CN108707236A - Click chemistry synthesizes the preparation method of graphene oxide grafted fluoropolymer - Google Patents
Click chemistry synthesizes the preparation method of graphene oxide grafted fluoropolymer Download PDFInfo
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Abstract
The invention discloses the preparation methods that a kind of click chemistry synthesizes graphene oxide grafted fluoropolymer, belong to Material Field.The preparation method of the click chemistry synthesis graphene oxide grafted fluoropolymer, including:(1) graphene oxide is prepared using improvement Hummer ' s methods；(2) alkynyl of graphene oxide；(3) fluoropolymer-containing Azide；(4) fluoropolymer of click chemistry synthesis graphene oxide grafting.The present invention is remarkably improved grafting rate, and preparation process is simple, is suitble to industrialized production；The material that the present invention prepares has the characteristics that tensile strength is high, thermal stability is good, high mechanical strength.
Description
Technical field
The present invention relates to Material Field, a kind of click chemistry synthesis graphene oxide grafted fluoropolymer is particularly related to
Preparation method.
Background technology
Graphene oxide is the oxidized derivatives of graphene, is just found by William S.Hummers early in 1958,
With huge specific surface area, largely oxygen-containing hydrophilic radical makes it have excellent hydrophilicity on surface, is also beneficial into one
The functional modification of step.As the filler of graphene oxide-polymer composite, can effectively enhance polymer mechanics and
Electric property improves its hydrophily and tensile strength, is excellent membrane modifying material.But its flexibility is relatively low, and with polymer it
Between compatibility it is also poor, therefore improve graphene oxide and polymer compatibility, enhance dissolubility in a solvent, become
Important research.
The critical functions material such as fluoropolymer, especially Kynoar, since material is flexible, low-density, processability
The advantages that energy is excellent, operating temperature range is wide and high-k becomes the good selection of matrices of composite material, wider temperature
Degree range makes its handling ease, there is preferable mouldability.In addition, polyvinylidene fluoride film has light, resist bending, piezoelectric property high
Etc. a series of advantages, it is widely used in fields such as hot monitor, shock sensor and signal verification systems.Certainly by using
Graphene oxide improves the hydrophilicity of polymer, realizes long-term modified also as research emphasis.
Therefore, a kind of preparation method of graphene oxide grafted fluoropolymer is for widening graphene oxide in macromolecule
Application study in Material Field and industrialization production, it is highly important to improve fluoropolymer-containing application range.
Invention content
The technical problem to be solved in the present invention is to provide a kind of dispersion performances, and click chemistry that is good, being not easy reunion synthesizes oxygen
The preparation method of graphite alkene grafted fluoropolymer solves the problems, such as that general method of modifying is unstable, realizes polymer film
Permanent modification.
In order to solve the above technical problems, present invention offer technical solution is as follows:
The present invention provides a kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, including：
(1) graphene oxide is prepared using improvement Hummer ' s methods
Under the conditions of ice-water bath, graphite powder, potassium permanganate is added fills the concentrated sulfuric acid that mass concentration is 98% successively
(H2SO4) beaker in stir, be warming up to 45 DEG C, stop after reacting 12h；Under the conditions of ice-water bath, reaction product is poured into and fills steaming
In the large beaker of distilled water, the hydrogen peroxide (H of 30% volumetric concentration is added dropwise2O2), solution colour becomes golden brown from dark brown；With
Molar concentration is dilute H of 1mol/L2SO4And distilled water is washed to solution and is in neutrality repeatedly, vacuum drying obtains graphene oxide.
Wherein, the mass ratio of graphite powder and potassium permanganate is 1:5~10；The mass ratio of graphite powder and the concentrated sulfuric acid is 1:50~
80；Warming temperature to 45-50 DEG C reaction 12~18h；The volume of hydrogen peroxide and the concentrated sulfuric acid is 1:5~10；
(2) alkynyl of graphene oxide
The graphene oxide that step (1) obtains is added to ultrasonic disperse in anhydrous solvent, under stirring condition, is sequentially added
Propiolic acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide react at room temperature, and filter, and vacuum drying obtains having alkynyl
Graphene oxide；
(3) fluoropolymer-containing Azide
Based on fluorochemical monomer, perfluor iodohexane is chain-transferring agent, adds initiator and solvent A, is brought it about certainly
It is polymerize by base, dry iodo fluoropolymer after reaction；
Obtained iodo fluoropolymer and Sodium azide are added in flask, solvent B is added, is stirred at room temperature, instead
It is precipitated with solvent C after answering, then puts the precipitate in vacuum drying oven and dry to obtain the fluoropolymer with azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting
Fluorine-containing with azido that graphene oxide with alkynyl that step (2) obtains and step (3) obtain is gathered
It closes object to be added in flask after ultrasonic disperse in solvent D, under the catalytic action of copper catalyst, on modified graphene oxide
Alkynyl occurs click chemistry with the azido group on fluoropolymer and reacts, and obtains the fluoropolymer of graphene oxide grafting.
