CN109438728A - A kind of Thermo-sensitive conductive hydrogel and preparation method thereof of metallic ion coordination effect enhancing - Google Patents
A kind of Thermo-sensitive conductive hydrogel and preparation method thereof of metallic ion coordination effect enhancing Download PDFInfo
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- CN109438728A CN109438728A CN201811269721.7A CN201811269721A CN109438728A CN 109438728 A CN109438728 A CN 109438728A CN 201811269721 A CN201811269721 A CN 201811269721A CN 109438728 A CN109438728 A CN 109438728A
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Abstract
The present invention relates to a kind of preparation methods of the Thermo-sensitive conductive hydrogel of metallic ion coordination effect enhancing, belong to Thermo-sensitive conductive hydrogel technical field.The described method includes: (1) dissolves monomer vinyl imidazoles and n-isopropyl acrylamide in deionized water, then crosslinking agent, initiator, accelerator is added, it dissolves and carries out prepolymerization after mixing and obtain the hydrogel precursor of chemical crosslinking to fully reacting；(2) hydrogel precursor made from step (1) is taken out, be soaked in containing divalent metal zinc, copper, cobalt, nickel ion solution in be coordinated, then it is soaked in and removes the extra ion not being coordinated in water, and reach swelling equilibrium to get the Thermo-sensitive conductive hydrogel of metallic ion coordination.The invention firstly uses the reversible physical crosslinkings between metal ion and specific ligand, realize the regulation to gel mechanical strength, and gel has the Thermo-sensitive and electric conductivity of quick response.
Description
Technical field
The invention belongs to high-intensitive Thermo-sensitive conductive hydrogel technical fields more particularly to a kind of metallic ion coordination to act on
Thermo-sensitive conductive hydrogel of enhancing and preparation method thereof.
Background technique
Hydrogel is as a kind of soft material, because of its good biocompatibility and stimulating responsive, in material, crude drug
Equal numerous areas have received widespread attention.The application of hydrogel material is usually limited by two aspects, on the one hand due to water
The characteristics of gel material " soft " itself, intensity is often lower；On the other hand, the speed of response of many stimulating responsive gels compared with
Slowly, this extensive use for limiting hydrogel to a certain extent.Under normal circumstances, a large amount of when being absorbed in the network structure of hydrogel
Water, while showing good swelling behavior, mechanical property can weaken significantly.Therefore, if wanting to realize as the intracorporal class of biology
Gel tissue is the same, can have biggish intensity and higher load capacity, processing machinery high-intensitive water-setting of good performance
Glue becomes one of the research hotspot in the field.
Another design direction to hydrogel is the fast-response for realizing it, and Thermo-sensitive is in stimulating responsive material
A kind of very important property.Temperature sensing polymer at a certain temperature can as a kind of typical stimulating responsive polymer
Volume-phase transition occurs, to make it dissolve state change, this volume mutually changes the change from polymer water conjunction state.
If polymer solution shows single-phase when temperature is lower than a certain temperature, and while being higher than the temperature, occurs mutually to separate, then the temperature
It is the minimum point mutually separated on the concentration-temperature phasor of the polymer solution on curve, claims this polymer to have minimum
Consolute temperature (LCST).Conversely, referred to as highest consolute temperature (UCST).
Currently, some research and utilization metallic ion coordinations improve the performance of hydrogel, for example, patent application
201710299845.9 disclosing a kind of metallic ion coordination natural polymer/polyacrylic acid selfreparing gel process for preparing, benefit
It is reacted with natural polymer chitosan and polyacrylic acid, adds metal ion participation coordination and prepare good mechanical properties and have
The hydrogel of self-repair function.Complexation reaction directly occurs for hydroxyethyl cellulose, polyacrylic acid, metal ion, prepares green
Environmentally friendly, good mechanical properties selfreparing hydrogels.This method is prepared one kind of multiple physics using the method for easy environmental protection and is made
With the double-network hydrogel of combination, the physical action of these dynamic reversibles imparts the certain mechanical strength of hydrogel and good
Self-reparing capability.Composite hydrogel prepared by the present invention has self-repairability excellent under good mechanical property and room temperature
Energy.
