CN108707236B - Preparation method of click chemistry synthesis graphene oxide grafted fluorine-containing polymer - Google Patents
Preparation method of click chemistry synthesis graphene oxide grafted fluorine-containing polymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis, and belongs to the field of materials. The preparation method of the graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps of (1) preparing graphene oxide by adopting an improved Hummer's method; (2) alkynylating graphene oxide; (3) azidation of the fluoropolymer; (4) and (3) synthesizing the graphene oxide grafted fluorine-containing polymer by click chemistry. The invention can obviously improve the grafting rate, has simple preparation process and is suitable for industrial production; the material prepared by the invention has the characteristics of high tensile strength, good thermal stability and high mechanical strength.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method of a graphene oxide grafted fluorine-containing polymer by click chemistry synthesis.
Background
Graphene oxide is an oxidized derivative of graphene, and is discovered by William s hummers as early as 1958, and has a large specific surface area, and a large number of oxygen-containing hydrophilic groups on the surface make the graphene oxide have excellent hydrophilic performance, and further functionalization modification is facilitated. As a filler of the graphene oxide-high molecular composite material, the graphene oxide-high molecular composite material can effectively enhance the mechanical and electrical properties of a polymer, improve the hydrophilicity and tensile strength of the polymer, and is an excellent film modification material. However, the flexibility of the graphene oxide is low, and the compatibility between the graphene oxide and the polymer is poor, so that the compatibility between the graphene oxide and the polymer is improved, the solubility in a solvent is enhanced, and important research is made.
The fluorine-containing polymer, especially the important functional material such as polyvinylidene fluoride, becomes a good choice for the composite material matrix due to the advantages of flexible material, low density, excellent processability, wide operating temperature range, high dielectric constant and the like, and the wide temperature range enables the processing to be easy and has better formability. In addition, the polyvinylidene fluoride film has a series of advantages of light weight, bending resistance, high piezoelectric performance and the like, and is widely applied to the fields of thermal monitors, vibration sensors, signal inspection systems and the like. Of course, the long-term modification is also important to be realized by using graphene oxide to improve the hydrophilic property of the polymer.
Therefore, the preparation method of the graphene oxide grafted fluoropolymer is very important for widening the application research and industrial production of the graphene oxide in the field of high polymer materials and improving the application range of the fluoropolymer.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a click chemistry synthesis graphene oxide grafted fluorine-containing polymer with good dispersion performance and difficult agglomeration, solving the problem of instability of a common modification method and realizing permanent modification of a polymer film.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a click chemistry synthesized graphene oxide grafted fluorine-containing polymer, which comprises the following steps:
(1) preparation of graphene oxide by improved Hummer's method
Under the condition of ice-water bath, graphite powder and potassium permanganate are added into concentrated sulfuric acid (H) with the mass concentration of 98 percent in sequence2SO4) Stirring in a beaker, heating to 45 ℃, and stopping after reacting for 12 hours; the reaction product was poured into a large beaker containing distilled water under ice-water bath conditions, and 30% by volume hydrogen peroxide (H) was added dropwise2O2) The color of the solution is changed from black brown to golden brown; with dilute H having a molar concentration of 1mol/L2SO4And repeatedly washing with distilled water until the solution is neutral, and drying in vacuum to obtain the graphene oxide.
Wherein the mass ratio of the graphite powder to the potassium permanganate is 1: 5-10; the mass ratio of the graphite powder to the concentrated sulfuric acid is 1: 50-80; heating to 45-50 ℃ and reacting for 12-18 h; the volume of the hydrogen peroxide and the concentrated sulfuric acid is 1: 5-10;
(2) alkynylation of graphene oxide
Adding the graphene oxide obtained in the step (1) into an anhydrous solvent for ultrasonic dispersion, sequentially adding propiolic acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide under the stirring condition, reacting at room temperature, filtering, and drying in vacuum to obtain graphene oxide with alkynyl;
(3) azidonation of fluoropolymers
Taking a fluorine-containing monomer as a main body, taking perfluoroiodohexane as a chain transfer agent, adding an initiator and a solvent A, carrying out free radical polymerization on the mixture, and drying the mixture after reaction to obtain an iodo-containing fluoropolymer;
adding the obtained iodo-fluoropolymer and sodium azide into a flask, adding a solvent B, stirring at room temperature, precipitating with a solvent C after the reaction is finished, and then placing the precipitate in a vacuum oven for drying to obtain the fluoropolymer with azido;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer
Ultrasonically dispersing the graphene oxide with the alkynyl group obtained in the step (2) and the fluorine-containing polymer with the azido group obtained in the step (3) in a solvent D, adding the mixture into a flask, and carrying out click chemical reaction on the alkynyl group on the modified graphene oxide and the azido group on the fluorine-containing polymer under the catalytic action of a copper catalyst to obtain the graphene oxide grafted fluorine-containing polymer.
