CN102516479A - 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 nanoparticle composite aquogel and preparation method thereof.
Background technology
Macromolecule hydrogel is the research focus in decades recently as the soft wet stock of a kind of " coupling hardness with softness " always.The property that hydrogel is different from other rigid materials makes it all demonstrate good application prospects in industry, agricultural, biology and field of materials.But the low poor toughness of most conventional gel intensity, to a certain degree limit its as the practical application of functional material in each field.The nanoparticle composite aquogel is that the particles of inorganic material with nano-scale is scattered in the matrix material that forms in the hydrogel; It combines the soft wet performance of rigidity, size stability and the hydrogel of nano material, obviously improves mechanical property and thermostability of hydrogel etc.
Successfully introduce inorganic nano-particle in the polymeric system; And preparation high mechanical strength hydrogel; The most representative research be people such as Haraguchi with the inorganic clay nanoparticle as cross-linking set; Under the effect of initiator and aided initiating; Make monomer N-NSC 11448 (NIPAAm) at the nanoparticle surface initiated polymerization, prepare nano-composite gel (NC gel) " Nanocomposite hydrogels:a unique organic-inorganic network structure with extraordinary mechanical, optical; and swelling/deswelling properties. " (Advanced Materials, 2002.14 (16): p.1120-1124.) with high mechanical strength.This gel interacts through polymer long-chain and clay particle sub-surface; Guarantee that macromolecular chain is that surface from clay layer begins to cause; And because the uniform distribution of clay particle in system; It is also even relatively to make that the macromolecular chain that makes in this way distributes, and structure is regular relatively, 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.Research shows; Graphene nanometer sheet can be dispersed in polymeric system; These matrix materials show favorable mechanical performance 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, 2010,46 (14): p.2376-2378.) after graphene oxide and PVA solution are mixed.Liu etc. carry out freeze-thaw after graphene oxide and PVA solution are mixed; 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.).
Have only physical actions such as hydrogen bond between nanoparticle in these composite aquogels (comprising Graphene or graphene oxide) and the polymkeric substance, and do not have strong chemical b `.Therefore, the adding of these nanoparticles is not very big to the help of the performance (especially mechanical property) of raising polymer materials.
If can between graphene-based nanoparticle and polymer chain, introduce covalent chemical bond, the performance of the graphene-based Nanometer composite hydrogel of gained will obtain very big improvement 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.Like people such as Wu NIPAAm and Acrylic Acid Monomer solution are mixed back re-initiation polymerization with graphene oxide; 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.).
Contriver Wang high-lightness of the present invention etc. with monodispersed polymer microsphere as original material; It is carried out gamma-radiation radiation peroxo-, then be that the water-soluble acrylic monomer polymerization is caused at the initiation center, " the macromolecular microspheres hydrogel " that obtained having higher compression intensity is (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. serve as to cause and crosslinked center with the snperoxiaized surfactant micelle of radiation, have prepared the hydrogel (publication number: CN 101397347A) with high mechanical strength; Serve as that initiation and crosslinked center have prepared high intensity hydrogel (Chinese patent: ZL 2,007 10122579.9) also with the snperoxiaized water-soluble polymer chain of radiation.
Also be not the report that initiation and crosslinked center prepare high-strength gel at present with the Graphene.
Summary of the invention
The present invention aims to provide a kind of graphene-based nanoparticle composite aquogel and preparation method thereof; To solve nano-composite gel in the prior art because the adding of initiator and linking agent; Possibly exist some compositions residual; When being applied to biological field, possibly exist potential to threaten 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, a kind of graphene-based nanoparticle composite aquogel is provided.This graphene-based nanoparticle composite aquogel is made up of graphene-based nanoparticle, water-soluble polymers and water; Wherein, Water-soluble polymers causes the polymerisation contain carbon-to-carbon double bond by the peroxy-radical on the graphene-based nanoparticle and forms, and is that crosslinked center is crosslinked with graphene-based nanoparticle.