Patent application 201710448483.5 discloses a kind of preparation method of metal coordination physics hydrogel thin film, packet
It includes: after monomer I (acrylic acid), monomer II (acrylamide or n-isopropyl acrylamide), potassium peroxydisulfate and deionized water mixing,
It is passed through inert gas, tetramethylethylenediamine is added after standing, places obtain polymer solution at room temperature, by polymer solution spin coating
On substrate, liquid film layer is obtained, liquid film layer, which is immersed in metal ion solution, obtains physical hydrogel film, by physical hydrogel
Film and substrate separation are impregnated in deionized water, and metal coordination (metal ion and acrylic acid) physical hydrogel film is obtained.
Patent application 201510778176.4 discloses a kind of be chemically crosslinked and complexing of metal ion (polyphenol and metal ion
Coordination) interpenetration network hydrogel preparation method, hydrogel be two kinds of networks being intertwined tangle and formed one kind
The continuous hydrogel of multiphase.This method is by utilizing amido-epoxide polymerization reaction controlling polymer chain tie point position sum number
The first converging network structure is made using click chemistry reaction in amount；Dopamine possesses good cell compatibility, bio-compatible
The good characteristics such as property.
It is above-mentioned that prepare that hydrogel utilizes is that (i.e. ligand is for coordination between metal ion and carboxyl, phenolic hydroxyl group
Oxygen-containing functional group), it is coordination mode common in the experiment of this field, the research of the coordination mode and mechanism have been relatively mature.
In addition, preparation method is cumbersome, high intensity obtained currently, preparing high intensity hydrogel often includes complicated organic synthesis step
Quickly and effectively response mechanism, application field are single for hydrogel shortage.Therefore, it is necessary to study a kind of new Thermo-sensitive conductivity waters
Gel and preparation method thereof.
Summary of the invention
For above-mentioned problems of the prior art, the present invention is intended to provide what a kind of effect of metallic ion coordination enhanced
Thermo-sensitive conductive hydrogel and preparation method thereof obtains relatively long strand the invention firstly uses chemical crosslinking, herein
On the basis of be crosslinked using the reversible physical between metal ion and imidazoles ligand, realize the stress dispersion of gel and keep solidifying
Glue elastomeric while stimuli responsive mechanism is introduced, makes gel that there is the Thermo-sensitive of quick response；And preparation of the invention
Method is simple, to material structure without destroying and the effective way controllable to crosslink density and the strength of materials.
An object of the present invention is to provide a kind of system of the Thermo-sensitive conductive hydrogel of metallic ion coordination effect enhancing
Preparation Method.
The second object of the present invention is to provide that the metallic ion coordination of the method for the present invention preparation is utilized to act on the temperature sensitive of enhancing
Property conductive hydrogel.
The third object of the present invention is to provide answering for the Thermo-sensitive conductive hydrogel of above-mentioned metallic ion coordination effect enhancing
With.
For achieving the above object, specifically, the invention discloses following technical proposals:
Firstly, the present invention discloses a kind of preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination, including as follows
Step:
(1) by monomer vinyl imidazoles and n-isopropyl acrylamide dissolution in deionized water, then be added crosslinking agent,
Initiator, accelerator, dissolution and carry out prepolymerization after mixing and obtain the hydrogel precursor of chemical crosslinking to fully reacting；
(2) hydrogel precursor made from step (1) is taken out, is soaked in containing divalent metal zinc, copper, cobalt, nickel ion
In be coordinated in any one solution, be then soaked in the ion that extra uncrosslinked coordination is removed in water, and reach molten
The swollen Thermo-sensitive conductive hydrogel balanced to get metallic ion coordination.