Further, in the step (2), the mass ratio of the graphene oxide to the propiolic acid is 1-10: 1, and the ratio of the graphene oxide to the anhydrous solvent is 5-10 g: 1L; the mass ratio of the graphene oxide to the 4-dimethylaminopyridine is 1-10: 1, and the mass ratio of the graphene oxide to the dicyclohexylcarbodiimide is 1-3: 1.
Further, in the step (2), the anhydrous solvent is one or a mixture of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dichloromethane, toluene, cyclohexane and dimethyl sulfoxide;
in the step (2), performing ultrasonic treatment for 5-30 min; reacting at room temperature for 1-72 h.
Further, in the step (3), the mass ratio of the fluorine-containing monomer to the perfluoroiodohexane is 15-30: 1, the mass ratio of the fluorine-containing monomer to the initiator is 1: 0.003-0.009, and the ratio of the fluorine-containing monomer to the solvent A is 50-250 g: 1L;
the mass ratio of the iodo-fluorinated polymer to the sodium azide is 5-20: 1, and the ratio of the iodo-fluorinated polymer to the solvent B is 50-250 g: 1L.
Further, in the step (3), the fluorine-containing monomer is vinylidene fluoride; or mixed gas with the mass ratio of vinylidene fluoride to hexafluoropropylene being 1-4: 1; or mixed gas of vinylidene fluoride and chlorotrifluoroethylene with the mass ratio of 1-4: 1.
Further, the initiator is tert-butyl peroxypivalate, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, potassium persulfate or ammonium persulfate;
the solvent A is one or a mixture of water, trichlorotrifluoroethane, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
the solvent B is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the solvent C is one or a mixture of water, methanol and absolute ethyl alcohol.
Further, in the step (3), the free radical polymerization reaction time is 12-24 hours; the stirring time at room temperature is 10-36 h; the drying temperature of the vacuum oven is 30 ℃.
Further, in the step (4), the mass ratio of the graphene oxide having an alkynyl group to the fluoropolymer having an azido group is 0.01 to 0.1: 1;
the ratio of the alkynyl graphene oxide to the solvent D is 1-100 g: 1L;
the mass ratio of the alkynyl graphene oxide to the copper ion compound is 0.1-0.5: 1.
Preferably, the solvent D is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethyl carbonate;
the copper catalyst is a complex of copper ions.
Further, in the step (4), the time of ultrasonic dispersion is 5-30 min; stirring the mixture at room temperature for 12 to 36 hours.
The invention has the following beneficial effects:
the invention provides a preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis, which is simple in process, can realize permanent modification, is beneficial to grafting of the polymer on graphene oxide through modifying the surface of graphene oxide, and improves the compatibility between graphene oxide and the fluoropolymer. The obtained polymer film has higher tensile strength reaching 4.2MPa which is 1.7 times that of the fluorine-containing polymer film before modification, and the dielectric constant is also improved by more than 2 times that before modification.
Drawings
FIG. 1 is an infrared characterization of a fluoropolymer having an azido group prepared in example 1 of the present invention;
FIG. 2 is an infrared characterization plot of graphene oxide grafted fluoropolymer prepared according to example 1 of the present invention;
fig. 3 is a graph of dielectric constant data of graphene oxide grafted fluoropolymer and unmodified fluoropolymer prepared in example 1 of the present invention, wherein three curves in the graph are from top to bottom, which are curves of rGO-PVDF, GO-PVDF, and PVDF.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Aiming at the problems that the graphene polymer is easy to agglomerate, poor in compatibility and difficult to industrially produce in the prior art, the invention provides a preparation method for synthesizing the graphene oxide grafted fluorine-containing polymer by click chemistry.