Further, in the step (2), the mass ratio of graphene oxide and propiolic acid is 1~10:1, with anhydrous solvent
Ratio be 5~10g:1L；Graphene oxide and the mass ratio of 4-dimethylaminopyridine are 1~10:1, graphene oxide and two
The mass ratio of carbodicyclo hexylimide is 1~3:1.
Further, in the step (2), anhydrous solvent is tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethyl
One or more of mixing of acetamide, dichloromethane, toluene, hexamethylene, dimethyl sulfoxide (DMSO)；
In the step (2), ultrasonic 5-30min；React at room temperature 1-72h.
Further, in the step (3), the mass ratio of fluorochemical monomer and perfluor iodohexane is 15~30:1, with initiation
The mass ratio of agent is 1:0.003~0.009, the ratio with solvent A is 50~250g:1L；
The mass ratio of the iodo fluoropolymer and Sodium azide is 5~20:1, the ratio with solvent B is 50~250g:
1L。
Further, in the step (3), fluorochemical monomer is vinylidene；Or vinylidene and hexafluoropropene quality
Than being 1~4:1 mixed gas；Or vinylidene and chlorotrifluoroethylene mass ratio are 1~4:1 mixed gas.
Further, the initiator is the peroxidating pivalic acid tert-butyl ester, benzoyl peroxide, azodiisobutyronitrile, idol
Two different heptonitrile of nitrogen, potassium peroxydisulfate or ammonium persulfate；
The solvent A is water, trifluorotrichloroethane, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO)
One or more of mixing；
The solvent B is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl Asia
One or more of mixing of sulfone；
The solvent C is one or more of mixing of water, methanol, absolute ethyl alcohol.
Further, in the step (3), the Raolical polymerizable time be 12~for 24 hours；The time being stirred at room temperature
For 10~36h；The temperature of the vacuum drying oven drying is 30 DEG C.
Further, in the step (4), in the step (4), the graphene oxide of alkynyl and containing with azido
The mass ratio of fluoropolymer is 0.01~0.1:1；
The graphene oxide of the alkynyl and the ratio of solvent D are 1~100g:1L；
The graphene oxide of the alkynyl and the mass ratio of copper ion compound are 0.1~0.5:1.
Preferably, solvent D is n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl
One or more of mixing of sulfoxide, dimethyl carbonate；
The copper catalyst is the complex compound of copper ion.
Further, in the step (4), the time of ultrasonic disperse is 5-30min；It is 12- that the reaction time, which is stirred at room temperature,
36h。
The invention has the advantages that：
The present invention provides a kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, the method technique
Simply, permanent modification, while being modified with conducive to polymer on graphene oxide to surface of graphene oxide can be realized
Grafting, improves the compatibility between graphene oxide and fluoropolymer.Obtained polymer film stretching intensity is higher, reaches
It is 1.7 times of fluoro-containing copolymer film before modified to 4.2MPa, dielectric constant also increases, and is before modified more than 2 times.
Description of the drawings
Fig. 1 is the fluoropolymer-containing IR Characterization figure with azido that in the present invention prepared by embodiment 1；
Fig. 2 is the IR Characterization figure for the graphene oxide grafted fluoropolymer that in the present invention prepared by embodiment 1；
Fig. 3 is the graphene oxide grafted fluoropolymer and unmodified fluoropolymer that in the present invention prepared by embodiment 1
Dielectric constant datagram, wherein three curves are from top to bottom as the curve of rGO-PVDF, GO-PVDF, PVDF in figure.