Further, water-soluble monomer is selected from the carboxylic-acid monomer, sulfonic acid class monomer, and in the group formed of the water-soluble monomer of non-ionic type one or more.
Further, the carboxylic-acid monomer is selected from one or both in vinylformic acid, the methylacrylic acid; Sulfonic acid class monomer is 2-acrylic amide-2-methyl propane sulfonic acid; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylic amide and verivate thereof, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, N-vinyl pyrrolidone form.
Further, acrylamide deriv is selected from USAF RH-1, N-n-propyl acrylic amide, N-NSC 11448, N, one or more in the group that N-divinyl acrylic amide, N hydroxymethyl acrylamide are formed.
Further, graphene-based nanoparticle is stannic oxide/graphene nano particle and/or graphene nano particle.
A kind of preparation method of graphene-based nanoparticle composite aquogel also is provided according to another aspect of the present invention.This preparation method may further comprise the steps: 1) pre-irradiation peroxidation step, in oxygen atmosphere, adopt the graphene-based nanoparticle homogeneous phase aqueous solution of high-energy radiation source irradiation, and make graphene-based nanoparticle peroxo-; 2) thermal-initiated polymerization step, the graphene-based nanoparticle aqueous solution that will pass through the pre-irradiation peroxidation step mixes with the water-soluble mono liquid solution that contains carbon-to-carbon double bond, and protection of inert gas reaction down then promptly gets graphene-based nanoparticle composite aquogel.
Further, the quality percentage composition of the graphene-based nanoparticle in the graphene-based nanoparticle homogeneous phase aqueous solution is 0.01%～3%, and the concentration of water-soluble monomer is 1～6mol/L.
Further, the graphene-based nanoparticle 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 0～100 ℃ irradiation temperature.
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, sulfonic acid class monomer, one or more in the group that the water-soluble monomer of non-ionic type is formed.
Further, the carboxylic-acid monomer is selected from one or both in vinylformic acid, the methylacrylic acid; Sulfonic acid class monomer is 2-acrylic amide-2-methyl propane sulfonic acid; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylic amide and verivate thereof, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, N-vinyl pyrrolidone form.
Further, acrylamide deriv is selected from USAF RH-1, N-n-propyl acrylic amide, N-NSC 11448, N, one or more in the group that N-divinyl acrylic amide, N hydroxymethyl acrylamide are formed.
Further, graphene-based nanoparticle is stannic oxide/graphene nano particle and/or graphene nano particle.
Further, rare gas element is nitrogen or argon gas.
Graphene-based nanoparticle composite aquogel of the present invention only is made up of graphene-based nanoparticle, soluble polymer and water three parts, does not have the residual of other compositions, reduces to the potential threat that is applied to fields such as biology minimum; And this graphene-based nanoparticle composite aquogel still can keep mechanical property preferably when being swelling to high-moisture or reaching swelling equilibrium.Adopt the preparation method of graphene-based nanoparticle composite aquogel of the present invention; Only need the graphene-based nanoparticle aqueous solution is handled through pre-irradiation; Mode through pre-irradiation, thermal initiation can be reacted with monomer solution, need not any initiator of extra interpolation and linking agent, has simplified the operating process and the reaction process of chemical initiated polymerization method to the full extent; And two processes of pre-irradiation and thermal initiation are not disturbed mutually, can under relatively independent process, carry out respectively.
Description of drawings
Figure of description is used to provide further understanding of the present invention, constitutes a part of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, does not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 shows pre-irradiation peroxo-process synoptic diagram; And
Fig. 2 shows polymerization crosslinking hydrogel structure synoptic diagram.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the present invention can make up each other.Below with reference to accompanying drawing and combine embodiment to specify the present invention.