Preferably, the present invention provides a kind of method of purification of n-isopropyl acrylamide in step 1), specifically: 1) by N-
N-isopropylacrylamide is added in toluene, adds n-hexane after heating for dissolving, 2) filtrate is rested on to -20 DEG C of ring after filtering
Cooling 2h, then filters and obtains white crystal in border, and 3) repeat step 2) three times, by obtained product after 30 DEG C of vacuum drying
Sealing is put into refrigerator in 5 DEG C of environment, spare.
Poly(N-isopropylacrylamide) is that most representational substance, homopolymer are minimum total in temperature sensing polymer
Solubility temperature is at 32 DEG C or so.N-isopropyl acrylamide has hydrophilic amide groups and hydrophobic isopropyl simultaneously in structure
Base, this structure make it that reversible expansion-contraction variation can occur in LCST after polymerisation, are macroscopically presented as that hydrogel can
To realize the change of quick volume and transparency within the scope of room temperature, set so as to complete to hydrogel high intensity fast-response
Count target.
In step (1), the crosslinking agent is N, N '-methylene-bisacrylamide；The initiator ammonium persulfate；It is described to add
Fast agent is N, N, N', N'- tetramethylethylenediamine.
Preferably, in step (1), the monomer vinyl imidazoles: the mass ratio of n-isopropyl acrylamide is 1-5:1-
2, solid content 20-40%, chemical crosslinking degree are 0.2-0.4%.If solid content and chemical crosslinking are spent low, water-setting colloid is soft not
Easily molded, if height is spent in solid content and chemical crosslinking, hydrogel segment is shorter, causes hydrogel brittleness big and elastic small, thus
Become frangible, intensity is too low.
Preferably, in step (1), the molar fraction of the initiator and accelerator is monomer vinyl imidazoles total amount
0.2-3%.
Preferably, in step (1), the reaction temperature is 20-30 DEG C, and the reaction time is 20-28 hours.
Preferably, in step (2), the divalent metal zinc, copper, cobalt, nickel ion can be sulfate, nitrate or villaumite
Deng；Further preferably sulfate, concentration 10-90mol/L.
Preferably, in step (2), the soaking time twice is 6-12 hours, and coordination occurs in soaking process.
Preferably, in step (2), it is described twice impregnate when temperature be 20-30 DEG C.
Secondly, the present invention discloses the Thermo-sensitive conductive hydrogel of above method preparation metallic ion coordination effect enhancing.
Finally, the Thermo-sensitive conductive hydrogel that the present invention discloses above-mentioned metallic ion coordination is led in material, biology, medicine etc.
Application in domain.
The present invention utilizes the first transition metal ion Zn2+、Cu2+、Co2+、Ni2+The reversible metal ion-between imidazoles
Imidazoles coordination increases one layer of reversible physical crosslinking on the basis of hydrogel chemical crosslinking, can either realize stress point
It dissipates, the elasticity of gel also can be enhanced, to improve the intensity of hydrogel.
Specifically, the method for inherently improving intensity realizes foot while being mainly included in generation biggish deformation
The stress of amount disperses and elasticity with higher, the shape before enabling gel to restore deformation.Realize the mechanism of stress dispersion
Specifically include that (1) dual network gel, principle is broken using moieties chain to realize that stress disperses；(2) non-covalent friendship is utilized
Connection effect, such as the reversible crosslink of metallic ion coordination effect, hydrogen bond, hydrophobic interaction etc., the dispersion of Lai Shixian stress；It is non-total
Valence interaction is a kind of presence relative to covalent interaction, and covalent bond is the extensive chemical formed using share electron pair
Key, bond strength is big, cannot spontaneously form, and spontaneous can not rebuild after fracture.And noncovalent interaction is one kind in specified conditions
Spontaneous, lasting formation/decomposable process of lower experience.Therefore coordinate bond can be by of short duration destruction, external force after external force application
As long as ligand and central ion exist after disappearance, spontaneous can restore.The stress of a part is undertaken by the fracture of coordinate bond
Dispersion, can replace covalent cross-linking network and undertakes stress, so that the structure of material does not have the destruction of essence, because coordinate bond is disconnected
It can also be spontaneously formed after splitting, reset condition can be then returned to after hydrogel deformation, that is, maintain the integrality of material, macroscopic view
On be presented as hydrogel elasticity with higher and biggish intensity, (3) are using large biological molecule as material, including protein and more
Sugar etc. realizes that stress disperses using the length of variable molecular chain length or variable crosslinking segment.
