CN103242656B - Multi-component super-molecular hydrogel and preparation method thereof - Google Patents
Multi-component super-molecular hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses multi-component super-molecular hydrogel and a preparation method of the multi-component super-molecular hydrogel. The hydrogel is formed by a component containing a strong hydrogen bond, a component containing a weak hydrogen bond and water, wherein the component containing the strong hydrogen bond is one or more of a carbon oxide nano tube, graphene oxide, a carboxylated ferroferric oxide nano particle, a carboxylated silver nano particle, a carboxylated quantum dot, polyacrylic acid, polypropylene glycol, polyvinyl alcohol, polyurethane, polyamide and poly(p-styrene) sodium sulfonate; and the component containing the weak hydrogen bond is a small-molecular compound or a high-molecular compound. A lot of cross-linking force of the hydrogel disclosed by the invention comes from the weak hydrogen bond so that the hydrogel is very sensitive to the stimulation of an external environment; when chemical components are proper, gel-sol conversion can be carried out under the effects of temperature rising, near-infrared light illumination and acids; and the conversion is reversible, namely the gel-sol conversion can be carried out under the effects of temperature reduction, removing of a near-infrared light source and alkalis.
Description
Technical field
The present invention relates to a kind of polycomponent supramolecular hydrogel and preparation method thereof.
Background technology
Along with the appearance of supramolecule science, supramolecular hydrogel starts by extensive concern at the beginning of 21 century.Compare the crosslinked hydrogel obtaining of traditional chemical method, the three-dimensional net structure of supramolecular hydrogel is formed by weak interaction induction.Because weak interaction is very responsive to the variation of environment, and usually there is reversibility, therefore, supramolecular hydrogel has not only kept traditional hydrogel high water content, biocompatibility, eco-friendly feature, and often has the excellent properties such as response, self-healing concurrently.But, can realize the hydrogel of several functions, type, the power etc. of crosslinked power are often had to strict requirement.How effectively to regulate and control the crosslinked power in supramolecular hydrogel, obtain the supramolecular hydrogel that possesses several functions, be the difficult problem in this field always.
Carbon nanotube is just found a kind of new one-dimensional carbon materials in 20 end of the centurys.Perfectly Single Walled Carbon Nanotube can be considered by sp
2the single-layer graphene film that bond is closed is along the curling seamless tubular shaped structure forming of specific direction, and multi-walled carbon nano-tubes can be considered the molectron of many coaxial single-walled pipe.The difference of curl direction, can make carbon nanotube show metallicity or semiconductive.The diameter of carbon nanotube can change between tens nanometer at 0.4nm, and its length also can change between hundreds of nanometers to tens centimetre, and length-to-diameter ratio can reach 10
7above.The length-to-diameter ratio of superelevation, the diversity of tubular structure, a large amount of π-electrons that dissociate on tube wall, make carbon nanotube aspect optics, electricity, mechanics, absorption, possess extremely excellent character.
Carbon nanotube has the character as many excellences, is therefore often used to aquogel system.Based on the hydrogel of carbon nanotube, can be formed by pure nano-carbon tube, also can be composited by carbon nanotube and other material.Due to the existence of carbon nanotube, this class hydrogel has electroconductibility and the mechanical strength higher than traditional hydrogel mostly, and also often has more excellent performance aspect absorption, response.But, there is self-healing function, or the hydrogel based on carbon nanotube that can simultaneously respond two or more external stimuluss rarely has report.
Summary of the invention
The object of this invention is to provide a kind of polycomponent supramolecular hydrogel and preparation method thereof, in method provided by the invention, by changing the relative content of each component, can simply and effectively regulate the crosslinked power in gel, and then obtain multi-functional supramolecular hydrogel.With respect to other hydrogel, supramolecular hydrogel provided by the invention can be realized the adhesion behavior that multiple response, self-healing and environment rely on simultaneously, can be widely used in the fields such as sensor, actuator, self-healing material and removable intelligent adhesive agent.
A kind of polycomponent supramolecular hydrogel provided by the present invention, by containing the component of strong hydrogen bonding, forming containing component and the water of weak hydrogen bond;
The described component containing strong hydrogen bonding is one or more in oxide/carbon nanometer tube, graphene oxide, carboxylated ferriferrous oxide nano-particle, carboxylated Nano silver grain, carboxylated quantum dot (as carboxylated carbon quantum dot, carboxylated ZnS quantum dots, carboxylated cadmiumsulfide quantum dot or carboxylated cadmium telluride quantum dot), polyacrylic acid, POLYPROPYLENE GLYCOL, polyvinyl alcohol, urethane, polymeric amide and poly (sodium 4-styrenesulfonate);
The described component containing weak hydrogen bond is micromolecular compound or macromolecular compound, and described micromolecular compound or described macromolecular compound are the described compound containing primary amine, secondary amine or tertiary amine.