A kind of typical embodiment according to the present invention, graphene-based nanoparticle composite aquogel.This graphene-based nanoparticle composite aquogel is made up of graphene-based nanoparticle, water-soluble polymers and water; Wherein, Water-soluble polymers causes the polymerisation contain carbon-to-carbon double bond by the peroxy-radical on the graphene-based nanoparticle and forms, and is that crosslinked center is crosslinked with graphene-based nanoparticle.Because this graphene-based nanoparticle composite aquogel is only generated by graphene-based nanoparticle, soluble and monomeric and water three partial reactions, does not have the residual of other compositions, reduces to the potential threat that is applied to fields such as biology minimum; And this graphene-based nanoparticle composite aquogel 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, sulfonic acid class monomer, and in the group formed of the water-soluble monomer of non-ionic type one or more.Further preferably, the carboxylic-acid monomer is selected from one or both in vinylformic acid, the methylacrylic acid; Sulfonic acid class monomer is 2-acrylic amide-2-methyl propane sulfonic acid; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylic amide and verivate thereof, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, N-vinyl pyrrolidone form.Acrylamide deriv is selected from USAF RH-1, N-n-propyl acrylic amide, N-NSC 11448, N, one or more in the group that N-divinyl acrylic amide, N hydroxymethyl acrylamide are formed.
Preferably, graphene-based nanoparticle is stannic oxide/graphene nano particle and/or graphene nano particle.
A kind of preparation method of above-mentioned nanoparticle composite aquogel is provided according to a further aspect in the invention.This preparation method may further comprise the steps: 1) pre-irradiation peroxidation step, in oxygen atmosphere, adopt the graphene-based nanoparticle homogeneous phase aqueous solution of high-energy radiation source irradiation, and make graphene-based nanoparticle peroxo-; 2) thermal-initiated polymerization step, the graphene-based nanoparticle aqueous solution that will pass through the pre-irradiation peroxidation step mixes with the water-soluble mono liquid solution that contains carbon-to-carbon double bond, and protection of inert gas reaction down then promptly gets graphene-based nanoparticle composite aquogel.
A kind of preparation method of above-mentioned graphene-based nanoparticle composite aquogel 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 nanoparticle composite aquogel may further comprise the steps: 1) pre-irradiation peroxidation step; In oxygen atmosphere; Adopt the graphene-based nanoparticle homogeneous phase aqueous solution of high-energy radiation source irradiation, make graphene-based nanoparticle peroxo-; 2) thermal-initiated polymerization step, the aqueous solution that will pass through the pre-irradiation peroxidation step are reacted under protection of inert gas after mixing with the water-soluble monomer that contains carbon-to-carbon double bond then, promptly get graphene-based nanoparticle composite aquogel.Fig. 1 is a pre-irradiation peroxo-process synoptic diagram, under the energetic ray irradiation, when having oxygen to exist, on the Graphene lamella, can connect a large amount of peroxy-radicals.Fig. 2 shows polymerization crosslinking hydrogel structure synoptic diagram, and with snperoxiaized graphene-based system and water-soluble monomer uniform mixing, at a certain temperature, the peroxo-Graphene can decomposite a large amount of radicals, thus the trigger monomer polymerization.On this basis, macromolecular chain is crosslinked central reaction with Graphene, obtains the good hydrogel of mechanical property.Adopt the preparation method of graphene-based nanoparticle composite aquogel of the present invention; Only need the graphene-based nanoparticle aqueous solution is handled through pre-irradiation; Mode through pre-irradiation, thermal initiation can be reacted with monomer solution, need not any initiator of extra interpolation and linking agent, has simplified the operating process and the reaction process of chemical initiated polymerization method to the full extent; And two processes of pre-irradiation and thermal initiation are not disturbed mutually, can under relatively independent process, carry out respectively.