Example 1
A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps:
1) preparation of graphene oxide by improved Hummer's method
Under the condition of ice-water bath, 3g of graphite is sequentially addedPowder, 15g KMnO4Adding 115mL of concentrated H with the mass concentration of 98%2SO4Stirring in a beaker, heating to 45 ℃, and stopping after reacting for 12 hours; pouring the reaction product into a large beaker filled with 200mL of distilled water under the ice-water bath condition, and dropwise adding 15mL of H with the volume concentration of 30%2O2The color of the solution is changed from black brown to golden brown; using 100mL of dilute H with a molar concentration of 1mol/L2SO4Repeatedly washing with distilled water until the solution is neutral, and drying in vacuum to obtain graphene oxide;
(2) alkynylation of graphene oxide
Weighing 0.1641g of graphene oxide obtained in the step (1), ultrasonically dispersing in 100mL of anhydrous tetrahydrofuran for 5min, adding the graphene oxide into a flask, stirring, sequentially adding 0.1g of propiolic acid, 0.0018g of 4-dimethylaminopyridine and 0.0092g of dicyclohexylcarbodiimide, carrying out esterification reaction on the graphene oxide, reacting at normal temperature for 1h, filtering, and carrying out vacuum drying to obtain graphene oxide with alkynyl;
(3) azidonation of fluoropolymers
Weighing 0.1359g of tert-butyl peroxypivalate and 1.0453g of perfluorohexane into a reaction kettle by using 200mL of trifluorotrichloroethane, introducing 15g of vinylidene fluoride gas monomer into the reaction kettle to perform free radical polymerization, reacting for 22 hours, and drying to obtain iodopolyvinylidene fluoride;
adding 2g of the obtained iodo-polyvinylidene fluoride and 0.2031g of sodium azide into a flask, adding 20mLN, N-dimethylformamide, stirring at normal temperature for 20h, precipitating with methanol after the reaction is finished, and then placing the precipitate in a vacuum oven at 30 ℃ for drying to obtain polyvinylidene fluoride with azide groups;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer
And (3) ultrasonically dispersing 0.05g of graphene oxide with alkynyl obtained in the step (2) and 1g of polyvinylidene fluoride with azido obtained in the step (3) in 20mL of N, N-dimethylformamide for 5min, adding the mixture into a flask, adding 0.2g of cuprous bromide and 0.24g of pentamethyldiethylenetriamine, mixing to form a copper ion complex, stirring and reacting at normal temperature for 24h under the protection of nitrogen, washing and drying to obtain the graphene oxide grafted polyvinylidene fluoride.
As can be seen from a comparison of FIGS. 1 and 2, the infrared characterization pattern of the graphene oxide-grafted fluoropolymer obtained in the examples is 2100cm-1The disappearance of the characteristic peak can prove the successful grafting of polyvinylidene fluoride chain on the graphene oxide. As can be seen from fig. 3, in the embodiment, the dielectric property of the graphene oxide grafted fluoropolymer (GO-PVDF) can be more than 2 times that of unmodified polyvinylidene fluoride (PVDF), and after the graphene oxide is reduced, the dielectric property of the grafted polymer (rGO-PVDF) can be further improved to 2.5 times that of the unmodified polyvinylidene fluoride, so that the possibility of applying the graphene oxide grafted fluoropolymer (GO-PVDF) to an electronic device is realized.
Dispersing the obtained modified polymer and polyvinylidene fluoride in N, N-dimethylformamide as a solvent, and obtaining the modified polymer film by using a solution casting method. The obtained graphene oxide grafted fluorine-containing polymer film improves the performance of the polymer, the surface appearance of the modified polymer film is consistent, the front side and the back side are gray, the load N and the elongation w of the film in the breaking process are measured by using an XQ-2 fiber strength elongation instrument, and the tensile strength of the film is 4.0MPa and is 1.6 times that of a polyvinylidene fluoride film calculated by using a formula.
Example 2
A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method, wherein the preparation process is the same as that of the embodiment 1;
(2) alkynylation of graphene oxide:
weighing 0.1641g of graphene oxide obtained in the step (1), ultrasonically dispersing in 100mL of anhydrous N, N-dimethylformamide for 10min, adding into a flask, stirring, sequentially adding 0.1032g of propiolic acid, 0.0018g of 4-dimethylaminopyridine and 0.0103g of dicyclohexylcarbodiimide, carrying out esterification reaction, reacting at normal temperature for 6h, filtering, and vacuum drying to obtain graphene oxide with alkynyl;
(3) azidonation of fluoropolymers
Taking 200mL of N-methylpyrrolidone, weighing 0.27g of tert-butyl peroxypivalate and 1.0324g of perfluorohexane iodide, adding into a reaction kettle, introducing 15g of vinylidene fluoride gas monomer, carrying out free radical polymerization, reacting for 12h, and drying to obtain iodopolyvinylidene fluoride.