In above-mentioned supramolecular hydrogel, it is that in 200710158315.9 or 201010263656.4 patent application, disclosed technical scheme is prepared that described oxide/carbon nanometer tube can adopt application number; It is that in 201010263656.4 patent application, disclosed technical scheme is prepared that described graphene oxide can adopt application number; Described carboxylated ferriferrous oxide nano-particle can be used W.Chen, S.Li, and C.Chen, L.Yan, Adv.Mater.2011, the method in 23,5679 is synthesized.
In above-mentioned supramolecular hydrogel, the mass ratio of the described component containing strong hydrogen bonding and the described component containing weak hydrogen bond can be 1:33～3500, specifically can be 1:100～3500,1:100,1:145,1:250,1:499,1:1000,1:2000 or 1:3500.
In above-mentioned supramolecular hydrogel, in described hydrogel, the quality percentage composition of described water can be 25%～90%, as 25wt%, 37.5wt%, 50wt%, 62.5wt% or 75wt%.
In above-mentioned supramolecular hydrogel, described macromolecular compound can be polyethylene polyamine, polymine (molecular weight is 300～3000), polyhexene imines (molecular weight is 300～3000), third generation daiamid dendritic polymer, the 4th generation daiamid dendritic polymer, the 5th generation daiamid dendritic polymer or over-branched polyamidoamine; Wherein, described third generation daiamid dendritic polymer, the 4th generation daiamid dendritic polymer and the 5th generation daiamid dendritic polymer can be according to document (D.A.Tom, E.Baker, J.Dewald, M.Hall, G.Kalla, S.Martin, J.Raeck, J.Ryder and P.Smith, Macromolecules, 1986,19,2466.) method of report is prepared; Described over-branched polyamidoamine can according to document (Sun Jing. ultrabranching polyamide synthetic with progress [J]. Shanghai chemical industry, 2011, (6): 19-24.) method of report is prepared.
In above-mentioned supramolecular hydrogel, described micromolecular compound can be trimeric cyanamide.
The preparation method who the present invention further provides above-mentioned supramolecular hydrogel, comprises the steps:
(1) aqueous solution of the described component containing strong hydrogen bonding of preparation;
(2) in the aqueous solution of the described component containing strong hydrogen bonding, add the described component containing weak hydrogen bond and mix, obtaining suspension;
(3) described suspension is through leaving standstill and obtain described supramolecular hydrogel.
In above-mentioned preparation method, in the aqueous solution of the described component containing strong hydrogen bonding, the quality-volumetric concentration of the described component containing strong hydrogen bonding can be 0.3～15mg/mL, as 0.3～10mg/mL, 3mg/mL, 4mg/mL or 10mg/mL.
In above-mentioned preparation method, in step (3), described standing temperature can be 5 DEG C～30 DEG C, specifically can be 12 DEG C, and the described standing time can 1min～72h, specifically can be 10min～24h, 10min, 6h, 12h or 24h.
Inclusion-free component in hydrogel prepared by preparation method provided by the invention, therefore without extra post-processing step, can directly be used.
Polycomponent supramolecular hydrogel provided by the invention can be used as thermal stress responsive materials, therefore can be used for preparation temperature sensor.Wherein, thermal stress response refers to that described supramolecular hydrogel, along with not coexisting of temperature changes between solid-state and liquid state, specifically at high temperature becomes liquid state, becomes at low temperatures solid-stately, and high temperature refers to 35～90 DEG C, and low temperature refers to 5～30 DEG C.This thermoinducible gel-sol reversible transition, because in this supermolecular gel system, most of crosslinked power is provided by weak hydrogen bond, and weak hydrogen bond can be destroyed by heating up, thereby makes three network structures of gel can be destroyed in the situation that heating up.Due to the reversibility of weak hydrogen bond, leave standstill for some time at lesser temps, gel network can be able to reconstruct.
Polycomponent supramolecular hydrogel provided by the invention can be used as near infrared light response material, therefore can be used for preparing near infrared light sensor.Wherein, described near infrared light response refer to described supramolecular hydrogel under the condition that has or not laser radiation solid-state and liquid between change, specifically can be at successive type 1064nm laser or pulse mode 1064nm laser, energy is 1～10mJ, power is 0.1～10
5w, when irradiation time is 10s～10min, changes liquid state into; Remove after laser, gained liquid can leave standstill 30s～30min and reply as immobilising gel at 5～20 DEG C.The photoinduced gel-sol reversible transition of this near infrared, because strong absorption effect near infrared light of carbon nanotube or Graphene and convert it to hot ability, this photo-thermal effect can be used for destroying the weak hydrogen bond in supermolecular gel system, thereby disintegrates three gel networks.Due to the reversibility of weak hydrogen bond, leave standstill for some time at lesser temps, gel network can be able to reconstruct.
