CN102516479B - Graphene-based nano particle composite hydrogel and preparation method thereof - Google Patents
Graphene-based nano particle composite hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses graphene-based nano particle composite hydrogel and a preparation method thereof. The nano particle composite hydrogel consists of graphene-based nano particles, a water-soluble polymer and water, wherein the water-soluble polymer is formed by polymerizing water-soluble monomers containing carbon-carbon double bonds under the initiation of peroxide groups on the graphene-based nano particles, and the water-soluble polymer is cross-linked by using the graphene-based nano particles as cross-linking centers. The preparation method for the graphene-based nano particle composite hydrogel comprises a pre-irradiation peroxidation step and a thermal initiated polymerization step. The graphene-based nano particle composite hydrogel has excellent mechanical properties, namely the tensile strength is hundreds of kPa to over 1MPa, and the elongation at break is more than 2,000 percent. The mechanical properties of the hydrogel can be conveniently adjusted by controlling the preparation technology to meet the requirements of different application occasions. The hydrogel can be applied in the fields of biology, medicine and the like.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of graphene-based nano particle composite hydrogel and preparation method thereof.
Background technology
Macromolecule hydrogel is study hotspot as the soft wet stock of a kind of " coupling hardness with softness " in decades recently always.The property that hydrogel is different from other rigid materials makes it all demonstrate good application prospect at industry, agricultural, biology and Material Field.But the low poor toughness of most conventional gel intensity has limited it to a certain extent as the practical application of functional material in each field.Nano particle composite hydrogel is that the particles of inorganic material with nano-scale is scattered in the matrix material that forms in hydrogel, it combines the rigidity of nano material, the stability of size and the soft wet performance of hydrogel, obviously improves the mechanical property of hydrogel and thermostability etc.
successfully introduce inorganic nano-particle in polymeric system, and preparation high mechanical strength hydrogel, the most representative research be the people such as Haraguchi with the inorganic clay nanoparticle as cross-linking set, under the effect of initiator and aided initiating, make monomer NIPA (NIPAAm) at the nanoparticle surface initiated polymerization, prepare nano-composite gel (NC gel) " the Nanocomposite hydrogels:a unique organic-inorganic network structure with extraordinary mechanical with high mechanical strength, optical, and swelling/deswelling properties. " (Advanced Materials, 2002.14 (16): p.1120-1124.).This gel interacts by polymer long-chain and clay particle sub-surface, guarantee that macromolecular chain is that surface from clay layer begins to cause, and the even distribution due to the clay particle in system, make the macromolecular chain that makes in this way distribute also relatively even, structure is relatively regular, has mechanical property preferably.
Graphene is a kind of two-dimensional nano material, has very excellent mechanics and electric property.In recent years, the report about graphene-based nano composite material and plural gel has a lot.2008, the scientific research personnel of Princeton university and Northwest University has also reported the correlative study of graphene-based nano composite material, and they are introduced in the polymeric systems such as polyacrylonitrile, polymethylmethacrylate by the functional graphene nanometer sheet after with a small amount of modification.Studies show that, graphene nanometer sheet can be dispersed in polymeric system, these matrix materials show good mechanical property and thermostability " Functionalized graphene sheets for polymer nanocomposites " (Nature Nanotechnology, 2008.3:p.327-331.).Shi etc. have obtained composite aquogel " A pH-sensitive graphene oxide composite hydrogel. " (Chemical Communications after graphene oxide and PVA solution are mixed, 2010,46 (14): p.2376-2378.).Liu etc. are by carrying out freeze-thaw after graphene oxide and the mixing of PVA solution, the mechanical property of the composite aquogel that makes " High strength graphene oxide/polyvinyl alcohol composite hydrogels " (the Journal of Materials Chemistry that is improved, 2011,21 (28): p.10399-10406.).
Only have the physical actions such as hydrogen bond between nanoparticle in these composite aquogels (comprising Graphene or graphene oxide) and polymkeric substance, and there is no strong chemical b `.Therefore, these nanoparticles to add the help to the performance (especially mechanical property) that improves polymer materials be not very large.