Preferably, the quality percentage composition of the graphene-based nanoparticle in the graphene-based nanoparticle 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 nanoparticle 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 TR, can control the polymerization velocity and the polymer chain length of reaction system more easily, 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 0～100 ℃ irradiation temperature.Preferably, irradiation temperature is 20～50 ℃ in the pre-irradiation peroxidation step, and radiation dose rate is 0.01-0.4kGy/min, and this condition irradiation efficiency is the highest relatively.A kind of typical embodiment according to the present invention, irradiation is 1～12 hour under 20～50 ℃ irradiation temperature, along with the increase of time, can make the graphene film layer connect peroxy-radical more, and the thermal initiation process is carried out better.And irradiated oxidising process and thermal initiation process needn't be carried out continuously in strictness, can under coldcondition, preserve irradiating soln, and instant getting simplified the 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 irradiation easily and efficiently.Rare gas element adopts nitrogen or argon gas, removes oxygen in the solution for effective, and then promotes the activity of peroxy radical, more helps 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, sulfonic acid class monomer, and in the group formed of the water-soluble monomer of non-ionic type one or more.Further preferably, the carboxylic-acid monomer is selected from one or both in vinylformic acid, the methylacrylic acid; Sulfonic acid class monomer is 2-acrylic amide-2-methyl propane sulfonic acid; The water-soluble monomer of non-ionic type is selected from one or more in the group that acrylic amide and verivate thereof, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, N-vinyl pyrrolidone form.Acrylamide deriv is selected from USAF RH-1, N-n-propyl acrylic amide, N-NSC 11448, N, one or more in the group that N-divinyl acrylic amide, N hydroxymethyl acrylamide are formed.Preferably, graphene-based nanoparticle is stannic oxide/graphene nano particle and/or graphene nano particle.
To combine specific embodiment to further specify beneficial effect of the present invention below.
Embodiment 1
Finely dispersed 0.1wt% graphite oxide colloidal solution was adopted cobalt-60 radiosterilize 4 hours under oxygen atmosphere, irradiation temperature is 100 ℃, and radiation dose rate is 0.2kGy/min; Pre-irradiation is measured irradiating soln 10mL after finishing; It is mixed with acrylamide monomer (2.843g), and the concentration of gained acrylic amide 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 promptly to get product after 24 hours.At ambient temperature, control crossbeam speed 40mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.25kGy/min, after pre-irradiation finishes with itself and each 5mL uniform mixing of acrylic acid aqueous solution; 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 promptly to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 the 100g zero(ppm) water, obtains the homogeneous dispersion liquid, place it under the oxygen atmosphere again and adopted cobalt-60 radiosterilize 10 hours, wherein, radiation dose rate is 0.4kGy/min, and irradiation temperature is 50 ℃.Pre-irradiation is measured irradiating soln 10mL after finishing; It is mixed with acrylamide monomer (2.843g), and the concentration of gained acrylic amide 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 promptly to get product after 48 hours.At ambient temperature, control crossbeam speed 40mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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
Present embodiment except that following characteristics with embodiment 3: institute's oxygenation quantity of graphite is 0.15g, and the pre-irradiation temperature is 40 ℃. products obtained therefrom at ambient temperature, control crossbeam speed 40mm/min stretches to it and compressive strength is tested with the electronics universal testing machine.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
To embodiment 3 Comparative Examples 1 is provided, this Comparative Examples adopts traditional irradiance method to prepare hydrogel.At first, the 0.3g graphite oxide is dispersed in after supersound process in the 100g zero(ppm) water, obtains the homogeneous dispersion liquid.With graphite oxide solution 10mL and 2.843g acrylamide monomer uniform mixing, the concentration of gained acrylic amide is 4mol/L then, and letting nitrogen in and deoxidizing will hold the container sealing of mixing solutions after 20 minutes.Adopt cobalt-60 radiosterilize promptly 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 stretches and the compressive strength test to it with the electronics universal testing machine.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 with Comparative Examples 1 through embodiment 3: under same experiment condition, the tensile break strength and the compressive strength that adopt the hydrogel that traditional radiation method prepares are all far below prepared graphene base nanoparticle composite aquogel among 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 ℃, and 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 promptly to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.3kGy/min, and pre-irradiation is measured irradiating soln 10mL after finishing; It is mixed with the 2.843g acrylamide monomer; The concentration of gained acrylic amide 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 promptly to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 the 100g zero(ppm) water, obtains the homogeneous dispersion liquid, place it under the oxygen atmosphere again and adopted cobalt-60 radiosterilize 3 hours, wherein, radiation dose rate is 0.4kGy/min, and irradiation temperature is 40 ℃.With 5mL postirradiation oxidation graphite solution and 5mL N-NSC 11448 monomer solution uniform mixing; Wherein N-NSC 11448 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 promptly to get product after 36 hours.At ambient temperature, control crossbeam speed 40mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.3kGy/min; Pre-irradiation is measured irradiating soln 5mL after finishing; It is mixed with 5mL acrylamide monomer (2.132g) solution, and the concentration of gained acrylic amide 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 promptly to get product after 48 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 the gained gel swelling balance is drawn: breaking tenacity is 0.04MPa, and elongation at break is 1200%.
