acid and distilled water is 1:5-1:10, the dosage of the distilled water
For 50-3000ml.
In the TiO of the fluorine-based dissaving polymer modification in end provided by the invention2In the preparation method of intercalation graphene oxide,
It has the advantages that：First, the TiO of the fluorine-based dissaving polymer modification in end obtained2Intercalation graphene oxide is water-soluble
It is good, there is super hydrophobic effect, and integrate the functions such as catalysis, super-hydrophobic, antibacterial；Secondly, the fluorine-based over-expense in end obtained
The TiO of fluidized polymer modification2Intercalation graphene oxide can effectively promote finish coating and fabric etc. by the connection of chemical bond
Fastness between substrate improves wearability.
Description of the drawings
In order to illustrate more clearly of this specification embodiment or technical solution in the prior art, below will to embodiment or
Attached drawing needed to be used in the description of the prior art is briefly described, it should be apparent that, the accompanying drawings in the following description is only
Some embodiments described in this specification, for those of ordinary skill in the art, in not making the creative labor property
Under the premise of, other drawings may also be obtained based on these drawings.
Fig. 1 is the TiO of the fluorine-based dissaving polymer modification of one embodiment of the invention middle-end2The preparation of intercalation graphene oxide
The flow chart of method；
Fig. 2 is that the fluorine-based dissaving polymer of one embodiment of the invention middle-end modifies TiO2The TEM of intercalation graphene oxide schemes.
Specific implementation mode
To keep the purpose, technical scheme and advantage of the application clearer, below in conjunction with the application specific embodiment and
Technical scheme is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only the application one
Section Example, instead of all the embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not doing
Go out the every other embodiment obtained under the premise of creative work, shall fall in the protection scope of this application.
Below in conjunction with attached drawing, the technical solution that each embodiment of this specification provides is described in detail.
One embodiment of the invention provides a kind of TiO of the fluorine-based dissaving polymer modification in end2Intercalation graphene oxide
Preparation method, as shown in FIG. 1, FIG. 1 is the TiO of the fluorine-based dissaving polymer modification of one embodiment of the invention middle-end2Intercalation aoxidizes
The flow chart of the preparation method of graphene.The preparation method includes：TiO is prepared according to graphene oxide2Intercalation graphite oxide
Alkene, such as the step S101 in Fig. 1；According to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide,
Such as the step S103 in Fig. 1；It is modified TiO according to the EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2
Intercalation graphene oxide, such as the step S105 in Fig. 1；And the TiO modified according to the dissaving polymer2Intercalation aoxidizes
Graphene prepares the TiO of the fluorine-based dissaving polymer modification in end2Intercalation graphene oxide, such as the step S107 in Fig. 1.
Such as the step S101 in Fig. 1, TiO is prepared according to graphene oxide2Intercalation graphene oxide.
The graphene oxide is prepared by following steps：
1）Under the conditions of ice-water bath, 1g natural flake graphites are slowly added into the concentrated sulfuric acid of 23ml, mechanical agitation is until mixed
It closes uniform；
2）Under the action of mechanical agitation, it is slowly added to 3gK2MnO4Until reaction completely；
3）150ml distilled water and 5ml H are added after completion of the reaction2O2, solution becomes glassy yellow by dark-brown；
4）25ml dilute hydrochloric acid and 125ml distilled water is added, cleaning solution obtains stable oxidation stone to neutrality under the conditions of Centrifugal dispersion
Black alkene solution.
Next, the graphene oxide prepared is put into hydrothermal reaction kettle, first is reacted under the first preset temperature
Preset time after ultrasonic second preset time, anhydrous state is dried under the second preset temperature and obtains dewatered oxidation stone
Black alkene；By the hydrochloric acid, butyl titanate, sodium hydroxide solution of the dewatered graphene oxide and the first preset ratio close
It closes in container after ultrasonic third preset time, acquisition TiO2Intercalation graphene oxide solution；According to the TiO2Intercalation graphite oxide
Alkene solution obtains TiO2Intercalation graphene oxide.
Wherein, first preset temperature is 110-130 DEG C, and first preset time is 3-4 hours, and described second is pre-
If the time is 30-50 minute, second preset temperature is 40-50 DEG C, the graphene oxide and hydrochloric acid, butyl titanate,
First preset ratio of the quality of sodium hydroxide is 1:3:50:3, the third preset time is 3-4 hours.