If can introduce covalent chemical bond between graphene-based nano particle and polymer chain, the performance of gained graphene based nano composite hydrogel will be very significantly improved undoubtedly.But at present about the report of this gellike also seldom, the preparation method who adopts in existing a small amount of report is generally all comparatively complicated, inconvenient practical application.As people such as Wu with NIPAAm and Acrylic Acid Monomer solution and initiated polymerization again after graphene oxide mixes, again further with a kind of linking agent with polymkeric substance and graphene oxide crosslinked " A one-step strategy for thermal-and pH-responsive graphene oxide interpenetrating polymer hydrogel networks " (Journal of Materials Chemistry, 2011,21 (12): p.4095-4097.).
the present inventor Wang high-lightness etc. with monodispersed polymer microsphere as original material, it is carried out gamma-radiation radiation peroxidation, then take cause the water-soluble acrylic monomer polymerization as the initiation center, obtained having " the macromolecular microspheres hydrogel " of higher compression intensity (referring to document Huang T, Xu HG, Jiao KX, Zhu LP, Brown H R, Wang H L.A Novel hydrogel with high mechanical strength:a macromolecular microsphere composite hydrogel.Adv.Mater.2007, 19 (12): p.1622-1626.).On this basis, Wang Huiliang etc. have prepared the hydrogel (publication number: CN 101397347A) with high mechanical strength take the snperoxiaized surfactant micelle of radiation as causing and crosslinked center; Also take the snperoxiaized water-soluble polymer chain of radiation as causing and crosslinked center has prepared high intensity hydrogel (Chinese patent: ZL 2,007 10122579.9).
Also do not prepare at present the report of high-strength gel take Graphene as initiation and crosslinked center.
Summary of the invention
The present invention aims to provide a kind of graphene-based nano particle composite hydrogel and preparation method thereof, to solve in prior art nano-composite gel adding due to initiator and linking agent, may exist some compositions residual, when being applied to biological field, may there be potential threat and when being swelling to high-moisture or reaching swelling equilibrium, the technical problem that its mechanical property can be a greater impact.
To achieve these goals, according to an aspect of the present invention, provide a kind of graphene-based nano particle composite hydrogel.This graphene-based nano particle composite hydrogel is comprised of graphene-based nano particle, water-soluble polymers and water, wherein, water-soluble polymers causes by the peroxy-radical on graphene-based nano particle the polymerisation that contains carbon-to-carbon double bond and forms, and crosslinked as crosslinked center take graphene-based nano particle.
Further, water-soluble monomer is selected from the carboxylic-acid monomer, sulphonic acids monomer, and one or more in the group that forms of the water-soluble monomer of non-ionic type.
Further, the carboxylic-acid monomer is selected from one or both in vinylformic acid, methacrylic acid; The sulphonic acids monomer is the 2-acrylamide-2-methyl propane sulfonic; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylamide and derivative thereof, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, NVP form.
Further, acrylamide derivative is selected from Methacrylamide, N-n-propyl acrylamide, NIPA, N, one or more in the group that N-divinyl acrylamide, N hydroxymethyl acrylamide form.
Further, graphene-based nano particle is stannic oxide/graphene nano particle and/or graphene nano particle.
A kind of preparation method of graphene-based nano particle composite hydrogel also is provided according to another aspect of the present invention.This preparation method comprises the following steps: 1) pre-irradiation peroxidation step, in oxygen atmosphere, adopt high-energy radiation source irradiation graphene-based nano particle homogeneous phase aqueous solution, and make the graphene-based nano particle peroxidation; 2) thermal-initiated polymerization step; to mix with the water-soluble mono liquid solution that contains carbon-to-carbon double bond through the graphene-based nano particle aqueous solution of pre-irradiation peroxidation step; then react under protection of inert gas, namely get graphene-based nano particle composite hydrogel.
Further, the quality percentage composition of the graphene-based nano particle in the graphene-based nano particle homogeneous phase aqueous solution is 0.01%～3%, and the concentration of water-soluble monomer is 1～6mol/L.
Further, the graphene-based nano particle aqueous solution of process pre-irradiation peroxidation step is 20 ℃～80 ℃ with the temperature of reaction of the mixing solutions of the water-soluble mono liquid solution that contains carbon-to-carbon double bond, and the reaction times is 1～48 hour.
Further, in the thermal-initiated polymerization step, temperature of reaction is 35 ℃～55 ℃.
Further, in the pre-irradiation peroxidation step, adopting radiation dose rate is the high-energy radiation source of 0.001-0.4kGy/min, and irradiation is 1～24 hour under the irradiation temperature of 0～100 ℃.
Further, the high-energy radiation source is for producing the rumbatron of gamma-ray cobalt source or generation high-power electron beam.
Further, water-soluble monomer is selected from the carboxylic-acid monomer, sulphonic acids monomer, one or more in the group that the water-soluble monomer of non-ionic type forms.
