CN108892905B - Preparation method of high-performance polyvinyl alcohol/graphene composite film - Google Patents
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Abstract
The invention belongs to the technical field of polymer composite material preparation, and particularly relates to a preparation method of a polyvinyl alcohol/graphene film. In the invention, a new process method is adopted to prepare the polyvinyl alcohol/graphene composite film, namely, a polyvinyl alcohol/graphene oxide solution is prepared through in-situ polymerization, then a small amount of dopamine is added, the reaction is carried out under certain temperature and alkaline conditions, and then the film is dried to form the polyvinyl alcohol/graphene composite film. Compared with a solution blending method, the composite film prepared by the method has more excellent mechanical property and heat resistance.
Description
Technical Field
The invention belongs to the technical field of polymer composite material preparation, and particularly relates to a preparation method of a polyvinyl alcohol/graphene film.
Background
Polyvinyl alcohol is a typical crystalline water-soluble polymer. Has excellent water solubility, high strength and high modulus, solvent resistance, gas barrier property, biodegradability and the like. Besides being used as vinylon fiber, the polyvinyl alcohol fiber can also be widely applied to products such as films, coatings, adhesives, emulsifiers, dispersing agents and the like, and the application range of the polyvinyl alcohol fiber is wide in the industries such as textile, medicine, wood, food, building, printing, steel, polymer chemical industry and the like. Polyvinyl alcohol is a flexible polymer, and the mechanical property and the heat resistance of the polyvinyl alcohol often cannot meet higher use requirements. Therefore, the mechanical property of the polyvinyl alcohol is improved by compounding with other materials with excellent performance, and the heat resistance is a common method at present.
Graphene is a carbon material with excellent performance, and is sp-form carbon atoms2The Young modulus of graphene is about 1100GPa, the breaking strength of the graphene is more than 130GPa, and the breaking strength of the graphene is 100 times higher than that of the best steel.
Dopamine, also known as 4- (2-aminoethyl) -1, 2-benzenediol, can self-polymerize into poly-dopamine under alkaline conditions, can adhere to almost all types of substrates including polymers, metals, glass, ceramics, carbon nanotubes, and has certain reducibility. The graphene oxide film has self-polymerization property, adhesion property and reduction property, can be well attached to the surface of graphene oxide, and can reduce the graphene oxide and repair structural defects generated during preparation of the graphene.
At present, the preparation method of the polyvinyl alcohol/graphene composite material reported is generally a solution blending method, namely, a polyvinyl alcohol stock solution with a certain concentration is blended with a graphene dispersion solution. CN105315476A discloses a method for preparing a modified graphene polyvinyl alcohol composite film, which comprises selecting 7-amino-4-methylcoumarin as a modifier, adding a modified graphene dispersion solution into a polyvinyl alcohol aqueous solution to obtain a uniformly dispersed modified graphene-polyvinyl alcohol mixed solution, and drying to obtain the modified graphene-polyvinyl alcohol composite film. CN104988592A discloses a preparation method of polyvinyl alcohol/graphene composite nanofiber material. Preparing graphite oxide by adopting an improved Hummers method, further preparing a uniform mixed solution of polyvinyl alcohol/graphene oxide, reducing the graphene oxide in the mixed solution into graphene under high-energy ionizing radiation, and preparing the polyvinyl alcohol/graphene composite nanofiber material by utilizing an electrostatic spinning technology. In the patents, the polyvinyl alcohol graphene composite material is prepared by a solution blending method, the interface bonding force is not strong enough, and the mechanical property and the thermal property are to be improved.
Disclosure of Invention
In order to further improve the performance of a polyvinyl alcohol/graphene composite material, in the invention, a novel process method is adopted to prepare a polyvinyl alcohol/graphene composite film, namely, a polyvinyl alcohol/graphene oxide solution is prepared through in-situ polymerization, then a small amount of dopamine is added, the reaction is carried out under a certain temperature and alkaline condition, and then the film is dried to form a film, so that the polyvinyl alcohol/graphene composite film is prepared. Compared with a solution blending method, the composite film prepared by the method has more excellent mechanical property and heat resistance.