Step S103, according to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide.
Specifically, by the TiO2Intercalation graphene oxide is dispersed in by the second preset ratio containing ethylene modulators, two
In the DMF solution of carbodicyclo hexylimide and 4- dimethyl-nitrine pyridine, after supersound process, it is heated to the default temperature of third
Degree after reacting the 4th preset time, washs DMF by deionized water and centrifugation obtains the EDA and is modified TiO2Intercalation oxygen
Graphite alkene.
Wherein, the TiO2Second preset ratio of intercalation graphene oxide and the quality of the DMF solution is 1:500,
The mass ratio of DMF and ethylene modulators, dicyclohexylcarbodiimide, 4- dimethyl-nitrine pyridine are 1:0.2：0.02:0.004,
The third preset temperature is 50-70 DEG C, and the 4th preset time is 9-12 hours.
Step S105 is modified TiO according to EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation oxygen
Graphite alkene.
Specifically, the EDA is modified TiO2Intercalation graphene oxide is dispersed in by third preset ratio containing two hexamethylenes
Dispersion is obtained in the nmp solution of base carbodiimide and 4- dimethyl-nitrine pyridine, pyridine and triphenyl phosphite；By the 4th
The LiCl powder and dissaving polymer of preset ratio are added in the dispersion and stirring and dissolving, obtains mixture；By institute
It states after mixture is heated to the 4th preset temperature under magnetic stirring, is added into being vigorously stirred to 10 times of mixture quality
In methanol；The 5th preset time of ultrasonic disperse, steams methanol under the 5th preset temperature, and acquisition is washed and centrifuged with DMF
The TiO of dissaving polymer modification2Intercalation graphene oxide.
Wherein, the TiO that EDA is modified2The third preset ratio of the quality of intercalation graphene oxide and nmp solution is 1:
160, NMP with DMAP, pyridine, triphenyl phosphite mass ratio be 1:0.006:0.06:0.1, the TiO that the EDA is modified2It inserts
The 4th preset ratio of layer graphene oxide and the quality of LiCl powder, dissaving polymer is 1:0.6:6, the described 4th
Preset temperature is 80-90 DEG C, and the 5th preset temperature is 70 DEG C -80 DEG C, and the 5th preset time is 9-10 hours, described
Dissaving polymer be Hyperbranched Polymer with Terminal Amido, Hyperbranched Polymer with Terminal Hydroxyl and end carboxyl super branched polymer in
Any one or more.
Step S107, the TiO modified according to the dissaving polymer2It is fluorine-based hyperbranched that intercalation graphene oxide prepares end
Polymer-modified TiO2Intercalation graphene oxide.
Specifically, the TiO that the dissaving polymer is modified2Intercalation graphene oxide be dispersed in absolute ethyl alcohol and go from
In the mixed solution of sub- water, it is ultrasonically treated the 6th preset time under the 6th preset temperature, obtains dissaving polymer modification
TiO2Intercalation graphene oxide dispersion；The TiO of dissaving polymer modification is adjusted using acetic acid2Intercalation graphene oxide disperses
The pH value of body, then under mechanical stirring by the 1H of the 5th preset ratio, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are slow
It is added to the TiO of dissaving polymer modification2In intercalation graphene oxide dispersion；Mixture is stirred under the 7th preset temperature
The 7th preset time of reflux is mixed, after reaction, obtains the TiO of the fluorine-based dissaving polymer modification in the end2Intercalation graphene oxide.
Wherein, the 6th preset temperature is room temperature, and the 6th preset time is 3-4 hours, the hyperbranched polymerization
The TiO of object modification2The mixed solution of intercalation graphene oxide and absolute ethyl alcohol and deionized water（The ratio of ethyl alcohol and water is 8:1）
The 5th preset ratio be 1:1.5, the wherein ratio of ethyl alcohol and water is 8:1, acetic acid adjusts dissaving polymer modification
TiO2The pH value of intercalated graphite olefinic oxide dispersion is 2.5-3, the TiO of dissaving polymer modification2Intercalation graphene oxide with
The mass ratio of 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane is 1:5, the 7th preset temperature is 80-90 DEG C, described
7th preset time is 6-8 hours.
Next, illustrating the TiO for holding fluorine-based dissaving polymer modification with two specific embodiments again2Intercalation aoxidizes
The preparation method of graphene.