Polycomponent supramolecular hydrogel provided by the invention can be used as potential of hydrogen (pH value) response material, therefore can be used for preparing acidity-basicity sensor; Wherein, soda acid response refer to described supramolecular hydrogel along with not coexisting of potential of hydrogen liquid and solid-state between change, specifically, under the effect of concentrated hydrochloric acid (volume ratio of gel and concentrated hydrochloric acid can be 1～20:1), in 30s～60min, change liquid state into; Gained liquid can, by adding and the potassium hydroxide of amount or the pressed powder of sodium hydroxide or the strong solution of hydrochloric acid same substance, stir, and room temperature leaves standstill 30s～60min, replys as immobilising gel.The gel-sol reversible transition of this soda acid (pH value) induction, because in this supermolecular gel system, most of crosslinked power is by the weak hydrogen bond N-H of amino key ... N provides, and amino can be by protonated in the situation that acid adds, thereby the weak hydrogen bond between amino is disappeared, then become strong electrostatic repulsion forces, thereby make three network structures of gel destroyed.By in exogenously added alkali and protonated amino, the weak hydrogen bond between amino can form again, thereby gel network can be able to reconstruct.
Polycomponent supramolecular hydrogel provided by the invention can be used as self-healing material.Hydrogel of the present invention is in the time that shear-stress is 1～3000Pa, and structure is destroyed, and can in 2s～120min, recover afterwards its original mechanical property, and the crosslinked power that this performance comes from gel is reversible hydrogen bond action.Hydrogel of the present invention is dry rear (drying temperature is 20～80 DEG C), still can keep self-healing performance: after being cut as polylith, can be after it is cut off after 30s～120h, directly by fracture surface simple concatenation, fracture surface can recover as before in 3s～10min, and can support the weight of whole gel; Or form after hole under external force collision, in 3s～10min, recover as before voluntarily, without any need for the input of extraneous energy or material, above-mentioned performance comes from a large amount of weak hydrogen bonds that exist in this gel, makes crosslinked in gel have very high reversibility.
Polycomponent supramolecular hydrogel provided by the invention can be used as binding agent.In component due to hydrogel of the present invention, contain the element such as oxygen, nitrogen that electronegativity is stronger, therefore there is stronger adhesive power.After dry, (drying temperature is 20～90 DEG C to gained supramolecular hydrogel, time is 1～14 day), evenly coat metal counterweight bottom surface, and at the bottom of being pressed in substrate of glass, Teflon substrate, polystyrene substrate, polymethyl methacrylate base, in the GaAs based end or polyethylene terephthalate (PET) substrate, at 5～15 DEG C of constant temperature 2h～48h, at 12 DEG C of test adhesive powers, acquired results is 2～8N/cm afterwards
2.
Hydrogel of the present invention is during as binding agent, and its cohesive force has dependency to temperature.Learn through experiment, when temperature changes to 35 DEG C from 12 DEG C, adhesive power is from 2～8N/cm
2drop to 2 × 10
-4～8 × 10
-4n/cm
2, and the variation of adhesive power is reversible.When temperature is reduced to after original numerical value, adhesive power can be recovered completely.
Hydrogel of the present invention is during as binding agent, and its cohesive force has dependency near infrared light.Learn through experiment, when load-bearing is 2N/cm
2time, use 1064nm laser (energy 3～10mJ, power 0.1～10
5w) irradiate bonded part, can make at 10s～10min the article desorption of bonding.When stopping irradiating also again after bonding, its adhesive power can be recovered completely.
Hydrogel of the present invention during as binding agent, can recycle.Learn through experiment, when make, after the article desorption of bonding, article can be bondd again by external force, intensification, near infrared light mode.If directly test, cohesive force is original 20%～90%; If after 5～15 DEG C of constant temperature 5min～48h, adhesive power can return to initial level.
Hydrogel of the present invention is during as binding agent, and its vertical direction adhesive power, much larger than its tangential adhesive power, therefore can play two bones of bonding in joint prosthesis, and it can tangentially be rotated freely, and don't as for the effect departing from.
The present invention has following beneficial effect:
1, preparation method provided by the invention has extremely strong universality, and in hydrogel, two classes provide the component of the hydrogen bond of varying strength, all can be made up of a series of materials, and gained gel all can be realized multifunction.In addition, by using or the extra material with specific function of introducing, as ferriferrous oxide nano-particle, Nano silver grain, also can give hydrogel with magnetic and electroconductibility.
2, the crosslinked power of the major part of polycomponent supramolecular hydrogel provided by the invention derives from weak hydrogen bond, therefore the hydrogel to external world stimulation of environment is very sensitive, in the time that its chemical constitution is suitable, can under the effect of intensification, near infrared light, acid, there is Gel-sol transition, and this transformation is reversible, under the effect of lowering the temperature, remove near-infrared light source, alkali, realize sol-gel transition.