Adding 2g of the obtained iodo-polyvinylidene fluoride and 0.2031g of sodium azide into a flask, adding 20mL of dimethyl sulfoxide, stirring at normal temperature for 12h, precipitating with methanol after the reaction is finished, and then placing the precipitate in a vacuum oven at 30 ℃ for drying to obtain polyvinylidene fluoride with azido;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer:
and (3) ultrasonically dispersing 0.05g of graphene oxide with alkynyl obtained in the step (2) and 1g of polyvinylidene fluoride with azido obtained in the step (3) in 30mL of N, N-dimethylformamide for 25min, adding into a flask, adding a copper ion complex formed by mixing 0.2g of cuprous bromide and 0.24g of pentamethyl diethylenetriamine, stirring and reacting at normal temperature for 23h under the protection of nitrogen, washing and drying to obtain the graphene oxide grafted polyvinylidene fluoride.
Dispersing the obtained modified polymer and polyvinylidene fluoride in N, N-dimethylformamide as a solvent, and obtaining the modified polymer film by using a solution casting method. The modified polymer film obtained in the embodiment has consistent surface appearance, the front side and the back side are gray, the load N and the elongation w of the film at the time of tensile failure are measured by using an XQ-2 fiber strength elongation instrument, the tensile strength of the film is calculated to be 4.2MPa by using a formula, the tensile strength is 1.7 times that of a polyvinylidene fluoride film, and the tensile property of the polymer is effectively improved.
Example 3
A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method, wherein the preparation process is the same as that of the embodiment 1;
(2) alkynylation of graphene oxide:
weighing 0.1641g of graphene oxide obtained in the step (1), ultrasonically dispersing in 40mL of anhydrous tetrahydrofuran for 5min, adding the graphene oxide into a flask, stirring, sequentially adding 0.019g of propiolic acid, 0.0018g of 4-dimethylaminopyridine and 0.006g of dicyclohexylcarbodiimide, carrying out esterification reaction on the graphene oxide, reacting at normal temperature for 1h, filtering, and carrying out vacuum drying to obtain graphene oxide with alkynyl;
(3) azidation of the fluoropolymer:
and (2) weighing 0.0718g of tert-butyl peroxypivalate and 0.669g of perfluorohexane in 200mL of trifluorotrichloroethane, adding into a reaction kettle, introducing 14.4g of vinylidene fluoride gas monomer, carrying out free radical polymerization, reacting for 22h, and drying to obtain iodopolyvinylidene fluoride.
Adding 2g of the obtained iodo-polyvinylidene fluoride and 0.2031g of sodium azide into a flask, adding 20mLN, N-dimethylacetamide, stirring at normal temperature for 24 hours, precipitating with methanol after the reaction is finished, and then placing the precipitate in a vacuum oven at 30 ℃ to dry to obtain polyvinylidene fluoride with azide groups;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer:
and (3) ultrasonically dispersing 0.05g of graphene oxide with alkynyl obtained in the step (2) and 1g of polyvinylidene fluoride with azido obtained in the step (3) in 30mL of N, N-dimethylformamide for 5min, adding into a flask, adding a copper ion complex formed by mixing 0.2g of cuprous bromide and 0.24g of pentamethyl diethylenetriamine, stirring and reacting at normal temperature for 23 hours under the protection of nitrogen, washing and drying to obtain the graphene oxide grafted polyvinylidene fluoride.
Dispersing the obtained modified polymer and polyvinylidene fluoride in N, N-dimethylformamide as a solvent, and obtaining the modified polymer film by using a solution casting method. The modified polymer film obtained in the embodiment has consistent surface appearance, the front side and the back side are gray, the load N and the elongation w of the film at the time of tensile failure are measured by using an XQ-2 fiber strength and elongation meter, and the tensile strength is calculated to be 3.8MPa by using a formula and is 1.5 times of that of the polyvinylidene fluoride film before modification.