Keeping the elastomeric method of hydrogel includes: that (1) using longer strand constructs interpenetrating networks, relative to shorter
Strand, it is not easy to break in deformation or solution crosslinking；(2) a more loose network is first constructed using chemical crosslinking, then
Increase crosslink density using reversible physical crosslinking, front and back can guarantee that the chemical structure of material is basically unchanged deformation occurs；
(3) more crosslinking points are constructed, a plurality of molecular chain length between two crosslinking points is different, unbroken after short chain is destroyed
Long-chain can still keep the elasticity of network；(4) construct the uniform network structure of molecular chain length, can to avoid length chain by
Power is uneven, reduces the inelastic deformation that can not restore.
The present invention is in order to realize that stress disperses, by that can enhance the elasticity of gel, to improve hydrogel
Intensity adds reversible physical crosslinking on this basis firstly, obtaining relatively long strand using chemical crosslinking to realize
The stress of gel disperses and keeps the high resiliency of gel, this is not only one kind and has both stress dispersion and keep the elastomeric side of gel
Method, and preparation method is simple, without destruction and controllable to crosslink density and the strength of materials to material structure.
Compared with prior art, the beneficial effect that the present invention obtains is:
(1) present invention is prepared for the water of a kind of conductive, regulatable mechanical performance and regulatable temperature sensitive performance
Gel.
(2) present invention adds infusion method using one-step polymerization, and reaction condition is mild, and preparation method is simple.
(3) present invention is excessively existing reversible metal ion-miaow between metal ion and imidazoles using four kind first
Azoles coordination site is coordinated, and the mechanical performance of gel is enhanced, and is changed the minimum consolute temperature of gel, is realized hydrogel height
Intensity, the design object of fast-response.
(4) it is compared with the traditional metal coordination mode mentioned in background technique content, imidazoles-transition that the present invention uses
The coordination (i.e. ligand is nitrogen-containing functional group) of metal ion belongs to the important coordination of the intracorporal one kind of biology, and this
Invention compares the difference of four kinds of coordination abilities between the first transition metal ion and imidazoles, the four kinds of hydrogels prepared
Mechanical performance is enhanced, and, wherein Zn effectively controllable to the crosslink density and mechanical performance of gel is realized2+It is coordinated with imidazoles
Its mechanical strength of hydrogel afterwards, which is not coordinated, has obtained highly significant with the hydrogel after the coordination of other three metal ion species
It is promoted.It is that transition metal ions atomic number itself is close, outer electronic structure is close due to four kind first, and present invention discover that
So similar ion can but generate visibly different reinforcing effect after coordination, and it is compared and is explained.Meanwhile
The preparation method of this hydrogel proposed by the present invention is simple, avoids such as organic synthesis step complicated in above-mentioned " click chemistry "
Suddenly, it is only necessary to the method for a step typical polymerization and immersion.
(5) coordination mode traditional described in part with respect to the background art, present invention finds only by changing metal
The type of ion can generate this ligand of vinyl imidazole of the difference of gel mechanical strength.
(6) present invention is copolymerized using with monomer n-isopropyl acrylamide, is the machine in order to utilize its Thermo-sensitive, with enhancing
Tool performance combines, and is prepared for such a hydrogel for having both high intensity and quick temperature-responsive, substantially increases water-setting
The application value of glue.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the infrared spectrogram of hydrogel prepared by embodiment 1.
Fig. 2 is that the balance of the hydrogel of different chemical crosslinking densities after dissimilar metals ion coordination in embodiment 1 contains
Water.