Further, the carboxylic-acid monomer is selected from one or both in vinylformic acid, methacrylic acid; The sulphonic acids monomer is the 2-acrylamide-2-methyl propane sulfonic; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylamide and derivative thereof, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, NVP form.
Further, acrylamide derivative is selected from Methacrylamide, N-n-propyl acrylamide, NIPA, N, one or more in the group that N-divinyl acrylamide, N hydroxymethyl acrylamide form.
Further, graphene-based nano particle is stannic oxide/graphene nano particle and/or graphene nano particle.
Further, rare gas element is nitrogen or argon gas.
Graphene-based nano particle composite hydrogel of the present invention only is comprised of graphene-based nano particle, soluble polymer and water three parts, does not have the residual of other compositions, is down to the potential threat that is applied to the fields such as biology minimum; And this graphene-based nano particle composite hydrogel still can keep mechanical property preferably when being swelling to high-moisture or reaching swelling equilibrium.Adopt the preparation method of graphene-based nano particle composite hydrogel of the present invention, only need the graphene-based nano particle aqueous solution is processed through pre-irradiation, mode through pre-irradiation, thermal initiation can be reacted with monomer solution, need not additionally to add any initiator and linking agent, operating process and the reaction process of chemical initiated polymerization method have been simplified to the full extent, and two processes of pre-irradiation and thermal initiation do not interfere with each other, and can carry out respectively under relatively independent process.
Description of drawings
Figure of description is used to provide a further understanding of the present invention, consists of a part of the present invention, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not consist of improper restriction of the present invention.In the accompanying drawings:
Fig. 1 shows pre-irradiation peroxidation process schematic diagram; And
Fig. 2 shows polymerization crosslinking hydrogel structure schematic diagram.
Embodiment
Need to prove, in the situation that do not conflict, embodiment and the feature in embodiment in the present invention can make up mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
A kind of typical embodiment according to the present invention, graphene-based nano particle composite hydrogel.This graphene-based nano particle composite hydrogel is comprised of graphene-based nano particle, water-soluble polymers and water, wherein, water-soluble polymers causes by the peroxy-radical on graphene-based nano particle the polymerisation that contains carbon-to-carbon double bond and forms, and crosslinked as crosslinked center take graphene-based nano particle.Because this graphene-based nano particle composite hydrogel is only generated by graphene-based nano particle, soluble and monomeric and water three partial reactions, there be not the residual of other compositions, be down to the potential threat that is applied to the fields such as biology minimum; And this graphene-based nano particle composite hydrogel still can keep mechanical property preferably when being swelling to high-moisture or reaching swelling equilibrium.
As long as above-mentioned water-soluble monomer contains carbon-to-carbon double bond, preferably, water-soluble monomer is selected from the carboxylic-acid monomer, sulphonic acids monomer, and one or more in the group that forms of the water-soluble monomer of non-ionic type.Further preferably, the carboxylic-acid monomer is selected from one or both in vinylformic acid, methacrylic acid; The sulphonic acids monomer is the 2-acrylamide-2-methyl propane sulfonic; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylamide and derivative thereof, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, NVP form.Acrylamide derivative is selected from Methacrylamide, N-n-propyl acrylamide, NIPA, N, one or more in the group that N-divinyl acrylamide, N hydroxymethyl acrylamide form.
Preferably, graphene-based nano particle is stannic oxide/graphene nano particle and/or graphene nano particle.
A kind of preparation method of above-mentioned nano particle composite hydrogel is provided according to a further aspect in the invention.This preparation method comprises the following steps: 1) pre-irradiation peroxidation step, in oxygen atmosphere, adopt high-energy radiation source irradiation graphene-based nano particle homogeneous phase aqueous solution, and make the graphene-based nano particle peroxidation; 2) thermal-initiated polymerization step; to mix with the water-soluble mono liquid solution that contains carbon-to-carbon double bond through the graphene-based nano particle aqueous solution of pre-irradiation peroxidation step; then react under protection of inert gas, namely get graphene-based nano particle composite hydrogel.
A kind of preparation method of above-mentioned graphene-based nano particle composite hydrogel is provided according to a further aspect in the invention.