Specific implementation mode
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
The present invention easily reunites for graphene polymer in the prior art, poor compatibility, is not easy the problem of industrialized production,
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer is provided.
Embodiment 1
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, includes the following steps：
1) graphene oxide is prepared using improvement Hummer ' s methods
Under the conditions of ice-water bath, successively by 3g graphite powders, 15g KMnO4Be added fill 115mL mass concentrations be 98% it is dense
H2SO4Beaker in stir, be warming up to 45 DEG C, stop after reacting 12h；Under the conditions of ice-water bath, reaction product is poured into and is filled
In the large beaker of 200mL distilled water, the H of 30% volumetric concentrations of 15mL is added dropwise2O2, solution colour becomes golden brown from dark brown；
The dilute H for being 1mol/L with 100mL molar concentrations2SO4And distilled water is washed to solution and is in neutrality repeatedly, vacuum drying is aoxidized
Graphene；
(2) alkynyl of graphene oxide
Graphene oxide ultrasound 5min dispersions in 100mL anhydrous tetrahydro furans that 0.1641g steps (1) obtain are weighed,
It is added in flask and stirs, sequentially add 0.1g propiolic acids, 0.0018g4- dimethylamino naphthyridines and 0.0092g dicyclohexyls
Carbodiimide makes it carry out esterification, and normal-temperature reaction 1h is filtered, and vacuum drying obtains the graphene oxide with alkynyl；
(3) fluoropolymer-containing Azide
Take 200mL trifluorotrichloroethanes, weigh the 0.1359g peroxidating pivalic acid tert-butyl esters and 1.0453g perfluors iodine oneself
Alkane is added in reaction kettle, then is passed through 15g vinylidene gaseous monomers, brings it about free radical polymerization, reacts dry after 22h
Iodo Kynoar；
Obtained iodo Kynoar 2g and 0.2031g Sodium azides are added in flask, 20mLN, N- are added
Dimethylformamide, stirring at normal temperature 20h use methanol extraction after reaction, then put the precipitate in 30 DEG C of vacuum drying ovens and dry
The dry Kynoar for obtaining that there is azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting
The gathering with azido that the graphene oxide 0.05g with alkynyl that step (2) obtains is obtained with step (3)
Vinylidene 1g is added to after ultrasonic disperse 5min in flask in 20mL n,N-Dimethylformamide, adds 0.2g brominations
It is cuprous mixed with 0.24g pentamethyl-diethylenetriamines after formed copper ion complex compound, under nitrogen protection stirring at normal temperature react
For 24 hours, the Kynoar of dry graphene oxide grafting is washed.
Comparison diagram 1 and Fig. 2 are it is found that the fluoropolymer-containing IR Characterization figure that gained graphene oxide is grafted in embodiment
In, in 2100cm-1The characteristic peak at place disappears, and can prove the successful grafting of Kynoar chain on graphene oxide.Compares figure 3
It is found that the dielectric properties of gained graphene oxide grafted fluoropolymer (GO-PVDF) can reach unmodified poly- in embodiment
More than 2 times of vinylidene (PVDF), and after being restored to graphene oxide, graft polymers (rGO-PVDF) can be made
Dielectric properties further increase, reach 2.5 times of unmodified Kynoar, be applied to electronic device to realize
On possibility.
By it is obtained it is polymer-modified disperse in solvent n,N-Dimethylformamide with Kynoar, utilize solution
The tape casting obtains modifying polymer film.Gained graphene oxide grafted fluoropolymer film improves the performance of polymer, modified
The surface topography of polymer film is consistent, and positive and negative is all grey, and load N when film is broken is measured using XQ-2 fiber strength and elongation instrument
And elongation w, it is 4.0MPa to calculate its tensile strength using formula, is 1.6 times of polyvinylidene fluoride film.
Embodiment 2
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, includes the following steps：
(1) graphene oxide is prepared using improvement Hummer ' s methods, preparation process is the same as above-described embodiment 1；
(2) alkynyl of graphene oxide:
It is ultrasonic in the anhydrous N,N-dimethylformamides of 100mL to weigh the graphene oxide that 0.1641g steps (1) obtain
10min disperse, be added in flask and stir, sequentially add 0.1032g propiolic acids, 0.0018g 4-dimethylaminopyridine and
0.0103g dicyclohexylcarbodiimides make it carry out esterification, and normal-temperature reaction 6h is filtered, and vacuum drying is obtained with alkynes
The graphene oxide of base；
(3) fluoropolymer-containing Azide
Take 200mL N-Methyl pyrrolidones, weigh the 0.27g peroxidating pivalic acid tert-butyl esters and 1.0324g perfluors iodine oneself
Alkane is added in reaction kettle, then is passed through 15g vinylidene gaseous monomers, brings it about free radical polymerization, reacts dry after 12h
Iodo Kynoar.