Fig. 3 is the scanning electron microscope image of hydrogel prepared by embodiment 1.
Fig. 4 is the load-deformation curve in embodiment 1 after different metal ions coordination when hydrogel progress compression test.
Fig. 5 is that hydrogel prepared by embodiment 1 shows transparency variation with temperature under room temperature and body temperature.
Fig. 6 a is that hydrogel electric conductivity prepared by embodiment 1 changes the photo that electric conductivity variation is presented with external force.
Fig. 6 b is that hydrogel electric conductivity prepared by embodiment 1 changes presentation curent change with external force.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, if wanting to realize as biological intracorporal gellike tissue, can have biggish
Intensity and higher load capacity, processing machinery high intensity hydrogel of good performance, become the field research hotspot it
One.Therefore, the present invention proposes a kind of Thermo-sensitive conductive hydrogel and preparation method thereof of metallic ion coordination effect enhancing, below
In conjunction with the drawings and the specific embodiments, the present invention is described further.
It should be noted that A-B-X%-Y-ZmM represents the hydrogel of different ratio in the following example and attached drawing,
Middle A-B is the mass ratio of monomer vinyl imidazoles (VIM) and n-isopropyl acrylamide monomer (NIPAM), and X% representative centainly rubs
The crosslinking agent of your score, Y represent the type of metal ion, and Z mM represents the concentration of metal ion soak.
Embodiment 1
1, it purifies n-isopropyl acrylamide: weighing 5g n-isopropyl acrylamide, be added in 8ml toluene, be heated to 50
DEG C dissolution, is added 25ml n-hexane, rests on filtrate after suction filtration in -20 DEG C of environment, filter after two hours and obtain white crystalline substance
30 DEG C of product obtained are dried in vacuo by body in triplicate, and sealing is put into spare in 5 DEG C of refrigerators.
2, the preparation method of the Thermo-sensitive conductive hydrogel of a kind of metallic ion coordination, includes the following steps:
(1) n-isopropyl acrylamide of the present embodiment purification and monomer vinyl imidazoles 2:5 in mass ratio are dissolved in
In deionized water, solid content 30%, chemical crosslinking degree is 0.3%., then add according to the 0.3% of monomer total amount molar fraction
Add crosslinking agent N, N '-methylene-bisacrylamide, according to monomer total amount molar fraction 1.0% addition initiator ammonium persulfate and
Accelerator N, N, N', N'- tetramethylethylenediamine, dissolution and after mixing in 25 DEG C of reactions progress prepolymerization in 24 hours, to anti-
The hydrogel precursor of chemical crosslinking should be obtained completely；
(2) hydrogel precursor made from step (1) is taken out, is divided into 4 groups, a kind of every group of metal ion solution of correspondence,
By this 4 groups of hydrogel precursors be separately immersed in containing zinc sulfate, copper sulphate, cobaltous sulfate, nickel sulfate aqueous solution (metal ion
Concentration is 50mM) in 12h be coordinated (25 DEG C of temperature), be then soaked in 12h in 25 DEG C of water and remove extra uncrosslinked match
The ion of position, and reach swelling equilibrium to get the Thermo-sensitive conductive hydrogel of 4 groups of different metallic ion coordinations: 2-5-
0.3%-Zn2+- 50mM, 2-5-0.3%-Cu2+- 50mM, 2-5-0.3%-Co2+- 50mM, 2-5-0.3%-Ni2+-50mM。
In the present embodiment and attached drawing, A-B-X%-Y-ZmM represents the hydrogel of different ratio, and wherein A-B is monomer ethylene
The mass ratio of base imidazoles (VIM) and n-isopropyl acrylamide monomer (NIPAM), X% represent the crosslinking agent of certain molar fraction,
Y represents the type of metal ion, and Z mM represents the concentration of metal ion soak.