Comparative Examples 2
To embodiment 8 Comparative Examples 2 is provided; 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 with Comparative Examples 2 through embodiment 8: under same experiment condition, in polyreaction, do not play without the graphite oxide colloidal solution of radiation treatment and to 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 ℃, and radiation dose rate is 0.25kGy/min, with irradiating soln and acrylamide monomer solution uniform mixing 10mL; Wherein the concentration of acrylic amide 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 promptly to get product after 24 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.3kGy/min; Pre-irradiation is measured irradiating soln 10mL after finishing; It is mixed with 4.14g 2-acrylic amide-2-methyl propane sulfonic acid 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 promptly to get product after 48 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.3kGy/min; Pre-irradiation is measured irradiating soln 5mL after finishing; It is mixed with 5mL acrylamide monomer (2.843g) solution, and the concentration of gained acrylic amide 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 promptly to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.2kGy/min; Pre-irradiation is measured irradiating soln 10mL after finishing; It is mixed with the 0.71g acrylamide monomer, and the concentration of gained acrylic amide 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 promptly to get product after 48 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.4kGy/min; Pre-irradiation is measured irradiating soln 5mL after finishing; It is mixed with 5mL acrylamide monomer (2.843g) solution, and the concentration of gained acrylic amide 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 promptly to get product after 4 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.3kGy/min; Pre-irradiation is measured irradiating soln 10mL after finishing; It is mixed with 5.65g N-NSC 11448 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 stretches and the compressive strength test to it with the electronics universal testing machine.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 ℃, and radiation dose rate is 0.1kGy/min, after pre-irradiation finishes with 7mL irradiating soln and 3mL methacrylic acid monomer uniform mixing; 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 promptly to get product after 36 hours.At ambient temperature, control crossbeam speed 20mm/min stretches and the compressive strength test to it with the electronics universal testing machine.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 nanoparticle composite aquogel of the present invention only is made up of graphene-based nanoparticle, soluble and monomeric and water three parts, does not have the residual of other compositions, reduces to the potential threat that is applied to fields such as biology minimum; And this graphene-based nanoparticle composite aquogel 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; Elongation at break reaches as high as more than the 30MPa greater than 2000%, 95% compressive strength).After hydrogel reaches swelling equilibrium, still can keep mechanical property preferably.
The preparation method of graphene-based nanoparticle composite aquogel of the present invention; Greatly simplified the preparation process of hydrogel owing to adopt pre-irradiation; Only need the nanoparticle aqueous solution is handled through pre-irradiation; Mode through deoxygenation, thermal initiation can be reacted with monomer solution, need not any initiator of extra interpolation and linking agent, has simplified the operating process and the reaction process of chemical initiated polymerization method to the full extent.And two processes of pre-irradiation and thermal initiation are not disturbed mutually, can under relatively independent process, carry out respectively.
The present invention introduces nanoparticle surface with monomer molecule; And at the nanoparticle surface initiated polymerization; Finally forming with the nanoparticle is the tridimensional network that causes crosslinked center, and through the ratio between control nanoparticle and the monomer, has obtained the graphene-based nanoparticle composite aquogel of different mechanical properties and swelling behavior; Method is simple, is convenient to industrialized enforcement.