A kind of typical embodiment according to the present invention, the preparation method of graphene-based nano particle composite hydrogel comprises the following steps: 1) pre-irradiation peroxidation step, in oxygen atmosphere, employing high-energy radiation source irradiation graphene-based nano particle homogeneous phase aqueous solution makes the graphene-based nano particle peroxidation; 2) thermal-initiated polymerization step after mixing with the water-soluble monomer that contains carbon-to-carbon double bond through the aqueous solution of pre-irradiation peroxidation step, is then reacted under protection of inert gas, namely gets graphene-based nano particle composite hydrogel.Fig. 1 is pre-irradiation peroxidation process schematic diagram, under the energetic ray irradiation, when having oxygen to exist, can connect a large amount of peroxy-radicals on graphene sheet layer.Fig. 2 shows polymerization crosslinking hydrogel structure schematic diagram, and snperoxiaized graphene-based system is evenly mixed with water-soluble monomer, and at a certain temperature, the peroxidation Graphene can decomposite a large amount of free radicals, thus the trigger monomer polymerization.On this basis, macromolecular chain obtains the good hydrogel of mechanical property take Graphene as crosslinked central reaction.Adopt the preparation method of graphene-based nano particle composite hydrogel of the present invention, only need the graphene-based nano particle aqueous solution is processed through pre-irradiation, mode through pre-irradiation, thermal initiation can be reacted with monomer solution, need not additionally to add any initiator and linking agent, operating process and the reaction process of chemical initiated polymerization method have been simplified to the full extent, and two processes of pre-irradiation and thermal initiation do not interfere with each other, and can carry out respectively under relatively independent process.
Preferably, the quality percentage composition of the graphene-based nano particle in the graphene-based nano particle homogeneous phase aqueous solution is 0.01%～3%, and the concentration of water-soluble monomer is 1～6mol/L.In the thermal-initiated polymerization step, the graphene-based nano particle aqueous solution of process pre-irradiation peroxidation step is 20 ℃～80 ℃ with the temperature of reaction of the mixing solutions of the water-soluble mono liquid solution that contains carbon-to-carbon double bond, and the reaction times is 1～48 hour.Preferably, temperature of reaction is preferably 35 ℃～55 ℃, in this temperature range, can more easily control polymerization velocity and the polymer chain length of reaction system, more benefits the formation of gel network.
A kind of typical embodiment according to the present invention, as long as it is identical with the logical oxygen time that the radiation parameter in the pre-irradiation peroxidation step can guarantee irradiation, can adopt radiation dose rate is the high-energy radiation source of 0.001-0.4kGy/min, and irradiation is 1～24 hour under the irradiation temperature of 0～100 ℃.Preferably, in the pre-irradiation peroxidation step, irradiation temperature is 20～50 ℃, and radiation dose rate is 0.01-0.4kGy/min, and this condition irradiation efficiency is relatively the highest.A kind of typical embodiment according to the present invention, irradiation is 1～12 hour under the irradiation temperature of 20～50 ℃, along with the increase of time, can make graphene sheet layer connect more peroxy-radical, and the thermal initiation process is carried out better.And irradiated oxidising process and thermal initiation process needn't strictly be carried out continuously, can preserve irradiating soln under cold condition, and instant getting simplified preparation process to the full extent.Preferably, the high-energy radiation source is the rumbatron that produces gamma-ray cobalt source or produce high-power electron beam, implements easily and efficiently irradiation.Rare gas element adopts nitrogen or argon gas, removes oxygen in solution for effective, and then promotes the activity of peroxy radical, more is conducive to polyreaction and carries out.
As long as above-mentioned water-soluble monomer contains carbon-to-carbon double bond, preferably, water-soluble monomer is selected from the carboxylic-acid monomer, sulphonic acids monomer, and one or more in the group that forms of the water-soluble monomer of non-ionic type.Further preferably, the carboxylic-acid monomer is selected from one or both in vinylformic acid, methacrylic acid; The sulphonic acids monomer is the 2-acrylamide-2-methyl propane sulfonic; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylamide and derivative thereof, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, NVP form.Acrylamide derivative is selected from Methacrylamide, N-n-propyl acrylamide, NIPA, N, one or more in the group that N-divinyl acrylamide, N hydroxymethyl acrylamide form.Preferably, graphene-based nano particle is stannic oxide/graphene nano particle and/or graphene nano particle.
Further illustrate beneficial effect of the present invention below in conjunction with specific embodiment.
Embodiment 1
Finely dispersed 0.1wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 4 hours under oxygen atmosphere, irradiation temperature is 100 ℃, radiation dose rate is 0.2kGy/min, pre-irradiation measures irradiating soln 10mL after finishing, it is mixed with acrylamide monomer (2.843g), and the concentration of gained acrylamide is 4mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 80 ℃, reacts namely to get product after 24 hours.At ambient temperature, control crossbeam speed 40mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.2MPa, and elongation at break is that the compressive strength of 600%, 95% compression ratio is 2.50MPa.