Comparative example 1
As the comparative example of embodiment 1, deionization is only soaked in after the hydrogel precursor prepared in step (2) is taken out
In water, the other conditions of immersion are identical to get being expressed as 2-5-0.3%-H2O。
Embodiment 2
A kind of preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination, includes the following steps:
(1) n-isopropyl acrylamide of the present embodiment purification and monomer vinyl imidazoles 1:1 in mass ratio are dissolved in
In deionized water, solid content 40%, chemical crosslinking degree is 0.4%, then according to 0.2% addition of monomer total amount molar fraction
Crosslinking agent N, N '-methylene-bisacrylamide adds initiator ammonium persulfate according to the 1.0% of monomer total amount molar fraction and adds
Fast agent N, N, N', N'- tetramethylethylenediamine, dissolution and after mixing in 30 DEG C of reactions progress prepolymerization in 20 hours, wait react
Completely, the hydrogel precursor of chemical crosslinking is obtained；
(2) hydrogel precursor made from step (1) is taken out, is soaked in 6h in the aqueous solution that concentration is 10mM cobalt chloride
It is coordinated (30 DEG C of temperature), 6h in 30 DEG C of water is then soaked in and removes the ion of extra uncrosslinked coordination, and reach swelling
Balance the Thermo-sensitive conductive hydrogel to get metallic ion coordination.
Embodiment 3
A kind of preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination, includes the following steps:
(1) n-isopropyl acrylamide of the present embodiment purification and monomer vinyl imidazoles 3:2 in mass ratio are dissolved in
In deionized water, solid content 20%, chemical crosslinking degree is 0.2%, then according to 2.0% addition of monomer total amount molar fraction
Crosslinking agent N, N '-methylene-bisacrylamide adds initiator ammonium persulfate according to the 3.0% of monomer total amount molar fraction and adds
Fast agent N, N, N', N'- tetramethylethylenediamine, dissolution and after mixing in 20 DEG C of reactions progress prepolymerization in 28 hours, wait react
Completely, the hydrogel precursor of chemical crosslinking is obtained；
(2) hydrogel precursor made from step (1) is taken out, is soaked in 10h in the zinc nitrate aqueous solution of 90mM and carries out
It is coordinated (20 DEG C of temperature), is then soaked in 10h in 20 DEG C of water and removes the ion of extra uncrosslinked coordination, and it is flat to reach swelling
It weighs to get the Thermo-sensitive conductive hydrogel (3-2-2%-Y-90mM) of metallic ion coordination.
Performance test:
(1) hydrogel that embodiment 1, comparative example 1 are prepared is tested, infrared spectrum characterization as shown in Figure 1,
Wherein 3448cm-1Locate it is corresponding be n-isopropyl acrylamide N-H stretching vibration peak；1385cm-1Locate corresponding to be N- isopropyl
- CH on base acrylamide3Flexural vibrations peak；1634cm-1Locate corresponding to be C=N stretching vibration peak on imidazole ring.Thus table
Bright, the present invention is successfully prepared copolymer aquagel.After metal ion and imidazole ring are coordinated, the stretching vibration peak of C=N
1554cm is moved to low frequency-1Place, this is because the introducing of metal ion, produces certain influence to the absorption of C=N double bond,
Caused by the outer-shell electron of transition metal may participate in weak conjugation, thus prove that the present invention successfully synthesizes and the metal ion of double cross connection is matched
The Thermo-sensitive conductive hydrogel of position.
(2) it is flat to measure it for the hydrogel that different metal ions coordination is prepared to embodiment 1, comparative example 1 at room temperature
Weigh water content, method particularly includes: the water for reaching the hydrogel sample excess surface of water suction balance is carefully dried with filter paper, in electronics
Its weight m is weighed on assay balancewet, then 50 DEG C vacuum drying 24 hours after measure its dry weight mdry.To the water of every kind of ratio
Gel takes three sample measurements, is averaged.The equilibrium moisture content calculation method of hydrogel are as follows:
Equilibrium moisture content (EWC) %=(mwet- mdry)/mwet* 100%.