Embodiment 1
It puts 1g graphene oxides into hydrothermal reaction kettle, 3h, ultrasonic 30min is reacted at 110 DEG C, filter, nothing is dried at 40 DEG C
Water state obtains dewatered graphene oxide；The above-mentioned graphene oxides of 0.1g are weighed, is placed in closed container, is added 0.3g's
Hydrochloric acid adds 5g butyl titanates, and the sodium hydroxide solution of 0.3g is then added, and ultrasonic 4h obtains TiO2Intercalation graphene oxide
Solution；Above-mentioned solution is placed in hydrothermal reaction kettle, crystalline forming under hot conditions.It is fully dry in 60 DEG C of drying box again
At TiO2Intercalation graphene oxide.
Above-mentioned reactant takes 0.1g to be dispersed in first containing 10g ethylene modulators（EDA）, 1g dicyclohexylcarbodiimides and
0.2g4- dimethyl-nitrine pyridine（DMAP）50gDMF solution in, by ultrasonication, under magnetic stirring by mixture
It is heated to 60 DEG C.After reaction 9 hours, the EDA for washing DMF by deionized water and centrifuging needed for acquisition is modified TiO2Intercalation
Graphene oxide.
The TiO that the EDA of synthesis is modified2Intercalation graphene oxide weighs 0.1g and is dispersed in containing 96mgDMAP, 0.96g pyrroles
In the 16gNMP solution of pyridine and 1.6g triphenyl phosphites；The LiCl powder of 60mg and 0.6g dissaving polymers are added to again
In dispersion and stirring and dissolving, mixture is heated to 90 DEG C under magnetic stirring.After the completion, mixture is added drop-wise to 6.6g plays
In the methanol of strong stirring.Then ultrasonic disperse 9 hours under the conditions of 70 DEG C after steaming methanol, are washed with DMF and centrifugation obtain
Obtain the TiO of dissaving polymer modification2Intercalation graphene oxide.
Weigh the TiO of the dissaving polymer modification of 0.1g2Intercalation graphene oxide is dispersed in 0.15g absolute ethyl alcohols and goes
The TiO of dissaving polymer modification is obtained in the mixed solution of ionized water2Intercalation graphene oxide dispersion, and surpass at room temperature
Sonication 3h.The TiO of dissaving polymer modification is adjusted using acetic acid2The pH value of intercalation graphene oxide dispersion is to 2.5, so
Afterwards under mechanical stirring by the 1H of 0.5g, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer
The TiO of modification2In intercalation graphene oxide dispersion.Mixture is stirred at reflux 6h at 80 DEG C.After reaction, centrifugation, washing,
Then it is freeze-dried, obtains the TiO of the fluorine-based dissaving polymer modification in required end2Intercalation graphene oxide.
The TiO of the fluorine-based dissaving polymer modification in opposite end2Intercalation graphene oxide carries out relevant identification, and TEM schemes such as
Shown in Fig. 2, Fig. 2 is that fluorine-based dissaving polymer is held to modify TiO2The TEM of intercalation graphene oxide schemes.
Embodiment 2
It puts 1g graphene oxides into hydrothermal reaction kettle, 4h, ultrasonic 30min is reacted at 120 DEG C, filter, nothing is dried at 50 DEG C
Water state obtains dewatered graphene oxide；The above-mentioned graphene oxides of 0.15g are weighed, are placed in closed container, 0.45g is added
Hydrochloric acid, add 7.5g butyl titanates, the sodium hydroxide solution of 0.45g be then added, ultrasonic 3h obtains TiO2Intercalation aoxidizes
Graphene solution；Above-mentioned solution is placed in hydrothermal reaction kettle, crystalline forming under hot conditions.It is filled in 60 DEG C of drying box again
Divide and is dried to TiO2Intercalation graphene oxide.
Above-mentioned reactant takes 0.15mg to be dispersed in first containing 15g ethylene modulators（EDA）, two Asia of 1.5g dicyclohexyls carbon
Amine and 0.3g4- dimethyl-nitrine pyridine（DMAP）75gDMF solution in, by ultrasonication, mixture is stirred in magnetic force
It mixes down and is heated to 60 DEG C.After reaction 11 hours, the EDA for washing DMF by deionized water and centrifuging needed for acquisition is modified
TiO2Intercalation graphene oxide.