A preparation method of a high-performance polyvinyl alcohol/graphene composite film mainly comprises the following process methods:
(1) preparing a graphene oxide dispersion liquid;
92mL of concentrated sulfuric acid (98%) was poured into a 500mL dry three-necked flask and cooled to 0 ℃. Then 4g of graphite, 2g of sodium nitrate, were slowly added to the concentrated sulfuric acid, taking care not to hang the graphite on the wall, and the graphite was dispersed uniformly by mechanical stirring for 20 minutes. Then slowly adding 12g of potassium permanganate, continuously stirring for 3h, and controlling the reaction temperature to be below 10 ℃. The three-necked flask was transferred to a 35 ℃ oil bath, kept at a constant temperature and stirred for 3 hours, and the mixture was found to turn from black to grey brown. Then, 200mL of deionized water is slowly added, and the temperature is kept between 90 ℃ and 98 ℃. Then quickly transferring the mixture into an oil bath kettle at 90 ℃, maintaining for 15min, and keeping stirring. 560mL of deionized water is added into the system for dilution, the color of the system becomes brown yellow, 30mL of hydrogen peroxide (30%) is added, and the mixture is stirred until the system becomes bright yellow. The product was filtered through dilute hydrochloric acid (5%) until the sulfate ion was removed (the filter cake was checked with 10% barium chloride to determine if there was a sulfate ion). And (4) washing twice with water to remove metal ions in the solution. The filter cake was placed in a vacuum oven and dried at 40 ℃ until constant weight. Ultrasonically dispersing 0.5g of graphite oxide in 100g of methanol for 30min to fully strip the graphite oxide to form brown yellow graphene oxide dispersion liquid with the mass concentration of 0.5%.
(2) Preparing a polyvinyl acetate/graphene oxide solution by in-situ polymerization: according to the mass percentage, under the protection of nitrogen, 5-30% of monomer, 40-65% of solvent, 0.1-1% of initiator and 5-35% of graphene oxide dispersion liquid are sequentially added into a polymerization reaction system, the temperature is raised to 30 ℃, the reaction is carried out for 3-6h under the condition of heat preservation, and then the reaction is carried out for 1-2h under the condition of raising the temperature to 50 ℃. Adding 0.1-1% polymerization inhibitor, stopping reaction to obtain polyvinyl acetate solution. The monomer can be selected from vinyl acetate, vinyl formate, vinyl butyrate and the like; the solvent can be selected from methanol, ethanol, isopropanol and the like; the initiator can be selected from azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, peroxydicarbonate and the like; the polymerization inhibitor can be hydroquinone or FeCl3。
(3) Polyvinyl acetate/graphene oxide alcoholysis: according to the weight percentage, 5% -40% of sodium hydroxide methanol solution is dripped into 60-95% of polyvinyl acetate solution, and alcoholysis is carried out for 1-5h, so as to obtain polyvinyl alcohol/graphene oxide solution. The mass concentration of the sodium hydroxide in the sodium hydroxide methanol solution is 10-25%.
(4) Preparation of polyvinyl alcohol/graphene (rGO) solution: according to the weight percentage, 99 to 99.9 percent of polyvinyl alcohol/graphene oxide solution and 0.1 to 1 percent of dopamine are sequentially added, the pH value is adjusted to be about 8 to 10, the temperature is kept at 40 to 80 ℃ for 12 hours, and the solution is changed from bright yellow to dark black;
(5) preparing a polyvinyl alcohol/graphene (rGO) nanocomposite film: the mixed solution was poured onto a glass plate and placed in an oven and dried at 60-70 ℃ to form a black film of 100-.
In the preparation method of the high-performance polyvinyl alcohol/graphene composite film, the in-situ polymerized substances are preferably prepared by the following steps: according to mass percentage, under the protection of nitrogen, 10-25% of monomer, 40-65% of solvent, 0.1-0.5% of initiator and 10-20% of graphene oxide dispersion liquid are sequentially added into the system. After the reaction is finished, 0.2 to 0.8 percent of polymerization inhibitor is added. The monomer is preferably vinyl acetate, the solvent is preferably methanol, and the polymerization inhibitor is preferably hydroquinone.
In the preparation method of the high-performance polyvinyl alcohol/graphene composite film, the graphene oxide has a polymerization inhibition effect on a polymerization reaction during in-situ polymerization, and the molecular weight of the polyvinyl alcohol is reduced, so that the performance of the composite film is reduced. Meanwhile, the lower the reaction temperature, the lower the effect of inhibiting polymerization. Preferably, the in-situ polymerization reaction temperature is 30 ℃, the reaction time is 3-5h, and the low-temperature initiator is azobisisoheptonitrile.
In the preparation method of the high-performance polyvinyl alcohol/graphene composite film, the polyvinyl acetate/graphene oxide enol solution ratio is preferably as follows: 80-95% of polyvinyl acetate solution and 5-20% of sodium hydroxide methanol solution.