Embodiment 2
Finely dispersed 0.15wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 10 hours under oxygen atmosphere, irradiation temperature is 40 ℃, radiation dose rate is 0.25kGy/min, pre-irradiation evenly mixes each 5mL of itself and acrylic acid aqueous solution after finishing, wherein acrylic acid concentration is 3mol/L, letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 20 minutes, temperature of reaction is 45 ℃, react namely to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 70%, and its tensile break strength is 0.3MPa, and elongation at break is that the compressive strength of 2400%, 95% compression ratio is 20.55MPa.
Embodiment 3
At first, the 0.3g graphite oxide is dispersed in after supersound process in 100g distilled water, obtains the homogeneous dispersion liquid, then place it under oxygen atmosphere and to adopt cobalt-60 radiosterilize 10 hours, wherein, radiation dose rate is 0.4kGy/min, and irradiation temperature is 50 ℃.Pre-irradiation measures irradiating soln 10mL after finishing, it is mixed with acrylamide monomer (2.843g), and the concentration of gained acrylamide is 4mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 20 minutes, temperature of reaction is 45 ℃, reacts namely to get product after 48 hours.At ambient temperature, control crossbeam speed 40mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.75MPa, and elongation at break is that the compressive strength of 3500%, 95% compression ratio is 29.30MPa.
Embodiment 4
The present embodiment except following characteristics with embodiment 3: to add the graphite oxide amount be 0.15g in institute, and the pre-irradiation temperature is 40 ℃. products obtained therefrom is controlled crossbeam speed 40mm/min at ambient temperature, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.35MPa, and elongation at break is that the compressive strength of 4100%, 95% compression ratio is 22.75MPa.
Comparative Examples 1
Provide Comparative Examples 1 for embodiment 3, this Comparative Examples adopts traditional irradiance method to prepare hydrogel.At first, the 0.3g graphite oxide is dispersed in after supersound process in 100g distilled water, obtains the homogeneous dispersion liquid.Then graphite oxide solution 10mL is evenly mixed with the 2.843g acrylamide monomer, the concentration of gained acrylamide is 4mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions after 20 minutes.Adopt cobalt-60 radiosterilize namely to get product after 4 hours, wherein, radiation dose rate is 0.4kGy/min, and irradiation temperature is 50 ℃.At ambient temperature, control crossbeam speed 40mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.24MPa, and elongation at break is that the compressive strength of 800%, 95% compression ratio is 11.60MPa.
Comparative Examples is analyzed
Can find out by embodiment 3 and Comparative Examples 1: under same experiment condition, adopt the tensile break strength of the hydrogel that traditional radiation method prepares and compressive strength all far below graphene-based nano particle composite hydrogel prepared in the present invention.
Embodiment 5
Finely dispersed 0.05wt% Graphene colloidal solution was adopted cobalt-60 radiosterilize 12 hours under oxygen atmosphere, irradiation temperature is 40 ℃, radiation dose rate is 0.3kGy/min, preparation irradiating soln and 2-hydroxyethyl methacrylate mixing solutions 10mL, wherein monomer concentration is 3.8mol/L, letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 50 ℃, react namely to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 68%, and its tensile break strength is 0.5MPa, and elongation at break is that the compressive strength of 800%, 95% compression ratio is 18.50MPa.
Embodiment 6
Finely dispersed 0.3wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 8 hours under oxygen atmosphere, irradiation temperature is 40 ℃, radiation dose rate is 0.3kGy/min, pre-irradiation measures irradiating soln 10mL after finishing, it is mixed with the 2.843g acrylamide monomer, the concentration of gained acrylamide is that the 4mol/L letting nitrogen in and deoxidizing will hold mixing solutions after 30 minutes container sealing is heated, and temperature of reaction is 50 ℃, reacts namely to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.7MPa, and elongation at break is that the compressive strength of 3000%, 95% compression ratio is 28.50MPa.
Embodiment 7
At first, the 0.2g graphite oxide is dispersed in after supersound process in 100g distilled water, obtains the homogeneous dispersion liquid, then place it under oxygen atmosphere and to adopt cobalt-60 radiosterilize 3 hours, wherein, radiation dose rate is 0.4kGy/min, and irradiation temperature is 40 ℃.5mL postirradiation oxidation graphite solution is evenly mixed with 5mL NIPA monomer solution, wherein NIPA concentration is 3mol/L, letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 20 minutes, temperature of reaction is 45 ℃, reacts namely to get product after 36 hours.At ambient temperature, control crossbeam speed 40mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 70%, and its tensile break strength is 0.15MPa, and elongation at break is that the compressive strength of 1200%, 95% compression ratio is 15.40MPa.
