CN105237930A - Method for preparing modified graphene-polymethyl methacrylate composite film - Google Patents
Method for preparing modified graphene-polymethyl methacrylate composite film Download PDFInfo
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- CN105237930A CN105237930A CN201510789675.3A CN201510789675A CN105237930A CN 105237930 A CN105237930 A CN 105237930A CN 201510789675 A CN201510789675 A CN 201510789675A CN 105237930 A CN105237930 A CN 105237930A
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Abstract
The invention discloses a method for preparing a modified graphene-polymethyl methacrylate composite film. 7-amino-4-methylcoumarin is selected as a modifier, a chemical reduction agent such as hydrazine hydrate, vitamin C or glucose is selected. The method comprises the following steps: first preparing modified graphene, then preparing a dispersion solution of the modified graphene, adding the modified graphene dispersion solution into a polymethyl methacrylate solution to obtain a uniformly-dispersed modified graphene-polymethyl methacrylate mixed solution; and finally pouring the mixed solution into a utensil, drying the solution at 40 to 80 DEG C in atmosphere or a vacuum environment until the weight is constant to obtain the modified graphene/polymethyl methacrylate composite film. The mass fraction of the modified graphene is 0.1 to 15 percent. The method has advantages of simple preparation, moderate reaction conditions, easy control and the like.
Description
Technical field
The invention belongs to polymer composites preparing technical field, and in particular to a kind of method for preparing modified graphene-polymethyl methacrylate laminated film.
Background technology
Polymethyl methacrylate（PMMA）, commonly referred to as lucite, its chemical stability is good, and light transmittance is high, and solubility property and filming performance, mechanical performance are high, and safety non-toxic, price is low, and is easy to processing and forming, is widely used in the fields such as aviation, optical instrument, building.But polymethyl methacrylate matter itself is crisp easy to crack, and heat endurance is poor so that polymethyl methacrylate and its composite are all restricted in the application of numerous areas.
Graphene is a kind of new two-dimensional nano-carbon material, with excellent electrical property, mechanical performance and hot property etc., therefore, is added as nanofiller component in polymer, can be effectively improved the performances such as the electricity, machinery and heat of polymer.Therefore, this method is by study hotspot and emphasis as polymer based nanocomposites field.But, the inert state in surface of graphene, interaction between other media is weak, and there is stronger Van der Waals force between graphene sheet layer, cause its hydrophilic, lipophile all very poor, this causes its bad dispersibility in polymethylmethacrylate matrix and easy reunion, thus can not be well with polymer matrix bluk recombination, further research and application which greatly limits graphene-composite material of polymethyl methacrylate.
The dispersity of graphene can be produced to the performance of composite and significantly affected, therefore, and the dispersion problem of graphene is the key issue in prepared by graphene-composite material of polymethyl methacrylate.
The content of the invention
For deficiencies of the prior art, the present invention is modified graphene using modifying agent, so as to improving and improve its dispersiveness in water and organic solvent, and then provide and a kind of prepare that simple, reaction condition is gentle, be easily manipulated system and the finely dispersed method for preparing modified graphene-polymethyl methacrylate laminated film.
To achieve these goals, the technical solution adopted by the present invention is as follows：
The preparation method of a kind of modified graphene-polymethyl methacrylate laminated film, it is characterised in that comprise the following steps：
1）The preparation of modified graphene：First that graphene oxide is scattered in deionized water, the 0.5-24h of ultrasonic vibration stirring at normal temperatures obtains graphene oxide-aqueous dispersions that concentration is 0.01-3.0mg/mL；7- amino -4- methylcoumarins are added in the graphene oxide-aqueous dispersions again, 0.1-12h is stirred at 20-50 DEG C；Then alkaline solution is added, 0.1-12h is stirred, and adjust pH value to 9-10；Chemical reducing agent is added, 12-100h is reacted at 60-100 DEG C and obtains being modified mixed liquor；The modification mixed liquor suction filtration is obtained into solid matter, then with ethanol and deionized water wash described solid matter to neutrality successively；It is placed under air or vacuum environment, is dried in 40-80 DEG C to constant weight, that is, obtain modified graphene.