In the preparation method of the high-performance polyvinyl alcohol/graphene composite film, the performance of the composite film is related to the addition amount of dopamine, the reaction temperature and the reaction time. When the amount of the dopamine is too small, the reduction amount of the graphene oxide is reduced, and the performance of the composite film is reduced. When the addition amount of dopamine is too large, graphene is agglomerated, so that the performance of the composite film is also reduced. Preferred preparation conditions of the composite solution are as follows: adding 0.5-1% by mass of dopamine into the polyvinyl alcohol/graphene oxide solution, adjusting the pH to about 9, and keeping the temperature at 40-60 ℃ for 12 hours to change the solution from bright yellow to dark black.
In the preparation method of the high-performance polyvinyl alcohol/graphene composite film, the process conditions of the polyvinyl alcohol/graphene nano composite film are preferably as follows: the mixed solution was poured onto a glass plate and put into an oven and dried at 70 ℃ to form a black film of 200. mu.m.
Compared with the preparation method of polyvinyl alcohol graphene in the prior art, the preparation method has the following outstanding advantages and technical effects:
(1) compared with the traditional solution blending method, the in-situ polymerization method adopted by the invention effectively enables polymer molecular chains and graphene to form stronger chemical bonds, so that the interface bonding force is stronger, the dispersion effect is better, and the mechanical property and the thermal property of the composite material are higher;
(2) dopamine is used, and its effects are as follows: the graphene oxide can be used as a reducing agent of graphene oxide to reduce partial oxygen-containing groups to form graphene. And secondly, the polydopamine can be formed by self-polymerization under an alkaline condition, is adhered to the surface of the graphene, and plays a coupling role between the graphene and polyvinyl alcohol molecules. The reducibility, self-polymerization and adhesiveness of dopamine can effectively improve the performance of the polyvinyl alcohol/graphene composite material polymerized in situ.
Detailed Description
Example 1
1.1 preparation of Graphene Oxide (GO) Dispersion
1.1.1 the specific operation is as follows:
92mL of concentrated sulfuric acid (98%) was poured into a 500mL dry three-necked flask and cooled to 0 ℃. Then 4g of graphite, 2g of sodium nitrate, were slowly added to the concentrated sulfuric acid, taking care not to hang the graphite on the wall, and the graphite was dispersed uniformly by mechanical stirring for 20 minutes. Then slowly adding 12g of potassium permanganate, continuously stirring for 3h, and controlling the reaction temperature to be below 10 ℃. The three-necked flask was transferred to a 35 ℃ oil bath, kept at a constant temperature and stirred for 3 hours, and the mixture was found to turn from black to grey brown. Then, 200mL of deionized water is slowly added, and the temperature is kept between 90 ℃ and 98 ℃. Then quickly transferring the mixture into an oil bath kettle at 90 ℃, maintaining for 15min, and keeping stirring. 560mL of deionized water is added into the system for dilution, the color of the system becomes brown yellow, 30mL of hydrogen peroxide (30%) is added, and the mixture is stirred until the system becomes bright yellow. The product was filtered through dilute hydrochloric acid (5%) until the sulfate ion was removed (the filter cake was checked with 10% barium chloride to determine if there was a sulfate ion). And (4) washing twice with water to remove metal ions in the solution. The filter cake was placed in a vacuum oven and dried at 40 ℃ until constant weight.
1.1.2 preparation of Graphene Oxide (GO) methanol Dispersion
Ultrasonically dispersing 5g of graphite oxide in 995g of methanol for 30min to fully strip the graphite oxide to form brown yellow graphene oxide dispersion liquid with the mass concentration of 0.5%.
1.2 preparation of polyvinyl alcohol/graphene composite film by in-situ polymerization method
Introducing nitrogen into a 500mL reaction bottle, sequentially adding 50g of vinyl acetate, 150g of methanol, 0.5g of azodiisoheptanonitrile and 40g of graphene oxide dispersion liquid, heating to 30 ℃, keeping the temperature for reaction for 5 hours, and then heating to 70 ℃ for reaction for 1 hour. 1g of hydroquinone was added to terminate the reaction, and 240g of a polyvinyl acetate/graphene oxide solution was obtained. And then, dropwise adding a methanol solution containing 30g of 20 wt% sodium hydroxide, and carrying out alcoholysis for 2 hours to obtain a polyvinyl alcohol/graphene oxide solution. 2g of dopamine was added, the pH was adjusted to 9, and the solution changed from bright yellow to dark black by incubation at 50 ℃ for 12 h. The mixed solution was poured onto a glass plate and put into an oven, and dried at 70 ℃ to form a film. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.4%. SEM shows that the section is flat and ordered, the tensile strength is 185MPa, and the melting point is 238 ℃ by DSC test.