Embodiment 8
Finely dispersed 0.2wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 12 hours under oxygen atmosphere, irradiation temperature is 30 ℃, radiation dose rate is 0.3kGy/min, pre-irradiation measures irradiating soln 5mL after finishing, it is mixed with 5mL acrylamide monomer (2.132g) solution, and the concentration of gained acrylamide is 3mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 50 ℃, reacts namely to get product after 48 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 80%, and its tensile break strength is 0.65MPa, and elongation at break is 3600%, and compressive strength is 26.80MPa.Its mechanical property of test after gained gel swelling balance is drawn: breaking tenacity is 0.04MPa, and elongation at break is 1200%.
Comparative Examples 2
Provide Comparative Examples 2 for embodiment 8, the finely dispersed 0.2wt% graphite oxide of 10mL colloidal solution is directly mixed with acrylamide monomer without irradiation, wherein monomer concentration is 3mol/L, letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 50 ℃, and reacting does not have gel to generate after 48 hours.
Comparative Examples is analyzed
Can find out by embodiment 8 and Comparative Examples 2: under same experiment condition, do not play in polyreaction without the graphite oxide colloidal solution of radiation treatment and cause and crosslinked effect, reaction is normally carried out.
Embodiment 9
Finely dispersed 0.25wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 8 hours under oxygen atmosphere, irradiation temperature is 40 ℃, radiation dose rate is 0.25kGy/min, irradiating soln is evenly mixed 10mL with acrylamide monomer solution, wherein the concentration of acrylamide is 5mol/L, letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 15 minutes, temperature of reaction is 45 ℃, react namely to get product after 24 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 70%, and its tensile break strength is 0.36MPa, and elongation at break is that the compressive strength of 1900%, 95% compression ratio is 22.45MPa.
Embodiment 10
Finely dispersed 0.05wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 12 hours under oxygen atmosphere, irradiation temperature is 40 ℃, radiation dose rate is 0.3kGy/min, pre-irradiation measures irradiating soln 10mL after finishing, it is mixed with 4.14g 2-acrylamide-2-methyl propane sulfonic monomer, and wherein monomer concentration is 2mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 45 ℃, reacts namely to get product after 48 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 70%, and its tensile break strength is 0.55MPa, and elongation at break is that the compressive strength of 3400%, 95% compression ratio is 26.80MPa.
Embodiment 11
Finely dispersed 1wt% Graphene colloidal solution was adopted cobalt-60 radiosterilize 6 hours under oxygen atmosphere, irradiation temperature is 30 ℃, radiation dose rate is 0.3kGy/min, pre-irradiation measures irradiating soln 5mL after finishing, it is mixed with 5mL acrylamide monomer (2.843g) solution, and the concentration of gained acrylamide is 4mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 50 ℃, reacts namely to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.8MPa, and elongation at break is that the compressive strength of 2000%, 95% compression ratio is 32.50MPa.
Embodiment 12
Finely dispersed 0.5wt% Graphene colloidal solution was adopted cobalt-60 radiosterilize 6 hours under oxygen atmosphere, irradiation temperature is 30 ℃, radiation dose rate is 0.2kGy/min, pre-irradiation measures irradiating soln 10mL after finishing, it is mixed with the 0.71g acrylamide monomer, and the concentration of gained acrylamide is 1.0mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 55 ℃, reacts namely to get product after 48 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 90%, and its tensile break strength is 0.1MPa, and elongation at break is that the compressive strength of 3800%, 95% compression ratio is 9.5MPa.
Embodiment 13
Finely dispersed 2.5wt% graphene oxide colloidal solution was adopted cobalt-60 radiosterilize 12 hours under oxygen atmosphere, irradiation temperature is 30 ℃, radiation dose rate is 0.4kGy/min, pre-irradiation measures irradiating soln 5mL after finishing, it is mixed with 5mL acrylamide monomer (2.843g) solution, and the concentration of gained acrylamide is 4mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 70 ℃, reacts namely to get product after 4 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 75%, and its tensile break strength is 0.5MPa, and elongation at break is that the compressive strength of 500%, 95% compression ratio is 14.50MPa.
Embodiment 14
Finely dispersed 0.04wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 12 hours under oxygen atmosphere, irradiation temperature is 25 ℃, radiation dose rate is 0.3kGy/min, pre-irradiation measures irradiating soln 10mL after finishing, it is mixed with 5.65g NIPA monomer, and the gained monomer concentration is 5mol/L, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 30 minutes, temperature of reaction is 20 ℃, reacts after 8 hours and takes out.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 73%, and its tensile break strength is 0.1MPa, and elongation at break is that the compressive strength of 800%, 95% compression ratio is 12.60MPa.