The TiO that the EDA of synthesis is modified2Intercalation graphene oxide weighs 0.15g and is dispersed in containing 0.144gDMAP,
In the 24gNMP solution of 1.44g pyridines and 2.4g triphenyl phosphites；Again by the hyperbranched polymerization of LiCl powder and 0.9g of 90mg
Object is added in dispersion and stirring and dissolving, and mixture is heated to 90 DEG C under magnetic stirring.After the completion, mixture is added dropwise
In the methanol being vigorously stirred to 9.9g.Then ultrasonic disperse 10 hours under the conditions of 80 DEG C, after steaming methanol, washed with DMF and
Centrifuge the TiO for obtaining dissaving polymer modification2Intercalation graphene oxide.
Weigh the TiO of the dissaving polymer modification of 0.15g2Intercalation graphene oxide be dispersed in 0.225g absolute ethyl alcohols and
The TiO of dissaving polymer modification is obtained in the mixed solution of deionized water2Intercalation graphene oxide dispersion, and at room temperature
It is ultrasonically treated 3h.The TiO of dissaving polymer modification is adjusted using acetic acid2The pH value of intercalation graphene oxide dispersion is to 3, so
Afterwards under mechanical stirring by the 1H of 0.75g, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer
The TiO of modification2In intercalation graphene oxide dispersion.Mixture is stirred at reflux 8h at 90 DEG C.After reaction, centrifugation, washing,
Then it is freeze-dried, obtains the TiO of the fluorine-based dissaving polymer modification in required end2Intercalation graphene oxide.
In the TiO of the fluorine-based dissaving polymer modification in end provided by the invention2In the preparation method of intercalation graphene oxide,
It has the advantages that：First, the TiO of the fluorine-based dissaving polymer modification in end obtained2Intercalation graphene oxide is water-soluble
It is good, there is super hydrophobic effect, and integrate the functions such as catalysis, super-hydrophobic, antibacterial；Secondly, the fluorine-based over-expense in end obtained
The TiO of fluidized polymer modification2Intercalation graphene oxide can effectively promote finish coating and fabric etc. by the connection of chemical bond
Fastness between substrate improves wearability.
Above is only an example of the present application, it is not intended to limit this application.For those skilled in the art
For, the application can have various modifications and variations.It is all within spirit herein and principle made by any modification, equivalent
Replace, improve etc., it should be included within the scope of claims hereof.
Claims (9)
1. a kind of TiO of the fluorine-based dissaving polymer modification in end2The preparation method of intercalation graphene oxide, which is characterized in that packet
It includes：
（1）TiO is prepared according to graphene oxide2Intercalation graphene oxide；
（2）According to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide；
（3）It is modified TiO according to the EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation graphite oxide
Alkene；
（4）The TiO modified according to the dissaving polymer2Intercalation graphene oxide prepares the fluorine-based dissaving polymer modification in end
TiO2Intercalation graphene oxide.
2. preparation method according to claim 1, which is characterized in that the step（1）It specifically includes：
Graphene oxide is put into hydrothermal reaction kettle, the first preset time is reacted under the first preset temperature, ultrasound second is pre-
If after the time, anhydrous state being dried under the second preset temperature and obtains dewatered graphene oxide；
By the hydrochloric acid, butyl titanate, sodium hydroxide solution of the dewatered graphene oxide and the first preset ratio close
It closes in container after ultrasonic third preset time, acquisition TiO2Intercalation graphene oxide solution；
According to the TiO2Intercalation graphene oxide solution obtains TiO2Intercalation graphene oxide.
3. preparation method according to claim 2, which is characterized in that first preset temperature is 110 DEG C -130 DEG C, institute
It is 3-4 hours to state the first preset time, and second preset time is 30-50 minutes, and second preset temperature is 40 DEG C -50
DEG C, the first preset ratio of the graphene oxide and the quality of hydrochloric acid, butyl titanate, sodium hydroxide is 1:3:50:3, institute
It is 3-4 hours to state third preset time.
4. preparation method according to claim 1, which is characterized in that the step（2）It specifically includes：
By the TiO2Intercalation graphene oxide is dispersed in sub- containing ethylene modulators, dicyclohexyl carbon two by the second preset ratio
In the DMF solution of amine and 4- dimethyl-nitrine pyridine, after supersound process, it is heated to third preset temperature, reaction the 4th is pre-
If after the time, washing DMF by deionized water and centrifuging the acquisition EDA modifications TiO2Intercalation graphene oxide.