Example 4
A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method, wherein the preparation process is the same as that of the embodiment 1;
(2) alkynylation of graphene oxide:
weighing 0.1641g of graphene oxide obtained in the step (1) in a mixed solution of 40mLN, N-dimethylformamide and 60mLN, N-dimethylacetamide, ultrasonically dispersing for 30min, adding the graphene oxide into a flask, stirring, sequentially adding 0.1029g of propiolic acid, 0.0021g of 4-dimethylaminopyridine and 0.012g of dicyclohexylcarbodiimide, carrying out esterification reaction, reacting for 8h at normal temperature, filtering, and carrying out vacuum drying to obtain graphene oxide with alkynyl;
(3) azidation of the fluoropolymer:
100mL of N-dimethylformamide and 100mL of N-methylpyrrolidone are mixed, 0.0447g of benzoyl peroxide and 1.0217g of perfluoroiodohexane are weighed and added into a reaction kettle, 4g of mixed gas monomer of vinylidene fluoride (VDF) and 12g of Hexafluoropropylene (HFP) is introduced to carry out free radical polymerization, and P (VDF-HFP) -I is obtained after reaction for 22 hours and drying.
Adding the obtained P (VDF-HFP) -I2 g and 0.1921g of sodium azide into a flask, adding 20mLN, N-dimethylacetamide, stirring at normal temperature for 24 hours, precipitating with absolute ethanol after the reaction is finished, and then placing the precipitate in a vacuum oven at 30 ℃ to dry to obtain the fluoropolymer with azide groups;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer
And (3) ultrasonically dispersing 0.05g of graphene oxide with alkynyl obtained in the step (2) and 1g of fluorine-containing polymer with azido obtained in the step (3) in 30ml of N-methyl pyrrolidone for 25min, adding the mixture into a flask, adding a copper ion complex formed by mixing 0.2g of cuprous bromide with 0.24g of pentamethyl diethylenetriamine, stirring and reacting at normal temperature for 23 hours under the protection of nitrogen, washing and drying to obtain the graphene oxide grafted P (VDF-HFP).
The resulting modified polymer and a P (VDF-HFP) matrix were dispersed in N, N-dimethylformamide as a solvent, and a modified polymer film was obtained by solution casting. The modified polymer film obtained in this example has a consistent surface morphology, both front and back sides are gray, the load N and elongation w at the time of film stretch-breaking are measured by using an XQ-2 fiber strength elongation meter, and the tensile strength is calculated by using a formula to be 8MPa, which is 1.4 times that of the P (VDF-HFP) film before modification.
Example 5
A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method, wherein the preparation process is the same as that of the embodiment 1;
(2) alkynylation of graphene oxide:
weighing 0.1641g of graphene oxide obtained in the step (1) in 100mL of dichloromethane, performing ultrasonic dispersion for 30min, adding the graphene oxide into a flask, stirring, sequentially adding 0.0912g of propiolic acid, 0.0018g of 4-dimethylaminopyridine and 0.096g of dicyclohexylcarbodiimide, performing esterification reaction, reacting at normal temperature for 72h, filtering, and performing vacuum drying to obtain graphene oxide with alkynyl;
(3) azidation of the fluoropolymer:
weighing 0.0102g of azodiisoheptanonitrile and 1.012g of perfluorohexane into a reaction kettle by taking 100mL of trifluorotrichloroethane and 100mL of dimethyl sulfoxide, introducing a mixed gas monomer of 4g of vinylidene fluoride (VDF) and 12g of Chlorotrifluoroethylene (CTFE) to perform free radical polymerization, reacting for 12h, and drying to obtain P (VDF-CTFE) -I.
Adding 2g of the obtained P (VDF-CTFE) -I and 0.2031g of sodium azide into a flask, adding 20mLN, N-dimethylformamide, stirring at normal temperature for 24h, precipitating with methanol after the reaction is finished, and then placing the precipitate in a vacuum oven at 30 ℃ for drying to obtain P (VDF-CTFE) with azide;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer:
and (3) ultrasonically dispersing 0.05g of graphene oxide with alkynyl obtained in the step (2) and 1g of P (VDF-CTFE) with azido obtained in the step (3) in 30mL of a mixed solution of dimethyl sulfoxide and dimethyl carbonate for 5min, adding the mixture into a flask, adding 0.2g of cuprous bromide and 0.24g of pentamethyldiethylenetriamine to form a copper ion complex, stirring and reacting for 10 hours at normal temperature under the protection of nitrogen, washing and drying to obtain the graphene oxide grafted P (VDF-CTFE).