3,, when the component containing strong hydrogen bonding in hydrogel provided by the invention is oxide/carbon nanometer tube or graphene oxide, can realizes the Gel-sol transition of near infrared induction, thereby can make gel as remote controlled sensor or actuator.
4, when two kinds of components in hydrogel provided by the invention are any one or the multiple replacement component of mentioning in experimental program, gained hydrogel all can be realized temperature and sour Gel-sol transition of inducing, thereby can make gel as remote controlled sensor or actuator.
5,, when two kinds of components in hydrogel provided by the invention are one or more replacement components of mentioning in experimental program arbitrarily, the crosslinked power in hydrogel all derives from reversible non-bonded interaction, therefore has self-healing function.The self-healing process of gel is auxiliary without extraneous energy (as light, heat) and material (as solvent, linking agent, high polymer monomer).
6, hydrogel provided by the invention has self-healing function.Gel is being cut to after polylith, in long-time rear splicing arbitrarily, all can recover as a whole.And gel, in moistening and drying regime, all can keep the function of self-healing.
7, hydrogel provided by the invention can be used as binding agent use.Except it has stronger adhesive power, different from most commercialization binding agents, this gel can be recycled as binding agent, and its adhesive power can be greatly weakened after intensification or near infrared light.Therefore, can take off bur by the way of heating or illumination, and place that it is transferred to other needs adheres to again.
8, hydrogel provided by the invention can be used as binding agent use.Be different from common binding agent, this gel in the vertical direction adhesive power, much larger than its tangential adhesive power, therefore can play two bones of bonding in joint prosthesis, it can tangentially be rotated freely and don't as for the effect mutually departing from.
9, hydrogel provided by the invention possesses the reversible adhesion behavior of multiple response, self-healing function, environment dependence simultaneously, can obtain important application in sensor, actuator, medicine controlled releasing, self-repair material, photo-thermal therapy, removable intelligent binding agent, joint prosthesis field.
Brief description of the drawings
Fig. 1 is the supramolecular hydrogel digital photograph that embodiment 1 obtains.
Fig. 2 is the digital photograph of embodiment 1,2,3,4,5,6 and 8 gained supramolecular hydrogels, respectively corresponding diagram 2(a in turn), Fig. 2 (b), Fig. 2 (c), Fig. 2 (d), Fig. 2 (e), Fig. 2 (f) and Fig. 2 (g).
Fig. 3 is the TEM picture of the supramolecular hydrogel that obtains of embodiment 1, and wherein in the gel shown in Fig. 3 (a) and Fig. 3 (b), oxide/carbon nanometer tube concentration is 0.025wt%, and in the gel shown in Fig. 3 (c) and Fig. 3 (d), oxide/carbon nanometer tube concentration is 0.2wt%.
Fig. 4 is the dried Fourier infrared spectrum figure of carbon nanotube/polyethylene polyamine supramolecular hydrogel that polyethylene polyamine and embodiment 1 obtain.
Fig. 5 is the thermoinducible gel-sol reversible transition photo of the supramolecular hydrogel that obtains of embodiment 1.
Fig. 6 is the photoinduced gel-sol reversible transition of the near infrared photo of the supramolecular hydrogel that obtains of embodiment 1.
Fig. 7 is the gel-sol reversible transition photo of soda acid (pH value) induction of the supramolecular hydrogel that obtains of embodiment 1, the digital photograph that wherein Fig. 7 (a) is transition process, the chemical equation that Fig. 7 (b) is transformation mechanism.
Fig. 8 is the supramolecular hydrogel of several different carbon nanotube concentration that obtain of embodiment 1 while applying periodically shearing force by rheometer, the respective change situation of its modulus.
Fig. 9 is that the supramolecular hydrogel that embodiment 1 obtains can pass through the photo of section self-healing after being cut off.
To be the supramolecular hydrogel that obtains of embodiment 1 be bonded in respectively in Teflon substrate the digital photograph of (Figure 10 (b)) on (Figure 10 (a)) and substrate of glass by metal counterweight to Figure 10.
The supramolecular hydrogel that Figure 11 obtains by embodiment 1 under differing temps, bond certainweight weight the lasting time (Figure 11 (a)) of energy, and in the time of multiple temperature cycle changing conditions curve (Figure 11 (b) of time length.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Oxide/carbon nanometer tube solution in following embodiment 1,2 and 8 prepares by the following method:
(1) take multi-walled carbon nano-tubes 500mg in 500ml24 mouth round-bottomed flask, adding wherein 187.5mL massfraction is the concentrated nitric acid that 98% the vitriol oil and 62.5mL massfraction are 65%.Then, by it ultrasonic 6h at 60 DEG C;
(2) 250mL ice cube is put into 2L beaker, then the mixed acid solution of carbon nanotube is poured into wherein, and continue to stir 20min;
(3) gained mixed solution is turned to lower high speed centrifugation 10000, discard supernatant liquid, the black mud slurry like material of gained is dialysed 8 times in deionized water, until it is neutral;
(4) gained material is scattered in deionized water, is formulated as the oxide/carbon nanometer tube aqueous dispersions of 0.3～12mg/mL.