2）Prepare modified graphene-tetrahydrofuran dispersion liquid：By step 1）Obtained modified graphene is added in tetrahydrofuran, stirs 0.5-12h, then ultrasonic vibration 0.5-24h, obtains modified graphene-tetrahydrofuran dispersion liquid that concentration is 0.01-2.0mg/mL.
3）Prepare film：Polymethyl methacrylate is dissolved in tetrahydrofuran, the polymethyl methacrylate solution that mass concentration is 1%-10% is obtained；By step 2）Obtained modified graphene-tetrahydrofuran dispersion liquid is added in above-mentioned polymethyl methacrylate solution, stirs 0.1-8h, then uses ultrasonic vibration 0.3-24h, obtains finely dispersed modified graphene-polymethyl methacrylate mixed solution.Above-mentioned graphene-polymethyl methacrylate mixed solution is poured into vessel, under air or vacuum environment, in being dried at 40-80 DEG C to constant weight, modified graphene-polymethyl methacrylate laminated film is obtained；Wherein, the mass fraction of modified graphene is 0.1%-15%.
Further, step 1）Described in alkaline solution be ammonia spirit that sodium hydroxide solution or mass fraction that concentration is 0.1-2.0mol/L are 25%-28%.
Further, step 1）Described in graphene oxide, 7- amino -4- methylcoumarins, chemical reducing agent mass ratio be 1：1-40：1-40.
Further, step 1）Described in chemical reducing agent be hydrazine hydrate, vitamin C or glucose.
Compared with prior art, the present invention has the advantages that：
1st, the polymeric matrix that the present invention chooses is polymethyl methacrylate（PMMA）, can be by buying commercially available product or synthetically prepared acquisition, safety non-toxic, chemical stability is good.Solubility property is good, and filming performance is good, is conducive to processing to prepare.
2nd, the modifying agent that the present invention chooses is 7- amino -4- methylcoumarins, its molecule contains amino, ester group and conjugated structure etc., the interaction such as hydrogen bond and e-e can occur with the oxy radical such as the carbonyl and carboxyl in graphene oxide, also contain amino groups in modified graphene obtained from by being reduced, interaction of hydrogen bond can be produced with the ester group in polymethyl methacrylate molecule, be conducive to improving and improve dispersiveness of the graphene in polymethyl methacrylate, strengthen interface binding power.
3rd, the modifying agent that the present invention chooses is 7- amino -4- methylcoumarins, can be by buying commercially available product or synthetically prepared acquisition, and material is easily obtained, and solubility property is good, and chemical stability is good, low cost.
4th, the chemical reducing agent that the present invention chooses, can be by buying commercially available product or synthetically prepared acquisition, and material is easily obtained, and solubility property is good, and chemical stability is good, cheap.
5th, the preparation method of a kind of modified graphene/polymethyl methacrylate laminated film of the present invention, the quality of polymethyl methacrylate hot property etc. can be adjusted by controlling the addition of modified graphene, the laminated film prepared is uniformly dispersed, and performance is stable.
6th, the preparation method is simple, mild condition, it is easy to operation and control.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Polymethyl methacrylate used in the present invention（PMMA）, can be by buying commercially available product or synthetically prepared acquisition.Its solubility property is good, is soluble in the organic solvents such as tetrahydrofuran, and filming performance is good, is easy to processing to prepare.
The present invention utilizes modifying agent, i.e. 7- amino -4- methylcoumarins, comes grapheme modified, so as to improve dispersiveness of the graphene in water and organic solvent.Wherein, modifying agent, i.e. 7- amino -4- methylcoumarins, Chinese nickname are coumarin 1 20, and its molecular structural formula is as follows：
It can be by buying commercially available product or synthetically prepared acquisition, and chemical stability is good, and solubility property is good.
Raw material of the present invention --- graphene oxide can be by buying commercially available product or synthetically prepared obtaining.