Obtained iodo Kynoar 2g and 0.2031g Sodium azides are added in flask, 20mL diformazans are added
Base sulfoxide, stirring at normal temperature 12h use methanol extraction, then put the precipitate in 30 DEG C of vacuum drying ovens and dry to obtain after reaction
Kynoar with azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting:
The gathering with azido that the graphene oxide 0.05g with alkynyl that step (2) obtains is obtained with step (3)
Vinylidene 1g is added to after ultrasonic disperse 25min in flask in 30mL n,N-Dimethylformamide, adds 0.2g brominations
It is cuprous mixed with 0.24g pentamethyl-diethylenetriamines after the copper ion complex compound that is formed, under nitrogen protection stirring at normal temperature react
23h, the Kynoar of dry the graphene oxide grafting of washing.
By it is obtained it is polymer-modified disperse in solvent n,N-Dimethylformamide with Kynoar, utilize solution
The tape casting obtains modifying polymer film.The surface topography for the modifying polymer film that the present embodiment obtains is consistent, and positive and negative is all ash
Color, load N and elongation w when film is broken are measured using XQ-2 fiber strength and elongation instrument, and calculating its tensile strength using formula is
4.2MPa is 1.7 times of polyvinylidene fluoride film, effectively increases the tensile property of polymer.
Embodiment 3
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, includes the following steps：
(1) graphene oxide is prepared using improvement Hummer ' s methods, preparation process is the same as above-described embodiment 1；
(2) alkynyl of graphene oxide:
Graphene oxide ultrasound 5min dispersions in 40mL anhydrous tetrahydro furans that 0.1641g steps (1) obtain are weighed, are added
Enter and stirred into flask, sequentially adds 0.019g propiolic acids, 0.0018g 4-dimethylaminopyridine and 0.006g dicyclohexyls
Carbodiimide makes it carry out esterification, and normal-temperature reaction 1h is filtered, and vacuum drying obtains the graphene oxide with alkynyl；
(3) fluoropolymer-containing Azide:
200mL trifluorotrichloroethanes are taken, the 0.0718g peroxidating pivalic acid tert-butyl esters and 0.669g perfluor iodohexanes are weighed
It is added in reaction kettle, then is passed through 14.4g vinylidene gaseous monomers, bring it about free radical polymerization, react dry after 22h
Iodo Kynoar.
Obtained iodo Kynoar 2g and 0.2031g Sodium azides are added in flask, 20mLN, N- are added
Dimethylacetylamide, stirring at normal temperature 24 hours use methanol extraction, then put the precipitate in 30 DEG C of vacuum drying ovens after reaction
Drying obtains the Kynoar with azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting:
The gathering with azido that the graphene oxide 0.05g with alkynyl that step (2) obtains is obtained with step (3)
Vinylidene 1g is added to after ultrasonic disperse 5min in flask in 30mL n,N-Dimethylformamide, adds 0.2g brominations
It is cuprous mixed with 0.24g pentamethyl-diethylenetriamines after the copper ion complex compound that is formed, under nitrogen protection stirring at normal temperature react
23 hours, the Kynoar of dry the graphene oxide grafting of washing.
By it is obtained it is polymer-modified disperse in solvent n,N-Dimethylformamide with Kynoar, utilize solution
The tape casting obtains modifying polymer film.The surface topography for the modifying polymer film that the present embodiment obtains is consistent, and positive and negative is all ash
Color, load N and elongation w when film is broken are measured using XQ-2 fiber strength and elongation instrument, and calculating its tensile strength using formula is
3.8MPa is 1.5 times of polyvinylidene fluoride film before modified.