Embodiment 15
Finely dispersed 0.5wt% redox graphene colloidal solution was adopted cobalt-60 radiosterilize 12 hours under oxygen atmosphere, irradiation temperature is 25 ℃, radiation dose rate is 0.1kGy/min, pre-irradiation evenly mixes the 7mL irradiating soln with the 3mL methacrylic acid monomer after finishing, wherein monomer concentration is 3.5mol/L, letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions and heat after 20 minutes, temperature of reaction is 45 ℃, react namely to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min, with almighty test machine, it is stretched and the compressive strength test.Measuring result is: this sample moisture content is 70%, and its tensile break strength is 0.15MPa, and elongation at break is that the compressive strength of 1100%, 95% compression ratio is 14.5MPa.
To sum up, the present invention has following remarkable advantage:
Graphene-based nano particle composite hydrogel of the present invention only is comprised of graphene-based nano particle, soluble and monomeric and water three parts, does not have the residual of other compositions, is down to the potential threat that is applied to the fields such as biology minimum; And this graphene-based nano particle composite hydrogel can lower nanoparticle and monomer concentration (≤5wt%) under, (tensile strength is more than hundreds of kPa to 1MPa for the hydrogel of acquisition high mechanical strength high-tenacity, more than elongation at break reaches as high as 30MPa greater than 2000%, 95% compressive strength).After hydrogel reaches swelling equilibrium, still can keep mechanical property preferably.
The preparation method of graphene-based nano particle composite hydrogel of the present invention, greatly simplified the preparation of gels process owing to adopting pre-irradiation, only need the nanoparticle aqueous solution is processed through pre-irradiation, mode through deoxygenation, thermal initiation can be reacted with monomer solution, need not additionally to add any initiator and linking agent, simplified to the full extent operating process and the reaction process of chemical initiated polymerization method.And two processes of pre-irradiation and thermal initiation do not interfere with each other, and can carry out respectively under relatively independent process.
The present invention introduces nanoparticle surface with monomer molecule, and at the nanoparticle surface initiated polymerization, final formation take nanoparticle as causing the tridimensional network at crosslinked center, and by controlling the ratio between nanoparticle and monomer, obtained the graphene-based nano particle composite hydrogel of different mechanical properties and swelling behavior, method is simple, is convenient to industrialized enforcement.
The above is only the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (16)
1. graphene-based nano particle composite hydrogel, it is characterized in that, formed by graphene-based nano particle, water-soluble polymers and water, wherein, described water-soluble polymers causes by the peroxy-radical on graphene-based nano particle the polymerisation that contains carbon-to-carbon double bond and forms, and crosslinked as crosslinked center take graphene-based nano particle
Described graphene-based nano particle composite hydrogel is prepared from by following steps:
1) pre-irradiation peroxidation step in oxygen atmosphere, adopts high-energy radiation source irradiation graphene-based nano particle homogeneous phase aqueous solution, makes described graphene-based nano particle peroxidation;
2) thermal-initiated polymerization step; to mix with the water-soluble mono liquid solution that contains carbon-to-carbon double bond through the graphene-based nano particle aqueous solution of described pre-irradiation peroxidation step; then react under protection of inert gas, namely get described graphene-based nano particle composite hydrogel.
2. nano particle composite hydrogel according to claim 1, is characterized in that, described water-soluble monomer is selected from the carboxylic-acid monomer, sulphonic acids monomer, and one or more in the group that forms of the water-soluble monomer of non-ionic type.
3. nano particle composite hydrogel according to claim 2, is characterized in that, described graphene-based nano particle is stannic oxide/graphene nano particle and/or graphene nano particle.
4. nano particle composite hydrogel according to claim 2, is characterized in that, described carboxylic-acid monomer is selected from one or both in vinylformic acid, methacrylic acid; Described sulphonic acids monomer is the 2-acrylamide-2-methyl propane sulfonic; The water-soluble monomer of described non-ionic type is selected from one or more in the group that acrylamide and derivative thereof, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, NVP form.
5. nano particle composite hydrogel according to claim 4, it is characterized in that, described acrylamide derivative is selected from Methacrylamide, N-n-propyl acrylamide, NIPA, N, one or more in the group that N-divinyl acrylamide, N hydroxymethyl acrylamide form.