The above is merely 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 changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. graphene-based nanoparticle composite aquogel; It is characterized in that; Form by graphene-based nanoparticle, water-soluble polymers and water; Wherein, said water-soluble polymers causes the polymerisation contain carbon-to-carbon double bond by the peroxy-radical on the graphene-based nanoparticle and forms, and is that crosslinked center is crosslinked with graphene-based nanoparticle.
2. nanoparticle composite aquogel according to claim 1; It is characterized in that; Said water-soluble monomer is selected from the carboxylic-acid monomer, sulfonic acid class monomer, and in the group formed of the water-soluble monomer of non-ionic type one or more; Preferably, said graphene-based nanoparticle is stannic oxide/graphene nano particle and/or graphene nano particle.
3. nanoparticle composite aquogel according to claim 2 is characterized in that, said carboxylic-acid monomer is selected from one or both in vinylformic acid, the methylacrylic acid; Said sulfonic acid class monomer is 2-acrylic amide-2-methyl propane sulfonic acid; The water-soluble monomer of said non-ionic type is selected from one or more in the group that acrylic amide and verivate thereof, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, N-vinyl pyrrolidone form; Preferably, said acrylamide deriv is selected from USAF RH-1, N-n-propyl acrylic amide, N-NSC 11448, N, one or more in the group that N-divinyl acrylic amide, N hydroxymethyl acrylamide are formed.
4. the preparation method of each described nanoparticle composite aquogel among the claim 1-3 is characterized in that, may further comprise the steps:
1) pre-irradiation peroxidation step in oxygen atmosphere, adopts the graphene-based nanoparticle homogeneous phase aqueous solution of high-energy radiation source irradiation, makes said graphene-based nanoparticle peroxo-;
2) thermal-initiated polymerization step; The graphene-based nanoparticle aqueous solution that will pass through said pre-irradiation peroxidation step mixes with the water-soluble mono liquid solution that contains carbon-to-carbon double bond; Reaction under protection of inert gas then promptly gets said graphene-based nanoparticle composite aquogel.
5. preparation method according to claim 4 is characterized in that, the quality percentage composition of the said graphene-based nanoparticle in the said graphene-based nanoparticle homogeneous phase aqueous solution is 0.01%～3%, and the concentration of said water-soluble monomer is 1～6mol/L.
6. preparation method according to claim 4; It is characterized in that; In the said thermal-initiated polymerization step; The graphene-based nanoparticle aqueous solution of said 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, in the said thermal-initiated polymerization step, said temperature of reaction is 35 ℃～55 ℃.
7. preparation method according to claim 4 is characterized in that, in the said 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 0～100 ℃ irradiation temperature; Preferably, said high-energy radiation source is for producing gamma-ray cobalt source or producing the rumbatron of high-power electron beam.
8. preparation method according to claim 4 is characterized in that said water-soluble monomer is selected from the carboxylic-acid monomer, sulfonic acid class monomer, one or more in the group that the water-soluble monomer of non-ionic type is formed; Preferably, said graphene-based nanoparticle is stannic oxide/graphene nano particle and/or graphene nano particle.
9. preparation method according to claim 8 is characterized in that, said carboxylic-acid monomer is selected from one or both in vinylformic acid, the methylacrylic acid; Said sulfonic acid class monomer is 2-acrylic amide-2-methyl propane sulfonic acid; The water-soluble monomer of said non-ionic type is selected from one or more in the group that acrylic amide and verivate thereof, 2-hydroxyethyl methacrylate, methylacrylic acid-2-hydroxypropyl acrylate, N-vinyl formamide, 4-vinylpridine, N-vinyl pyrrolidone form; Preferably, said acrylamide deriv is selected from USAF RH-1, N-n-propyl acrylic amide, N-NSC 11448, N, one or more in the group that N-divinyl acrylic amide, N hydroxymethyl acrylamide are formed.
10. preparation method according to claim 4 is characterized in that, said rare gas element is nitrogen or argon gas.
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