Graphene oxide solution in following embodiment 3 and 4 prepares by the following method:
(1) sulfuric acid that is 98wt% by 25mL concentration adds in 100mL flask, is heated to 90 DEG C, slowly adds successively 5g Potassium Persulphate and 5g Vanadium Pentoxide in FLAKES under agitation condition.Then be cooled to 80 °, add 5g Graphite Powder 99, stirring reaction 4.5 hours, adds the distilled water of 1L to leave standstill 12h, obtains preoxidation graphite.
(2) with 2L distilled water, the preoxidation graphite obtaining is carried out after filtering and washing, by preoxidation graphite dry 12h at 50 DEG C.
(3) getting 230mL concentration is the flask that the sulfuric acid of 98wt% is placed in 1L, with the cooling 20min of ice bath, then slowly adds successively dried preoxidation graphite and 30g potassium permanganate, magnetic agitation 20min; Flask is reacted after 2h in 35 DEG C of water-baths, slowly add 460mL distilled water, then add the distilled water diluting of 1.4L, after stirring reaction 2h, add the hydrogen peroxide of 25mL30wt%, now the color of reaction solution becomes khaki color.
(4) to the hydrochloric acid that adds 5wt% in reaction solution, after standing sedimentation, supernatant liquor is poured out, repeated 3 times; Add again 2L distilled water, after standing sedimentation, supernatant liquor is poured out, centrifugal after repeating 2 times, obtain graphene oxide, described graphene oxide is made into and needs the graphene oxide of concentration solution, its concentration is 0.3～12mg/mL.
The water-sol of the carboxylated ferriferrous oxide nano-particle in following embodiment 5 prepares by the following method:
(1) 0.85mL concentrated hydrochloric acid (massfraction 35～38%) is joined in 25mL deionized water, under vigorous stirring, add continuously wherein 5.2g iron trichloride and 2.0g iron protochloride;
(2), under vigorous stirring, in gained solution, dropwise add the sodium hydroxide solution of 250mL1.5mol/L;
(3), in previous step process, there is black precipitate to produce.By magnetic force, precipitation is held to abandoning supernatant;
In precipitation, add appropriate amount of deionized water (200～500mL), centrifugal 10～30min under the rotating speed of 4000 revs/min, centrifugal rear abandoning supernatant.This step 3 times repeatedly;
(4), under agitation condition, by 500mL, 0.01mol/L aqueous hydrochloric acid joins in precipitation.Recentrifuge (4000 revs/min) 10～30min, abandoning supernatant;
(5) add again suitable quantity of water (200～500mL) by it dissolving, can obtain the aqueous solution of transparent, yellow carboxylated ferriferrous oxide nano-particle.
In following embodiment 7, carboxylated tellurium chromium quantum dot is buied (article No. QD-11-560) from Nanjing Jie Nasi novel material company limited, and its finishing has carboxyl, has good solvability in water.
Embodiment 1, prepare supramolecular hydrogel
1) get the oxide/carbon nanometer tube aqueous solution that 1mL concentration is 4mg/mL, add 1mL polyethylene polyamine, by system sealing and at 50 DEG C of heating in water bath 30s;
2) gained mixture, at 12 DEG C of constant temperature 10min, can obtain carbon nanotube/polyethylene polyamine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulation and control oxide/carbon nanometer tube and the mass ratio (1:33～3500) of polyethylene polyamine and the quality percentage composition (25%～90%) of water, prepare the hydrogel of a series of compositions.
Fig. 1 is carbon nanotube/polyethylene polyamine supramolecular hydrogel digital photograph that embodiment 1 obtains.
Wherein shown in Fig. 1 (a) in hydrogel, oxide/carbon nanometer tube concentration is 0.2wt%, and water content is from left to right respectively 25wt%, 37.5wt%, 50wt%, 62.5wt% and 75wt%; Shown in Fig. 1 (b), the water content of hydrogel is 50wt%, and from left to right oxide/carbon nanometer tube concentration is respectively 0.015wt%, 0.025wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.35wt% and 0.5wt%.
The digital photograph of the hydrogel (oxide/carbon nanometer tube concentration is 0.1wt%, and water content is 50wt%, and the mass ratio of oxide/carbon nanometer tube and polyethylene polyamine is 1:499) of a kind of composition that wherein prepared by this embodiment as shown in Figure 2 (a) shows.