Embodiment 4
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, includes the following steps：
(1) graphene oxide is prepared using improvement Hummer ' s methods, preparation process is the same as above-described embodiment 1；
(2) alkynyl of graphene oxide:
Graphene oxide that 0.1641g steps (1) obtain is weighed in 40mLN, dinethylformamide and 60mLN, N- bis-
In methylacetamide mixed solution ultrasound 30min disperse, be added in flask and stir, sequentially add 0.1029g propiolic acids,
0.0021g 4-dimethylaminopyridine and 0.012g dicyclohexylcarbodiimides make it carry out esterification, normal-temperature reaction 8h, mistake
Filter, vacuum drying, obtains the graphene oxide with alkynyl；
(3) fluoropolymer-containing Azide:
100mLN, dinethylformamide and the mixing of 100mL N-Methyl pyrrolidones are taken, 0.0447g benzoyl peroxides are weighed
Formyl and 1.0217g perfluor iodohexanes are added in reaction kettle, then are passed through 4g vinylidenes (VDF) and 12g hexafluoropropenes
(HFP) mixed gas monomer, brings it about free radical polymerization, reacts dry P (VDF-HFP)-I after 22h.
Obtained P (VDF-HFP)-I 2g and 0.1921g Sodium azides are added in flask, 20mLN, N- bis- are added
Methylacetamide, stirring at normal temperature 24 hours, is precipitated with absolute ethyl alcohol after reaction, is then put the precipitate in 30 DEG C of vacuum and is dried
Case dries to obtain the fluoropolymer with azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting
The containing with azido that the graphene oxide 0.05g with alkynyl that step (2) obtains is obtained with step (3)
Fluoropolymer 1g is added to after ultrasonic disperse 25min in flask in 30mLN- methyl pyrrolidones, adds 0.2g protobromides
The copper ion complex compound that copper is formed after being mixed with 0.24g pentamethyl-diethylenetriamines, under nitrogen protection stirring at normal temperature reaction 23
Hour, the P (VDF-HFP) of dry the graphene oxide grafting of washing.
By it is obtained it is polymer-modified disperse in solvent n,N-Dimethylformamide with P (VDF-HFP) matrixes, utilize
Solution casting method obtains modifying polymer film.The surface topography for the modifying polymer film that the present embodiment obtains is consistent, and positive and negative is all
For grey, load N and elongation w when film is broken are measured using XQ-2 fiber strength and elongation instrument, calculating it using formula stretches by force
Degree is 8MPa, is 1.4 times of P (VDF-HFP) film before modified.
Embodiment 5
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, includes the following steps：
(1) graphene oxide is prepared using improvement Hummer ' s methods, preparation process is the same as above-described embodiment 1；
(2) alkynyl of graphene oxide:
Graphene oxide ultrasound 30min dispersions in 100mL dichloromethane that 0.1641g steps (1) obtain are weighed, are added
To being stirred in flask, 0.0912g propiolic acids, 0.0018g 4-dimethylaminopyridine and 0.096g dicyclohexyl carbon are sequentially added
Diimine makes it carry out esterification, and normal-temperature reaction 72h is filtered, and vacuum drying obtains the graphene oxide with alkynyl；
(3) fluoropolymer-containing Azide:
Take 100mL trifluorotrichloroethanes and 100mL dimethyl sulfoxide (DMSO)s, weigh 0.0102g azobisisoheptonitrile and
1.012g perfluor iodohexanes are added in reaction kettle, then are passed through the mixed of 4g vinylidenes (VDF) and 12g chlorotrifluoroethylene (CTFE)
Gaseous monomer is closed, brings it about free radical polymerization, reacts dry P (VDF-CTFE)-I after 12h.
Obtained P (VDF-CTFE)-I 2g and 0.2031g Sodium azides are added in flask, 20mLN, N- are added
Dimethylformamide, stirring at normal temperature for 24 hours, use methanol extraction after reaction, then put the precipitate in 30 DEG C of vacuum drying ovens and dry
The dry P (VDF-CTFE) for obtaining that there is azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting:
The P with azido that the graphene oxide 0.05g with alkynyl that step (2) obtains is obtained with step (3)
(VDF-CTFE) 1g is added to flask in the mixed solution of 30mL dimethyl sulfoxide (DMSO)s and dimethyl carbonate after ultrasonic disperse 5min
In, the copper ion complex compound formed after 0.2g cuprous bromides are mixed with 0.24g pentamethyl-diethylenetriamines is added, is protected in nitrogen
The lower stirring at normal temperature of shield is reacted 10 hours, washing it is dry graphene oxide grafting P (VDF-CTFE).