5. preparation method according to claim 4, which is characterized in that the TiO2Intercalation graphene oxide and the DMF are molten
Second preset ratio of the quality of liquid is 1:500, DMF with ethylene modulators, dicyclohexylcarbodiimide, 4- dimethyl-nitrine
The mass ratio of pyridine is 1:0.2：0.02:0.004, the third preset temperature is 50 DEG C -70 DEG C, and the 4th preset time is
9-12 hours.
6. preparation method according to claim 1, which is characterized in that the step（3）It specifically includes：
The EDA is modified TiO2Intercalation graphene oxide be dispersed in containing dicyclohexylcarbodiimide by third preset ratio and
Dispersion is obtained in the nmp solution of 4- dimethyl-nitrine pyridine, pyridine and triphenyl phosphite；
The LiCl powder of 4th preset ratio and dissaving polymer are added in the dispersion simultaneously stirring and dissolving, mixed
Close object；
After the mixture is heated to the 4th preset temperature under magnetic stirring, it is added into the play of 10 times of mixture quality
In the methanol of strong stirring；
The 5th preset time of ultrasonic disperse, steams methanol under the 5th preset temperature, is washed and is centrifuged with DMF and is overspend
The TiO of fluidized polymer modification2Intercalation graphene oxide.
7. preparation method according to claim 6, which is characterized in that the TiO that EDA is modified2Intercalation graphene oxide and NMP
The third preset ratio of the quality of solution is 1:160, NMP with DMAP, pyridine, triphenyl phosphite mass ratio be 1:
0.006:0.06:0.1, the TiO that the EDA is modified2Intercalation graphene oxide and the quality of LiCl powder, dissaving polymer
4th preset ratio is 1:0.6:6, the 4th preset temperature is 80-90 DEG C, and the 5th preset temperature is 70-80
DEG C, the 5th preset time is 9-10 hours, and the dissaving polymer is Hyperbranched Polymer with Terminal Amido, terminal hydroxy group is super
Any one or more in branched polymer and end carboxyl super branched polymer.
8. preparation method according to claim 1, which is characterized in that the step（4）It specifically includes：
The TiO that the dissaving polymer is modified2Intercalation graphene oxide is dispersed in absolute ethyl alcohol and the mixing of deionized water is molten
In liquid, it is ultrasonically treated the 6th preset time under the 6th preset temperature, obtains the TiO of dissaving polymer modification2Intercalation aoxidizes
Graphene dispersion body；
The TiO of dissaving polymer modification is adjusted using acetic acid2The pH value of intercalation graphene oxide dispersion, is then stirred in machinery
The lower 1H by the 5th preset ratio, 1H, 2H are mixed, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer and repair
The TiO of decorations2In intercalation graphene oxide dispersion；
Mixture is stirred at reflux the 7th preset time under the 7th preset temperature, after reaction, it is fluorine-based hyperbranched to obtain the end
Polymer-modified TiO2Intercalation graphene oxide.
9. preparation method according to claim 8, which is characterized in that the 6th preset temperature be room temperature, the described 6th
Preset time is 3-4 hours, the TiO of the dissaving polymer modification2Intercalation graphene oxide and absolute ethyl alcohol and deionization
The mixed solution of water（The ratio of ethyl alcohol and water is 8:1）The 5th preset ratio be 1:1.5, the wherein ratio of ethyl alcohol and water
It is 8:1, acetic acid adjusts the TiO of dissaving polymer modification2The pH value of intercalation graphene oxide dispersion is 2.5-3, hyperbranched
Polymer-modified TiO2The mass ratio of intercalation graphene oxide and 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are 1:
5, the 7th preset temperature is 80-90 DEG C, and the 7th preset time is 6-8 hours.
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| CN110743585A (en) * | 2019-11-20 | 2020-02-04 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
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| CN102826539A (en) * | 2012-07-31 | 2012-12-19 | 上海交通大学 | Hyperbranched polyaramide functionalized graphene, as well as preparation method and applications of hyperbranched polyaramide functionalized graphene |
| CN104789124A (en) * | 2014-12-30 | 2015-07-22 | 中国科学院兰州化学物理研究所 | A preparing method of a stable superamphiphobic surface |
| CN106544752A (en) * | 2016-09-30 | 2017-03-29 | 旷达纤维科技有限公司 | It is a kind of that there is self-purification function polyster fibre and preparation method thereof |
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| CN110743585B (en) * | 2019-11-20 | 2022-02-18 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
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