Fig. 3 is the TEM picture of carbon nanotube/polyethylene polyamine supramolecular hydrogel of the different concns that obtains of the present embodiment, in gel shown in Fig. 3 (a) and Fig. 3 (b), oxide/carbon nanometer tube concentration is 0.025wt%, and in the gel shown in Fig. 3 (c) and Fig. 3 (d), oxide/carbon nanometer tube concentration is 0.2wt%.
Can find out from Fig. 1, Fig. 2 and Fig. 3, for carbon nanotube/polyethylene polyamine supramolecular hydrogel, can see that carbon nanotube outer wall is wrapped up by polyethylene polyamine, the carbon nanotube being wrapped by overlaps mutually, thereby forms three network structures of gel.
Fig. 4 is the dried Fourier infrared spectrum figure of carbon nanotube/polyethylene polyamine supramolecular hydrogel that polyethylene polyamine and embodiment 1 obtain.Can be learnt by this figure, with respect to polyethylene polyamine, dried gel is at 3300cm
-1the slightly broadening of amino N-H stretching vibration peak at place, the asymmetric (2941cm of methylene radical
-1) and symmetrical stretching vibration peak (2827cm
-1) move 2～4cm to high wave number
-1, and 1639cm
-1near occurred-COO
-nH
+vibration peak, these signs all show in system to exist a large amount of weak hydrogen bonds and a small amount of strong hydrogen bonding simultaneously.
Embodiment 2, prepare supramolecular hydrogel
1) get the oxide/carbon nanometer tube aqueous solution that 1mL concentration is 4mg/mL, adding 1mL molecular weight is 300 branched polyethylene imine, by system sealing and at 50 DEG C of heating in water bath 30s;
2) gained mixture, at 12 DEG C of constant temperature 6h, can obtain carbon nano-tube/poly ethyleneimine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulation and control carbon nanotube and the mass ratio (1:33～3500) of polymine and the quality percentage composition (25%～75%) of water, prepare the hydrogel of a series of compositions.
The digital photograph of the hydrogel (oxide/carbon nanometer tube concentration is 0.2wt%, and water content is 50wt%, and the mass ratio of oxide/carbon nanometer tube and polymine is 1:250) of a kind of composition prepared by this embodiment is as shown in Fig. 2 (b).
Embodiment 3, prepare supramolecular hydrogel
1) get the graphite oxide aqueous solution that 1mL concentration is 3mg/mL, add 1mL polyethylene polyamine, by system sealing and at 50 DEG C of heating in water bath 30s;
2) gained mixture, at 12 DEG C of constant temperature 12h, can obtain Graphene/polyethylene polyamine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulation and control graphene oxide and the mass ratio (1:33～3500) of polyethylene polyamine and the quality percentage composition (25%～90%) of water, prepare the hydrogel of a series of compositions.
(oxide/carbon nanometer tube concentration is 0.15wt% to the hydrogel of a kind of composition prepared by this embodiment, and water content is 50wt%, and the digital photograph that the mass ratio of graphene oxide and polyethylene polyamine is 1:333.3 as shown in Figure 2 (c).
Embodiment 4, prepare supramolecular hydrogel
1) get the graphite oxide aqueous solution that 1mL concentration is 3mg/mL, adding 1mL molecular weight is 300 branched polyethylene imine, by system sealing and at 50 DEG C of heating in water bath 30s;
2) gained mixture, at 12 DEG C of constant temperature 12h, can obtain Graphene/polymine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulation and control graphene oxide and the mass ratio (1:33～3500) of polymine and the quality percentage composition (25%～90%) of water, prepare the hydrogel of a series of compositions.
(oxide/carbon nanometer tube concentration is 0.15wt% to the hydrogel of a kind of composition prepared by this embodiment, and water content is 50wt%, and the digital photograph that the mass ratio of graphene oxide and polymine is 1:333.3 as shown in Figure 2 (d) shows.
Embodiment 5, prepare supramolecular hydrogel
1) get the carboxylated ferriferrous oxide nano-particle aqueous solution that 1mL concentration is 10mg/mL, add 1mL polyethylene polyamine, by system sealing and at 50 DEG C of heating in water bath 20s;
2) gained mixture, at 12 DEG C of constant temperature 24h, can obtain Z 250/polyethylene polyamine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulating and controlling the mass ratio (1:33～3500) of carboxylated ferriferrous oxide nano-particle and polyethylene polyamine and the quality percentage composition (25%～90%) of water, prepare the hydrogel of a series of compositions.
(carboxylated ferriferrous oxide nano-particle concentration is 0.5wt% to the hydrogel of a kind of composition prepared by this embodiment, water content is 50wt%, and the digital photograph that the mass ratio of carboxylated ferriferrous oxide nano-particle and polyethylene polyamine is 1:100 is as shown in Fig. 2 (e).