6. the preparation method of the described nano particle composite hydrogel of any one in a claim 1-5, is characterized in that, comprises the following steps:
1) pre-irradiation peroxidation step in oxygen atmosphere, adopts high-energy radiation source irradiation graphene-based nano particle homogeneous phase aqueous solution, makes described graphene-based nano particle peroxidation;
2) thermal-initiated polymerization step; to mix with the water-soluble mono liquid solution that contains carbon-to-carbon double bond through the graphene-based nano particle aqueous solution of described pre-irradiation peroxidation step; then react under protection of inert gas, namely get described graphene-based nano particle composite hydrogel.
7. preparation method according to claim 6, is characterized in that, the quality percentage composition of the described graphene-based nano particle in described graphene-based nano particle homogeneous phase aqueous solution is 0.01%～3%, and the concentration of described water-soluble monomer is 1～6mol/L.
8. preparation method according to claim 6, it is characterized in that, in described thermal-initiated polymerization step, the graphene-based nano particle aqueous solution of described process pre-irradiation peroxidation step is 20 ℃～80 ℃ with the temperature of reaction of the mixing solutions of the water-soluble mono liquid solution that contains carbon-to-carbon double bond, and the reaction times is 1～48 hour.
9. preparation method according to claim 8, is characterized in that, in described thermal-initiated polymerization step, described temperature of reaction is 35 ℃～55 ℃.
10. preparation method according to claim 6, is characterized in that, in described pre-irradiation peroxidation step, adopting radiation dose rate is the high-energy radiation source of 0.001-0.4kGy/min, and irradiation is 1～24 hour under the irradiation temperature of 0～100 ℃.
11. preparation method according to claim 10 is characterized in that, described high-energy radiation source is for producing gamma-ray cobalt source or producing the rumbatron of high-power electron beam.
12. preparation method according to claim 6 is characterized in that, described water-soluble monomer is selected from the carboxylic-acid monomer, sulphonic acids monomer, one or more in the group that the water-soluble monomer of non-ionic type forms.
13. preparation method according to claim 12 is characterized in that, described graphene-based nano particle is stannic oxide/graphene nano particle and/or graphene nano particle.
14. according to claim 12 or 13 described preparation methods is characterized in that, described carboxylic-acid monomer is selected from one or both in vinylformic acid, methacrylic acid; Described sulphonic acids monomer is the 2-acrylamide-2-methyl propane sulfonic; The water-soluble monomer of described non-ionic type is selected from one or more in the group that acrylamide and derivative thereof, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, NVP form.
15. preparation method according to claim 14, it is characterized in that, described acrylamide derivative is selected from Methacrylamide, N-n-propyl acrylamide, NIPA, N, one or more in the group that N-divinyl acrylamide, N hydroxymethyl acrylamide form.
16. preparation method according to claim 6 is characterized in that, described rare gas element is nitrogen or argon gas.
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| CN104030272A (en) * | 2014-05-04 | 2014-09-10 | 浙江理工大学 | Graphene peroxide preparation method |
| CN104232108B (en) * | 2014-09-10 | 2016-03-09 | 浙江碳谷上希材料科技有限公司 | A kind of preparation method of the pure inorganic substances compound membrane based on Graphene |
| CN106268631B (en) * | 2015-06-04 | 2019-11-12 | 中国科学院上海应用物理研究所 | Graphene-noble metal nano particles Compound Water, aeroge and preparation method thereof, application |
| CN106031857B (en) * | 2015-03-19 | 2019-11-22 | 中国科学院上海应用物理研究所 | Graphene-inorganic nanoparticles composite hydrogel, aeroge and preparation method thereof, application |
| CN104910568B (en) * | 2015-01-28 | 2017-02-01 | 云南中烟工业有限责任公司 | Graphene-polymer composite aerogel filter perfume rod and preparation method thereof |
| CN104910748B (en) * | 2015-07-08 | 2017-10-20 | 常州大学 | A kind of automobile-used functionalization graphene damping pulp and preparation method thereof |
| CN105131210A (en) * | 2015-09-30 | 2015-12-09 | 河南科技大学 | Preparation method for nano-composite multi-response hydrogel |
| CN106188393B (en) * | 2016-07-18 | 2019-04-30 | 河南工业大学 | Pre-irradiated method prepares high-elastic high-ductility graphene oxide/polyacrylamide composite gel |
| CN108409925A (en) * | 2018-03-29 | 2018-08-17 | 北京化工大学 | A kind of Organic-inorganic covalent cross-linked hydrogel and preparation method thereof |
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