By it is obtained it is polymer-modified disperse in solvent n,N-Dimethylformamide with P (VDF-CTFE) matrixes, profit
Modifying polymer film is obtained with solution casting method.The surface topography for the modifying polymer film that the present embodiment obtains is consistent, positive and negative
It is all grey, measures load N and elongation w when film is broken using XQ-2 fiber strength and elongation instrument, its stretching is calculated using formula
Intensity is 14MPa, is 1.6 times of P (VDF-CTFE) film before modified.
Embodiment 6
A kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, includes the following steps：
(1) graphene oxide is prepared using improvement Hummer ' s methods, preparation process is the same as above-described embodiment 1；
(2) alkynyl of graphene oxide:
The graphene oxide that 0.1641g steps (1) obtain is weighed in 40mL toluene and 60mL hexamethylene mixed solutions to surpass
Sound 15min dispersion, is added in flask and stirs, sequentially add 0.0992g propiolic acids, 0.0021g 4-dimethylaminopyridine and
0.011g dicyclohexylcarbodiimides make it carry out esterification, and normal-temperature reaction 36h is filtered, and vacuum drying is obtained with alkynes
The graphene oxide of base；
(3) fluoropolymer-containing Azide:
150mL trifluorotrichloroethanes and 50mL water, 0.102g potassium peroxydisulfates and 1.025g perfluor iodohexanes is taken to be added to
In reaction kettle, then 15g vinylidene gaseous monomers are passed through, bring it about free radical polymerization, reaction is dry that iodo is poly- inclined afterwards for 24 hours
Vinyl fluoride.
Obtained iodo Kynoar 2g and 0.2031g Sodium azides are added in flask, 20mLN- first is added
Base pyrrolidones, stirring at normal temperature 36 hours use methanol extraction after reaction, then put the precipitate in 30 DEG C of vacuum drying ovens and dry
The dry Kynoar for obtaining that there is azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting:
The gathering with azido that the graphene oxide 0.05g with alkynyl that step (2) obtains is obtained with step (3)
Vinylidene 1g is added to after ultrasonic disperse 5min in flask in 30mL dimethyl carbonates, add 0.2g cuprous bromides with
0.24g pentamethyl-diethylenetriamines form copper ion complex compound, and stirring at normal temperature is reacted 23 hours under nitrogen protection, wash drying
Obtain the Kynoar of graphene oxide grafting.
By it is obtained it is polymer-modified disperse in solvent n,N-Dimethylformamide with Kynoar, utilize solution
The tape casting obtains modifying polymer film.The surface topography for the modifying polymer film that the present embodiment obtains is consistent, and positive and negative is all ash
Color, load N and elongation w when film is broken are measured using XQ-2 fiber strength and elongation instrument, and calculating its tensile strength using formula is
4.3MPa is 1.7 times of polyvinylidene fluoride film before modified.
Comparative example 1
A kind of preparation method of modified polyvinilidene fluoride, includes the following steps:
(1) graphene oxide is prepared using improvement Hummer ' s methods, preparation process is the same as above-described embodiment 1；
(2) dispersion liquid by graphene oxide in solvent N,N-dimethylformamide and Kynoar are in N, N- diformazans
Solution mixing in base formamide, modifying polymer film is obtained using solution casting method.
The problem of obtained modifying polymer film is due to poor compatibility, positive and negative face color is inconsistent, uses XQ-2 fibers
Strength and elongation instrument measures load N and elongation w when film is broken, and it is 3.5MPa to calculate its tensile strength using formula, is before modified
1.4 times of Kynoar, there is certain modified effect, but can not achieve permanent modification.