Embodiment 6, prepare supramolecular hydrogel
1) get the polyacrylic acid aqueous solution that 1mL concentration is 10mg/mL, add 1mL polyethylene polyamine, by system sealing and at 50 DEG C of heating in water bath 20s;
2) gained mixture, at 12 DEG C of constant temperature 24h, can obtain polyacrylic acid/polyethylene polyamine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulation and control polyacrylic acid and the mass ratio (1:33～3500) of polyethylene polyamine and the quality percentage composition (25%～90%) of water, prepare the hydrogel of a series of compositions.
(polyacrylic acid concentration is 0.5wt% to the hydrogel of a kind of composition prepared by this embodiment, and water content is 50wt%, and the digital photograph that the mass ratio of polyacrylic acid and polyethylene polyamine is 1:100 is as shown in Fig. 2 (f).
Embodiment 7, prepare supramolecular hydrogel
1) get the carboxylated tellurium chromium quantum dot aqueous solution that 1mL concentration is 3mg/mL, add 1mL polyethylene polyamine, by system sealing and at 50 DEG C of heating in water bath 20s;
2) gained mixture, at 12 DEG C of constant temperature 24h, can obtain Nano silver grain/polyethylene polyamine supramolecular hydrogel.
Then,, according to above-mentioned steps, by regulating and controlling the mass ratio (1:50～3500) of carboxylated tellurium chromium quantum dot and polyethylene polyamine and the quality percentage composition (25%～90%) of water, prepare the hydrogel of a series of compositions.
Embodiment 8, prepare supramolecular hydrogel
1) get the oxide/carbon nanometer tube aqueous solution that 0.5mL concentration is 4mg/mL, adding 0.5mL concentration is the carboxylated ferriferrous oxide nano-particle aqueous solution of 4mg/mL, then adds 1mL polyethylene polyamine, by system sealing and at 50 DEG C of heating in water bath 30s;
2) gained mixture, at 12 DEG C of constant temperature 6h, can obtain oxide/carbon nanometer tube/Z 250/polyethylene polyamine three component supramolecular hydrogels.
Then, according to above-mentioned steps, by the quality percentage composition (25%～90%) of regulation and control oxide/carbon nanometer tube and the total mass of carboxylated ferriferrous oxide nano-particle and the mass ratio of polyethylene polyamine (1:33～3500) and water, prepare the hydrogel of a series of compositions.
(oxide/carbon nanometer tube concentration is 0.1wt% to the hydrogel of a kind of composition prepared by this embodiment, Z 250 concentration is 0.1wt%, water content is 50wt%, and the total mass of oxide/carbon nanometer tube and carboxylated ferriferrous oxide nano-particle and the mass ratio of polyethylene polyamine are 1:250) digital photograph as shown in Fig. 2 (g).
The thermal stress responsiveness of embodiment 9, hydrogel
The thermoinducible gel-sol reversible transition of carbon nanotube/polyethylene polyamine supramolecular hydrogel that test implementation example 1 obtains: in the time that this hydrogel is placed in 55 DEG C, can change liquid state in 30s; Gained liquid can be replied as immobilising gel at 20 DEG C of standing 2min, and the digital photograph of above-mentioned transition process is shown in Fig. 5.
The near infrared light response of embodiment 10, hydrogel
The photoinduced gel-sol reversible transition of near infrared of carbon nanotube/polyethylene polyamine supramolecular hydrogel that test implementation example 1 obtains: when this supramolecular hydrogel is at pulse mode 1064nm laser, energy 6mJ, pulse-repetition 20ns, irradiates under 2min, changes liquid state into; Remove after laser, gained liquid can be replied as immobilising gel at 20 DEG C of standing 2min, and the digital photograph of above-mentioned transition process is shown in Fig. 6.
The potential of hydrogen response of embodiment 11, hydrogel
The gel-sol reversible transition of soda acid (pH value) induction of carbon nanotube/polyethylene polyamine supramolecular hydrogel that test implementation example 1 obtains: when this supramolecular hydrogel is under the effect of concentrated hydrochloric acid (volume ratio of gel and hydrochloric acid is 20:1), change liquid state in 3min; Gained liquid can be by adding and the potassium hydroxide of amount or the pressed powder of sodium hydroxide or the strong solution of hydrochloric acid same substance, stir, room temperature leaves standstill 5min, reply as immobilising gel, the corresponding digital photograph of above-mentioned transition process is shown in Fig. 7 (a), the chemical equation that Fig. 7 (b) is above-mentioned transformation mechanism.
The self-healing performance of embodiment 12, hydrogel
Characterize the self-healing character of gel by rheometer.