Example 2
The same operation and conditions as in example 1 were followed except that the amount of the graphene oxide dispersion was changed to 20 g. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.2%. SEM shows that the section is flat and ordered, the measured tensile strength is 153MPa, and the DSC measured melting point is 235 ℃.
Example 3
The same operation and conditions as in example 1 were followed except that the amount of the graphene oxide dispersion was changed to 60 g. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with 0.6 mass percent of graphene. SEM shows that the section is slightly wrinkled, the tensile strength is 123MPa, and the melting point is 231 ℃ in DSC test.
Example 4
The same procedure and conditions as in example 1 were followed except that dopamine was not added. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.4%. SEM shows that the section is flat and orderly, the measured tensile strength is 113MPa, and the DSC measured melting point is 232 ℃.
Comparative example 1
(1) The preparation method of the graphene oxide dispersion liquid is the same as that of example 1.
(2) Preparing a polyvinyl alcohol/graphene composite film by adopting traditional solution blending: introducing nitrogen into a 500mL reaction bottle, sequentially adding 50g of vinyl acetate, 150g of methanol and 0.5g of azobisisoheptonitrile, heating to 30 ℃, preserving heat for reaction for 5 hours, and then heating to 70 ℃ for reaction for 1 hour. 1g of hydroquinone was added to terminate the reaction, to obtain a polyvinyl acetate solution. And then, adding 30g of methanol solution containing 20 wt% of sodium hydroxide dropwise, and carrying out alcoholysis for 2h to obtain a polyvinyl alcohol solution. Adding 40g of graphene oxide dispersion liquid and 2g of dopamine, keeping the temperature at 50 ℃ for 12h, adjusting the pH to 9, and changing the solution from bright yellow to dark black. The mixed solution was poured onto a glass plate and put into an oven, and dried at 70 ℃ to form a film. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.4%. SEM shows that the section is flat and ordered, the measured tensile strength is 149MPa, and the DSC measured melting point is 220 ℃.
Comparative example 2
The same operation and conditions as in comparative example 1 were followed except that the amount of the graphene oxide dispersion was changed to 20 g. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.2%. SEM shows that the cross section is rough, the tensile strength is 126MPa, and the melting point is 219 ℃ by DSC.
Comparative example 3
The same operation and conditions as in comparative example 1 were followed except that the amount of the graphene oxide dispersion was changed to 60 g. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.6%. SEM shows that the section has more wrinkles, the tensile strength is measured to be 135MPa, and the melting point is 218 ℃ by DSC measurement.
Comparative example 4
The same procedure and conditions as in comparative example 1 were used except that dopamine was not added. And preparing the 200 mu m polyvinyl alcohol/graphene oxide nano composite film with the mass fraction of the graphene oxide of 0.2%. SEM shows that the cross section is rough, the tensile strength is 102MPa, and the melting point is 218 ℃ when measured by DSC.
Comparative example 5
The raw polyvinyl alcohol film was prepared as follows: introducing nitrogen into a 500mL reaction bottle, sequentially adding 50g of vinyl acetate, 150g of methanol and 0.5g of azobisisoheptonitrile, heating to 30 ℃, preserving heat for reaction for 5 hours, and then heating to 70 ℃ for reaction for 1 hour. 1g of hydroquinone was added to terminate the reaction, to obtain a polyvinyl acetate solution. And then, adding 30g of methanol solution containing 20 wt% of sodium hydroxide dropwise, and carrying out alcoholysis for 2h to obtain a polyvinyl alcohol solution. The mixed solution was poured onto a glass plate and put into an oven, and dried at 70 ℃ to form a 200 μm polyvinyl alcohol raw film. SEM shows that the section is smooth, the tensile strength is 92MPa, and the melting point is 221 ℃ when measured by DSC.
Comparative example 6
6.1 preparation of graphene oxide aqueous Dispersion
6.1.1 preparation of graphite oxide
Graphite oxide was prepared in the same manner as in example 1,
6.1.2 preparation of graphene oxide aqueous Dispersion
Ultrasonically dispersing 5g of graphite oxide in 995g of water for 30min to fully strip the graphite oxide to form brown yellow graphene oxide dispersion liquid with the mass concentration of 0.5%.
6.2 preparation of polyvinyl alcohol/graphene composite film
And sequentially adding 40g of graphene oxide dispersion liquid, 2g of dopamine and 50g of polyvinyl alcohol, keeping the temperature at 50 ℃ for 12h, adjusting the pH to 9, and changing the solution from bright yellow to dark black. The mixed solution was poured onto a glass plate and put into an oven, and dried at 70 ℃ to form a film. And preparing the 200 mu m polyvinyl alcohol/graphene nano composite film with the graphene mass fraction of 0.4%. SEM shows that the section is flat and ordered, the measured tensile strength is 108MPa, and the DSC measured melting point is 217 ℃.