First, a kind of method for preparing modified graphene-polymethyl methacrylate laminated film, comprise the following steps：
1）The preparation of modified graphene：First that graphene oxide is scattered in deionized water, the 0.5-24h of ultrasonic vibration stirring at normal temperatures obtains graphene oxide-aqueous dispersions that concentration is 0.01-3.0mg/mL；7- amino -4- methylcoumarins are added in the graphene oxide-aqueous dispersions again, 0.1-12h is stirred at 20-50 DEG C；Then alkaline solution is added, 0.1-12h is stirred, and adjust pH value to 9-10；Chemical reducing agent is added, 12-100h is reacted at 60-100 DEG C and obtains being modified mixed liquor；The modification mixed liquor suction filtration is obtained into solid matter, then with ethanol and deionized water wash described solid matter to neutrality successively；It is placed under air or vacuum environment, is dried in 40-80 DEG C to constant weight, that is, obtain modified graphene.
This step operation is to prepare modified graphene using the method for addition modifying agent and electronation graphene oxide.In the graphene oxide, 7- amino -4- methylcoumarins, chemical reducing agent, 7- amino -4- methylcoumarins, chemical reducing agent should be excessively used, the reaction modifying agent and chemical reducing agent that excess is removed by washing operation.
2）By step 1）Obtained modified graphene is added in tetrahydrofuran, stirs 0.5-12h, then ultrasonic vibration 0.5-24h, obtains modified graphene-tetrahydrofuran dispersion liquid that concentration is 0.01-2.0mg/mL.
3）Prepare film：Prepare film：Polymethyl methacrylate is dissolved in tetrahydrofuran, the polymethyl methacrylate solution that mass concentration is 1%-10% is obtained；By step 2）Obtained modified graphene-tetrahydrofuran dispersion liquid is added in above-mentioned polymethyl methacrylate solution, stirs 0.1-8h, then uses ultrasonic vibration 0.3-24h, obtains finely dispersed modified graphene-polymethyl methacrylate mixed solution；Above-mentioned graphene-polymethyl methacrylate mixed solution is poured into vessel, under air or vacuum environment, in being dried at 40-80 DEG C to constant weight, modified graphene-polymethyl methacrylate laminated film is obtained；Wherein, the mass fraction of modified graphene is 0.1%-15%.
This step operation is that modified graphene-polymethyl methacrylate laminated film is prepared using solution blended process.
Wherein, step 1）Described in alkaline solution be ammonia spirit that sodium hydroxide solution or mass fraction that concentration is 0.1-2.0mol/L are 25%-28%；Described chemical reducing agent is hydrazine hydrate, vitamin C or glucose.
Step 1）Described in graphene oxide, 7- amino -4- methylcoumarins, chemical reducing agent mass ratio be 1：1-40：1-40.The ratio is a kind of prioritization scheme, and the effect of preparation is best.
Modifying agent of the present invention selects 7- amino -4- methylcoumarins, and the present invention selects hydrazine hydrate, the chemical reducing agent such as vitamin C or glucose；Modified graphene is first prepared, then prepares the dispersion liquid of modified graphene, then the dispersion liquid of modified graphene is added in polymethyl methacrylate solution, finely dispersed modified graphene-polymethyl methacrylate mixed solution is obtained；Finally above-mentioned mixed solution is poured into vessel, under air or vacuum environment, is dried in 40-80 DEG C to constant weight, obtains modified graphene-polymethyl methacrylate laminated film.Wherein, the mass fraction of modified graphene is 0.1%-15%.
2nd, embodiment
Embodiment 1
Adopt and prepare with the following method modified graphene-polymethyl methacrylate laminated film：
1）The preparation of modified graphene：First that graphene oxide is scattered in deionized water, the 6h of ultrasonic vibration stirring at normal temperatures obtains graphene oxide-aqueous dispersions that concentration is 0.05mg/mL；
7- amino -4- methylcoumarins are added in the graphene oxide-aqueous dispersions again, 0.5h is stirred at 25 DEG C；Then the sodium hydrate aqueous solution that concentration is 0.5mol/L is added, 2h is stirred, and adjust pH value for 9-10；Chemical reducing agent hydrazine hydrate is added, 30h is reacted at 95 DEG C and obtains being modified mixed liquor；
The modification mixed liquor suction filtration is obtained into solid matter, then with ethanol and deionized water wash described solid matter to neutrality successively；It is placed under atmospheric environment, is dried in 60 DEG C to constant weight, that is, obtain modified graphene；
Described graphene oxide, 7- amino -4- methylcoumarins, the mass ratio of hydrazine hydrate are 1：20：4；
2）Prepare modified graphene-tetrahydrofuran dispersion liquid：By step 1）Obtained modified graphene is added in tetrahydrofuran as solute, stirs 1h, then ultrasonic vibration 16h, obtains modified graphene-tetrahydrofuran dispersion liquid that concentration is 0.05mg/mL；
3）Prepare film：Polymethyl methacrylate is dissolved in tetrahydrofuran, the polymethyl methacrylate solution that mass concentration is 5% is obtained；By step 2）Obtained modified graphene-tetrahydrofuran dispersion liquid is added in above-mentioned polymethyl methacrylate solution, stirs 2h, then uses ultrasonic vibration 12h, obtains finely dispersed modified graphene-polymethyl methacrylate mixed solution；
Above-mentioned graphene-polymethyl methacrylate mixed solution is poured into vessel, under atmospheric environment, in being dried at 65 DEG C to constant weight, modified graphene-polymethyl methacrylate laminated film is obtained；Wherein, the mass fraction of modified graphene is 0.3%.