Carbon nanotube/polyethylene polyamine supramolecular hydrogel (oxide/carbon nanometer tube concentration is respectively 0.025wt%, 0.1wt%, 0.2wt% and 0.5wt%) of the different carbon nanotube concentration that embodiment 1 is obtained is placed in the test of carrying out shearing strain-recovery on cone-and-plate-rheometer, distortion shear-stress used is respectively 5Pa, 20Pa, 35Pa and 200Pa, while being recorded in shearing force periodical change, the storage modulus of gel and the changing conditions of out-of-phase modulus.Concrete outcome is shown in Fig. 8.As can be seen from this figure, gel is under large shear action, and storage modulus reduces rapidly, and after replying as little shearing force, storage modulus can be recovered rapidly, embodies self-healing behavior fast.
Macroscopical self-healing performance of embodiment 13, hydrogel
Carbon nanotube/polyethylene polyamine supramolecular hydrogel that embodiment 1 is obtained is directly stitched together section after cutting off again, and gel can again restore as a wholely in 2min, and can support self weight.Corresponding digital photograph is shown in Fig. 9.
Embodiment 14, hydrogel are as the application of binding agent
Carbon nanotube/polyethylene polyamine supramolecular hydrogel that embodiment 1 is obtained, as binding agent, is coated on the bottom surface of metal counterweight, afterwards by it by being pressed in Teflon substrate or substrate of glass, constant temperature 12h at 5 DEG C.Afterwards, device is placed upside down on iron stand, below hangs the hook code of specified weight, measures its adhesive power.At 12 DEG C, the adhesive power in Teflon substrate and substrate of glass is respectively 2.8N/cm
2(28kPa) and 3.7N/cm
2(37kPa).Corresponding digital photograph is shown in Figure 10.
Embodiment 15, gel are as the application of binding agent
Carbon nanotube/polyethylene polyamine supramolecular hydrogel that embodiment 1 is obtained, as binding agent, is coated on the bottom surface of metal counterweight, afterwards by it by being pressed in substrate of glass, constant temperature 12h at 5 DEG C.Afterwards, device is placed upside down on iron stand, below hanged hook code, making born power is 1.8N/cm
2(18kPa), respectively 12 DEG C, 22 DEG C with 35 DEG C at test the lasting time of weight bonding institute energy.Equally, in substrate of glass, load 1.8N/cm
2(18kPa) time, alternately 40 DEG C with 5 DEG C at constant temperature 30min test bonding institute can be lasting time (use all the time the gel being initially coated with as binding agent, additionally do not add gel midway), do many group circulations, impact with probe temperature on it, and binding agent recycle character.Experimental result is shown in Figure 11.Wherein, Figure 11 (a) is that the adhesivity that carbon nanotube/polyethylene polyamine supramolecular hydrogel temperature relies on characterizes, and this figure shows, raises with temperature, and the adhesive power of gel is index decreased; Figure 11 (b) is bonded in substrate of glass by metal counterweight and carries weight (power of bearing is 1.8N/cm
2), alternately constant temperature 30min at 5 DEG C and 40 DEG C, does multiple circulations, the weight obtaining like this in substrate, adhere to the figure that can the lasting time do experimental period, this figure shows, varies with temperature, to there is noticeable change in adhesive power, and this variation is completely reversibility.This also illustrates, this supermolecular gel, can Reusability as binding agent.
After tested, the supramolecular hydrogel that prepared by embodiment of the present invention 2-8 has same temperature response performance, near infrared light response performance, soda acid response performance, self-healing performance and the adhesive property of supramolecular hydrogel of preparing with embodiment 1.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a polycomponent supramolecular hydrogel, is characterized in that: described hydrogel is by containing the component of strong hydrogen bonding, forming containing component and the water of weak hydrogen bond;
The described component containing strong hydrogen bonding is one or more in oxide/carbon nanometer tube, graphene oxide, carboxylated ferriferrous oxide nano-particle and carboxylated Nano silver grain;
The described component containing weak hydrogen bond is polyethylene polyamine;
The mass ratio of the described component containing strong hydrogen bonding and the described component containing weak hydrogen bond is 1:33 ~ 3500;
In described polycomponent supramolecular hydrogel, the quality percentage composition of described water is 25% ~ 90%.
2. the preparation method of supramolecular hydrogel described in claim 1, comprises the steps:
(1) aqueous solution of the described component containing strong hydrogen bonding of preparation;
(2) in the aqueous solution of the described component containing strong hydrogen bonding, add the described component containing weak hydrogen bond and mix, obtaining suspension;
(3) described suspension is through leaving standstill and obtain described supramolecular hydrogel.
3. preparation method according to claim 2, is characterized in that: in the aqueous solution of the described component containing strong hydrogen bonding, the quality-volumetric concentration of the described component containing strong hydrogen bonding is 0.3 ~ 15 mg/mL.
4. according to the preparation method described in claim 2 or 3, it is characterized in that: in step (3), described standing temperature is 5
oc ~ 30
oc, the described standing time is 1min ~ 72h.
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