Claims (6)
1. A preparation method of a high-performance polyvinyl alcohol/graphene composite film is characterized by comprising the following process steps: (1) preparing a graphene oxide dispersion liquid;
(2) preparing a polyvinyl acetate/graphene oxide solution by in-situ polymerization: according to the mass percentage, under the protection of nitrogen, sequentially adding 5-30% of monomer, 40-65% of solvent, 0.1-1% of initiator and 5-35% of graphene oxide dispersion liquid into a polymerization reaction system, heating to 30 ℃, carrying out heat preservation reaction for 3-6h, and then heating to 50 ℃ for reaction for 1-2 h; adding 0.1-1% of polymerization inhibitor, stopping the reaction to obtain polyvinyl acetate/graphene oxide solution;
(3) polyvinyl acetate/graphene oxide alcoholysis: dropwise adding 5-40% of sodium hydroxide methanol solution into 60-95% of polyvinyl acetate/graphene oxide solution by weight percentage, and carrying out alcoholysis for 1-5h to obtain polyvinyl alcohol/graphene oxide solution, wherein the mass percentage of sodium hydroxide in the sodium hydroxide methanol solution is 10-25%;
(4) preparation of polyvinyl alcohol/graphene rGO solution: according to the weight percentage, 99 to 99.9 percent of polyvinyl alcohol/graphene oxide solution and 0.1 to 1 percent of dopamine are sequentially added, the pH value is adjusted to be 8 to 10, the temperature is kept at 40 to 80 ℃ for 12 hours, and the solution is changed from bright yellow to dark black;
(5) preparing a polyvinyl alcohol/graphene rGO nano composite film: the mixed solution was poured onto a glass plate and placed in an oven and dried at 60-70 ℃ to form a black film of 100-.
2. The preparation method of the high-performance polyvinyl alcohol/graphene composite film according to claim 1, wherein the process for preparing the graphene oxide dispersion liquid comprises the following steps:
pouring 92mL of 98% concentrated sulfuric acid into 500mL of dry three-neck flask, cooling to 0 ℃, slowly adding 4g of graphite and 2g of sodium nitrate into the concentrated sulfuric acid, and mechanically stirring for 20 minutes to uniformly disperse the graphite; slowly adding 12g of potassium permanganate, continuously stirring for 3 hours, and controlling the reaction temperature to be below 10 ℃; transferring the three-neck flask into an oil bath kettle at 35 ℃, keeping the constant temperature and stirring for 3 hours, wherein the mixture is changed from black to grey brown; then slowly adding 200mL of deionized water, and keeping the temperature between 90 and 98 ℃; then quickly transferring the mixture into an oil bath pan at 90 ℃, maintaining for 15min, and keeping stirring; adding 560mL of deionized water into the system for dilution, wherein the color of the system becomes brown yellow, adding 30mL of 30% hydrogen peroxide, and stirring until the system becomes bright yellow; filtering with diluted hydrochloric acid until the sulfate ions in the product are removed, washing with water twice to remove metal ions in the product; putting the filter cake into a vacuum oven, and drying at 40 ℃ until the weight is constant; ultrasonically dispersing 0.5g of graphite oxide in 100g of methanol for 30min to fully strip the graphite oxide to form brown yellow graphene oxide dispersion liquid with the mass percentage of 0.5%.
3. The method for preparing a high-performance polyvinyl alcohol/graphene composite film according to claim 1, wherein the solvent is methanol, ethanol or isopropanol; the initiator is azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide or peroxydicarbonate; the polymerization inhibitor is hydroquinone or FeCl3。
4. The method for preparing a high performance polyvinyl alcohol/graphene composite film according to claim 1, wherein in the step (3), 80-95% of polyvinyl acetate/graphene oxide solution and 5-20% of sodium hydroxide methanol solution are calculated by weight percentage.
5. The method for preparing a high-performance polyvinyl alcohol/graphene composite film according to claim 1, wherein in the step (4), 0.5% -1% of dopamine by weight percentage is adjusted to pH 9, and the solution is kept at 40-60 ℃ for 12 hours to change from bright yellow to dark black.
6. The method for preparing a high-performance polyvinyl alcohol/graphene composite film according to claim 1, wherein the mixed solution is poured onto a glass plate in the step (5), and the glass plate is placed into an oven and dried at 70 ℃ to form a black film of 200 μm.
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