The obtained modified polymer and a P (VDF-CTFE) matrix are dispersed in N, N-dimethylformamide as a solvent, and a modified polymer film is obtained by a solution casting method. The modified polymer film obtained in this example has consistent surface morphology, both front and back sides are gray, the load N and elongation w at the time of tensile failure of the film are measured by using an XQ-2 fiber tensile tester, and the tensile strength is calculated by using a formula to be 14MPa, which is 1.6 times that of the P (VDF-CTFE) film before modification.
Example 6
A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis comprises the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method, wherein the preparation process is the same as that of the embodiment 1;
(2) alkynylation of graphene oxide:
weighing 0.1641g of graphene oxide obtained in the step (1) in a mixed solution of 40mL of methylbenzene and 60mL of cyclohexane, performing ultrasonic dispersion for 15min, adding the graphene oxide into a flask, stirring, sequentially adding 0.0992g of propiolic acid, 0.0021g of 4-dimethylaminopyridine and 0.011g of dicyclohexylcarbodiimide, performing esterification reaction, reacting at normal temperature for 36h, filtering, and performing vacuum drying to obtain graphene oxide with alkynyl;
(3) azidation of the fluoropolymer:
150mL of trifluorotrichloroethane, 50mL of water, 0.102g of potassium persulfate and 1.025g of perfluorohexane are added into a reaction kettle, 15g of vinylidene fluoride gas monomer is introduced to carry out free radical polymerization, and the iodopolyvinylidene fluoride is obtained after 24 hours of reaction and drying.
Adding 2g of the obtained iodo-polyvinylidene fluoride and 0.2031g of sodium azide into a flask, adding 20 mLN-methyl pyrrolidone, stirring at normal temperature for 36 hours, precipitating with methanol after the reaction is finished, and then placing the precipitate in a vacuum oven at 30 ℃ for drying to obtain polyvinylidene fluoride with azide groups;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer:
and (3) ultrasonically dispersing 0.05g of graphene oxide with alkynyl obtained in the step (2) and 1g of polyvinylidene fluoride with azido obtained in the step (3) in 30mL of dimethyl carbonate for 5min, adding the mixture into a flask, adding 0.2g of cuprous bromide and 0.24g of pentamethyl diethylenetriamine to form a copper ion complex, stirring and reacting at normal temperature for 23 hours under the protection of nitrogen, washing and drying to obtain the graphene oxide grafted polyvinylidene fluoride.
Dispersing the obtained modified polymer and polyvinylidene fluoride in N, N-dimethylformamide as a solvent, and obtaining the modified polymer film by using a solution casting method. The modified polymer film obtained in the embodiment has consistent surface appearance, the front side and the back side are gray, the load N and the elongation w of the film at the time of tensile failure are measured by using an XQ-2 fiber strength and elongation meter, and the tensile strength is calculated to be 4.3MPa by using a formula and is 1.7 times of that of the polyvinylidene fluoride film before modification.
Comparative example 1
A preparation method of modified polyvinylidene fluoride comprises the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method, wherein the preparation process is the same as that of the embodiment 1;
(2) and mixing the dispersion liquid of the graphene oxide in the solvent N, N-dimethylformamide with the solution of the polyvinylidene fluoride in the N, N-dimethylformamide, and obtaining the modified polymer film by using a solution casting method.
The obtained modified polymer film has poor compatibility and inconsistent front and back colors, the load N and the elongation w of the film at the time of tensile failure are measured by using an XQ-2 fiber strength and elongation meter, the tensile strength of the film is calculated to be 3.5MPa by using a formula, the tensile strength is 1.4 times that of polyvinylidene fluoride before modification, a certain modification effect is achieved, but permanent modification cannot be realized.