Embodiment 2
Adopt and prepare with the following method modified graphene-polymethyl methacrylate laminated film：
1）The preparation of modified graphene：First that graphene oxide is scattered in deionized water, the 8h of ultrasonic vibration stirring at normal temperatures obtains graphene oxide-aqueous dispersions that concentration is 0.1mg/mL；
7- amino -4- methylcoumarins are added in the graphene oxide-aqueous dispersions again, 1h is stirred at 30 DEG C；Then the sodium hydrate aqueous solution that concentration is 1.0mol/L is added, 1h is stirred, and adjust pH value for 9-10；Chemical reducing agent vitamin C is added, 24h is reacted at 90 DEG C and obtains being modified mixed liquor；
The modification mixed liquor suction filtration is obtained into solid matter, then with ethanol and deionized water wash described solid matter to neutrality successively；It is placed under atmospheric environment, is dried in 55 DEG C to constant weight, that is, obtain modified graphene；
Described graphene oxide, 7- amino -4- methylcoumarins, ascorbic mass ratio are 1：10：10；
2）Prepare modified graphene-tetrahydrofuran dispersion liquid：By step 1）Obtained modified graphene is added in tetrahydrofuran as solute, stirs 2h, then ultrasonic vibration 10h, obtains modified graphene-tetrahydrofuran dispersion liquid that concentration is 0.1mg/mL；
3）Prepare film：Polymethyl methacrylate is dissolved in the organic solvents such as tetrahydrofuran, the polymethyl methacrylate solution that mass concentration is 5% is obtained；By step 2）Obtained modified graphene-tetrahydrofuran dispersion liquid is added in above-mentioned polymethyl methacrylate solution, stirs 4h, then uses ultrasonic vibration 18h, obtains finely dispersed modified graphene-polymethyl methacrylate mixed solution；
Above-mentioned graphene-polymethyl methacrylate mixed solution is poured into vessel, under atmospheric environment, in being dried at 55 DEG C to constant weight, modified graphene-polymethyl methacrylate laminated film is obtained；Wherein, the mass fraction of modified graphene is 0.7%.
Embodiment 3
Adopt and prepare with the following method modified graphene-polymethyl methacrylate laminated film：
1）The preparation of modified graphene：First that graphene oxide is scattered in deionized water, the 12h of ultrasonic vibration stirring at normal temperatures obtains graphene oxide-aqueous dispersions that concentration is 0.5mg/mL；
7- amino -4- methylcoumarins are added in the graphene oxide-aqueous dispersions again, 2h is stirred at 35 DEG C；Then the ammonia spirit that mass fraction is 25%-28% is added, 0.5h is stirred, and adjust pH value for 9-10；Chemical reducing agent glucose is added, 16h is reacted at 85 DEG C and obtains being modified mixed liquor.
The modification mixed liquor suction filtration is obtained into solid matter, then with ethanol and deionized water wash described solid matter to neutrality successively；It is placed under atmospheric environment, is dried in 50 DEG C to constant weight, that is, obtain modified graphene.