It is tested by tensile strength, click chemistry synthesis graphene oxide grafted fluoropolymer tensile strength carries significantly
Height reaches 4.3MPa, is 1.7 times of Kynoar.It is tested by thermal weight loss, click chemistry synthesis graphene oxide grafting contains
The decomposition temperature of fluoropolymer is 450 DEG C, more contour than Kynoar and polytrifluorochloroethylene, illustrates that stability enhances.Gained
Polymer can be good in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), N- crassitudes
Dispersion is dissolved in these polar non-solutes of ketone, dimethyl carbonate, is improved graphene oxide and is easily reunited, is not easy and solvent phase
The shortcomings that appearance.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer, which is characterized in that including：
(1) graphene oxide is prepared using improvement Hummer ' s methods；
(2) alkynyl of graphene oxide
The graphene oxide that step (1) obtains is added to ultrasonic disperse in anhydrous solvent, under stirring condition, sequentially adds propine
Acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide react at room temperature, and filter, and vacuum drying obtains the oxidation with alkynyl
Graphene；
(3) fluoropolymer-containing Azide
Based on fluorochemical monomer, perfluor iodohexane is chain-transferring agent, adds initiator and solvent A, brings it about free radical
Polymerization, dry iodo fluoropolymer after reaction；
Obtained iodo fluoropolymer and Sodium azide are added in flask, solvent B is added, is stirred at room temperature, reaction knot
Shu Houyong solvent Cs precipitate, and then put the precipitate in vacuum drying oven and dry to obtain the fluoropolymer with azido；
(4) fluoropolymer of click chemistry synthesis graphene oxide grafting
The fluoropolymer with azido that the graphene oxide with alkynyl that step (2) obtains is obtained with step (3)
It is added in flask after ultrasonic disperse in solvent D, is catalyzed by copper catalyst, reaction is stirred at room temperature under nitrogen protection, then
Wash the fluoropolymer of dry graphene oxide grafting.
2. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 1, special
Sign is, in the step (2), the mass ratio of graphene oxide and propiolic acid is 1~10:1, the ratio with anhydrous solvent is 1
~10g:1L；Graphene oxide and the mass ratio of 4-dimethylaminopyridine are 50~100:1, graphene oxide and dicyclohexyl carbon
The mass ratio of diimine is 10~50:1.
3. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 2, special
Sign is, in the step (2), anhydrous solvent is tetrahydrofuran, n,N-Dimethylformamide, n,N-dimethylacetamide, two
One or more of mixing of chloromethanes, toluene, hexamethylene, dimethyl sulfoxide (DMSO)；
In the step (2), ultrasonic 5-30min；React at room temperature 1-72h.
4. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 1, special
Sign is, in the step (3), the mass ratio of fluorochemical monomer and perfluor iodohexane is 15~30:1, the mass ratio with initiator
It is 1:0.003~0.009, the ratio with solvent A is 50~250g:1L；
The mass ratio of the iodo fluoropolymer and Sodium azide is 5~20:1, the ratio of iodo fluoropolymer and solvent B is
50~250g:1L.
5. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 1, special
Sign is that in the step (3), fluorochemical monomer is vinylidene；Or vinylidene and hexafluoropropene mass ratio are 1~4:1
Mixed gas；Or vinylidene and chlorotrifluoroethylene mass ratio are 1~4:1 mixed gas.
6. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 5, special
Sign is, in the step (3), initiator is the peroxidating pivalic acid tert-butyl ester, benzoyl peroxide, azodiisobutyronitrile, idol
Two different heptonitrile of nitrogen, potassium peroxydisulfate or ammonium persulfate；
The solvent A be water, trifluorotrichloroethane, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) one
Kind or several mixing；
The solvent B is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO)
One or more mixing；
The solvent C is one or more of mixing of water, methanol, absolute ethyl alcohol.
7. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 6, special
Sign is, in the step (3), the Raolical polymerizable time be 12~for 24 hours；The time being stirred at room temperature is 10~36h；
The temperature of the vacuum drying oven drying is 30 DEG C.
8. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 1, special
Sign is, in the step (4), the graphene oxide of alkynyl with azido fluoropolymer-containing mass ratio be 0.01~
0.1:1；
The graphene oxide of the alkynyl and the ratio of solvent D are 1~100g:1L；
The graphene oxide of the alkynyl and the mass ratio of copper catalyst are 0.1~0.5:1.
9. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 8, special
Sign is that the solvent D is n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl Asia
One or more of mixing of sulfone, dimethyl carbonate；
The copper catalyst is the complex compound of copper ion.
10. the preparation method of click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 9, special
Sign is, in the step (4), the time of ultrasonic disperse is 5-30min；It is 12-36h that the reaction time, which is stirred at room temperature,.
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