Through a tensile strength test, the tensile strength of the graphene oxide grafted fluoropolymer synthesized by click chemistry is greatly improved to 4.3MPa, which is 1.7 times that of polyvinylidene fluoride. Through a thermal weight loss test, the decomposition temperature of the graphene oxide grafted fluoropolymer synthesized by click chemistry is 450 ℃, and the decomposition temperature is higher than that of polyvinylidene fluoride and polychlorotrifluoroethylene, which indicates that the stability is enhanced. The obtained polymer can be well dissolved and dispersed in polar aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and dimethyl carbonate, and the defects that graphene oxide is easy to agglomerate and is not easy to be compatible with the solvents are overcome.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A preparation method of a graphene oxide grafted fluoropolymer through click chemistry synthesis is characterized by comprising the following steps:
(1) preparing graphene oxide by adopting an improved Hummer's method;
(2) alkynylation of graphene oxide
Adding the graphene oxide obtained in the step (1) into an anhydrous solvent for ultrasonic dispersion, sequentially adding propiolic acid, 4-dimethylaminopyridine and dicyclohexylcarbodiimide under the stirring condition, reacting at room temperature, filtering, and drying in vacuum to obtain graphene oxide with alkynyl;
(3) azidonation of fluoropolymers
Taking a fluorine-containing monomer as a main body, taking perfluoroiodohexane as a chain transfer agent, adding an initiator and a solvent A, carrying out free radical polymerization on the mixture, and drying the mixture after reaction to obtain an iodo-containing fluoropolymer;
adding the obtained iodo-fluoropolymer and sodium azide into a flask, adding a solvent B, stirring at room temperature, precipitating with a solvent C after the reaction is finished, and then placing the precipitate in a vacuum oven for drying to obtain the fluoropolymer with azido;
the fluorine-containing monomer is vinylidene fluoride; or
A mixed gas of vinylidene fluoride and hexafluoropropylene in a mass ratio of 1-4: 1; or mixed gas with the mass ratio of vinylidene fluoride to chlorotrifluoroethylene being 1-4: 1;
(4) click chemistry synthesis of graphene oxide grafted fluoropolymer
Ultrasonically dispersing the graphene oxide with alkynyl obtained in the step (2) and the fluorine-containing polymer with azido obtained in the step (3) in a solvent D, adding the mixture into a flask, carrying out stirring reaction at room temperature under the protection of nitrogen under the catalysis of a copper catalyst, washing, and drying to obtain the graphene oxide grafted fluorine-containing polymer.
2. The preparation method of the graphene oxide-grafted fluoropolymer according to claim 1, wherein in the step (2), the mass ratio of graphene oxide to propiolic acid is 1-10: 1, and the ratio of graphene oxide to anhydrous solvent is 1-10 g: 1L; the mass ratio of the graphene oxide to the 4-dimethylaminopyridine is 50-100: 1, and the mass ratio of the graphene oxide to the dicyclohexylcarbodiimide is 10-50: 1.
3. The preparation method of the graphene oxide grafted fluoropolymer according to claim 2, wherein in the step (2), the anhydrous solvent is one or a mixture of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dichloromethane, toluene, cyclohexane and dimethyl sulfoxide;
in the step (2), performing ultrasonic treatment for 5-30 min; reacting at room temperature for 1-72 h.
4. The preparation method of the graphene oxide grafted fluoropolymer according to claim 1, wherein in the step (3), the mass ratio of the fluorine-containing monomer to perfluoroiodohexane is 15-30: 1, the mass ratio of the fluorine-containing monomer to the initiator is 1: 0.003-0.009, and the ratio of the fluorine-containing monomer to the solvent A is 50-250 g: 1L;
the mass ratio of the iodo-containing polymer to the sodium azide is 5-20: 1, and the ratio of the iodo-containing polymer to the solvent B is 50-250 g: 1L.
5. The preparation method of the graphene oxide-grafted fluoropolymer according to claim 1, wherein in the step (3), the initiator is tert-butyl peroxypivalate, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, potassium persulfate or ammonium persulfate;
the solvent A is one or a mixture of water, trichlorotrifluoroethane, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
the solvent B is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the solvent C is one or a mixture of water, methanol and absolute ethyl alcohol.
6. The preparation method of the graphene oxide-grafted fluoropolymer according to claim 5, wherein in the step (3), the free radical polymerization reaction time is 12-24 h; the stirring time at room temperature is 10-36 h; the drying temperature of the vacuum oven is 30 ℃.
7. The method for preparing graphene oxide-grafted fluoropolymer according to claim 1, wherein in the step (4), the mass ratio of graphene oxide having alkynyl group to fluoropolymer having azido group is 0.01-0.1: 1;
the ratio of the alkynyl graphene oxide to the solvent D is 1-100 g: 1L;
the mass ratio of the alkynyl graphene oxide to the copper catalyst is 0.1-0.5: 1.
8. The preparation method of the graphene oxide grafted fluoropolymer according to claim 7, wherein the solvent D is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and dimethyl carbonate;
the copper catalyst is a complex of copper ions.
9. The preparation method of the click chemistry synthesis graphene oxide grafted fluoropolymer according to claim 8, wherein in the step (4), the time of ultrasonic dispersion is 5-30 min; stirring the mixture at room temperature for 12 to 36 hours.
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