Described graphene oxide, 7- amino -4- methylcoumarins, the mass ratio of glucose are 1：4：15；
2）Prepare modified graphene-tetrahydrofuran dispersion liquid：By step 1）Obtained modified graphene is added in tetrahydrofuran as solute, stirs 3h, then ultrasonic vibration 8h, obtains modified graphene-tetrahydrofuran dispersion liquid that concentration is 0.5mg/mL；
3）Prepare film：Polymethyl methacrylate is dissolved in tetrahydrofuran, the polymethyl methacrylate solution that mass concentration is 7% is obtained；By step 2）Obtained modified graphene-tetrahydrofuran dispersion liquid is added in above-mentioned polymethyl methacrylate solution, stirs 6h, then uses ultrasonic vibration 15h, obtains finely dispersed modified graphene-polymethyl methacrylate mixed solution；
Above-mentioned graphene-polymethyl methacrylate mixed solution is poured into vessel, under atmospheric environment, in being dried at 50 DEG C to constant weight, modified graphene-polymethyl methacrylate laminated film is obtained；Wherein, the mass fraction of modified graphene is 1.5%.
Postmenstruation experiment proves that the thermal weight loss temperature of modified graphene-polymethyl methacrylate laminated film of different quality containing is different, refers to table 1：
The thermal weight loss temperature of the modified graphene of the different quality containing of table 1-polymethyl methacrylate laminated film
The above embodiment of the present invention is only example to illustrate the invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, other various forms of changes and variation can also be made on the basis of the above description.Here all embodiments can not be exhaustive.It is every to belong to obvious change that technical scheme amplifies out or change row still in protection scope of the present invention.
Claims (4)
1. the preparation method of a kind of modified graphene-polymethyl methacrylate laminated film, it is characterised in that comprise the following steps：
1）The preparation of modified graphene：First that graphene oxide is scattered in deionized water, the 0.5-24h of ultrasonic vibration stirring at normal temperatures obtains graphene oxide-aqueous dispersions that concentration is 0.01-3.0mg/mL；
7- amino -4- methylcoumarins are added in the graphene oxide-aqueous dispersions again, 0.1-12h is stirred at 20-50 DEG C；Then alkaline solution is added, 0.1-12h is stirred, and adjust pH value to 9-10；Chemical reducing agent is added, 12-100h is reacted at 60-100 DEG C and obtains being modified mixed liquor；
The modification mixed liquor suction filtration is obtained into solid matter, then with ethanol and deionized water wash described solid matter to neutrality successively；It is placed under air or vacuum environment, is dried in 40-80 DEG C to constant weight, that is, obtain modified graphene；
2）Prepare modified graphene-tetrahydrofuran dispersion liquid：By step 1）Obtained modified graphene is added in tetrahydrofuran, stirs 0.5-12h, then ultrasonic vibration 0.5-24h, obtains modified graphene-tetrahydrofuran dispersion liquid that concentration is 0.01-2.0mg/mL；
3）Prepare film：Polymethyl methacrylate is dissolved in tetrahydrofuran, the polymethyl methacrylate solution that mass concentration is 1%-10% is obtained；By step 2）Obtained modified graphene-tetrahydrofuran dispersion liquid is added in above-mentioned polymethyl methacrylate solution, stirs 0.1-8h, then uses ultrasonic vibration 0.3-24h, obtains finely dispersed modified graphene-polymethyl methacrylate mixed solution；
Above-mentioned graphene-polymethyl methacrylate mixed solution is poured into vessel, under air or vacuum environment, in being dried at 40-80 DEG C to constant weight, modified graphene-polymethyl methacrylate laminated film is obtained；Wherein, the mass fraction of modified graphene is 0.1%-15%.
2. the method according to claim 1 for preparing modified graphene-polymethyl methacrylate laminated film, it is characterised in that step 1）Described in alkaline solution be ammonia spirit that sodium hydroxide solution or mass fraction that concentration is 0.1-2.0mol/L are 25%-28%.
3. the method according to claim 1 for preparing modified graphene-polymethyl methacrylate laminated film, it is characterised in that step 1）Described in graphene oxide, 7- amino -4- methylcoumarins, chemical reducing agent mass ratio be 1：1-40：1-40.
4. the method for preparing modified graphene-polymethyl methacrylate laminated film according to claim 1 or 2 or 3, it is characterised in that step 1）Described in chemical reducing agent be hydrazine hydrate, vitamin C or glucose.
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Application publication date: 20160113 |