By test, the equilibrium moisture content of the hydrogel that embodiment 1, comparative example 1 obtain as shown in Fig. 2, different metal from
Gel equilibrium moisture content after son impregnates is different, according to the following sequence Ni of equilibrium moisture content having from high to low2+>Co2+>Cu2+>
H2O>Zn2+。
As can be seen that hydrogel equilibrium moisture content generates difference after different metal ions coordination, the main reason is that due to
The coordination mode and coordination ability of different metal ions have differences, so that the crosslink density of hydrogel generates difference, and then lead
Cause the difference of equilibrium moisture content.Precisely due to difference existing for this coordination mode and coordination ability, so that the water of different component
Gel has different mechanical performance reinforcing effects.
(3) 2-5-0.3%-Zn that embodiment 1 is obtained2+- 50mM hydrogel is observed under a scanning electron microscope, as a result
As shown in Figure 3, it will thus be seen that the microstructure of the hydrogel is more uniform close porous structure, and aperture size is less than 1
μm, and aperture and pore size distribution are uniform, and close structure, so that material structure is uniform, more conducively average dispersive stress improves machine
Tool performance (if hole is unevenly close, can make the structure of the different parts of material different, meeting different to the ability of stress dispersion
Generate stress to concentrate, stress raiser, material is easily destroyed) avoid material from generating stress in fault location concentrating, caused by bear
Loading capability decline, material are destroyed.
(4) hydrogel and the load-deformation curve of comparative example 1 after the different metal ions coordination obtained to embodiment 1
It is tested, as a result as shown in figure 4, as can be seen from the figure: after metallic ion coordination, being handed over due to being added to reversible coordination
Connection realizes stress dispersion, and the compressive strength of obtained hydrogel is all larger than not coordination cross-linked gel, and intensity sequence is
Zn2+>Cu2+>Co2+≈Ni2+>H2O.Wherein, 2-5-0.3%-Zn2+The intensity amplification of the hydrogel of -70mM is maximum, compressive strength
It can achieve 4638.17kPa.This explanation is relative to the coordination between other metal ions and imidazoles, Zn2+Matching between imidazoles
Position crosslinking can greatly enhance hydrogel compressive strength, effectively realize stress dispersion, keep the high resiliency of gel, realize system
The purpose of standby high intensity hydrogel.The coordination mode and coordination ability of different metal ions have differences, so that the friendship of hydrogel
Join density and generate difference, and then lead to the difference of equilibrium moisture content, just because of existing for this coordination mode and coordination ability
Difference, so that the hydrogel of different component has different mechanical performance reinforcing effects.
(5) 2-5-0.3%-Zn that embodiment 1 is obtained2+The Thermo-sensitive response of -50mM hydrogel is tested, as a result such as
Shown in Fig. 5, as can be seen from the figure: transparence is presented in hydrogel at room temperature, becomes opaque with finger touching 1min, by
Volume contraction has partial moisture and is extruded after heating, restore to after room temperature can fast quick-recovery its transparency, illustrate the gel
LCST between room temperature and body temperature, and respond rapidly, utility value with higher.
(6) 2-5-0.3%-Zn that embodiment 1 is obtained2+The electric conductivity response of -50mM hydrogel is tested, as a result such as
Shown in Fig. 6, as can be seen from the figure: due in hydrogel containing can be with free-moving zwitterion, and machine with higher
Tool intensity, can bear a degree of stretching, and responsiveness is presented with the change of external force in conductive capability.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for those skilled in the art
For member, various changes and changes are possible in this application.Within the spirit and principles of this application, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination, characterized by the following steps:
(1) in deionized water by monomer vinyl imidazoles and n-isopropyl acrylamide dissolution, crosslinking agent is then added, causes
Agent, accelerator, dissolution and carry out prepolymerization after mixing and obtain the hydrogel precursor of chemical crosslinking to fully reacting；
(2) hydrogel precursor made from step (1) is taken out, is soaked in containing in divalent metal zinc, copper, cobalt, nickel ion
It is coordinated in the solution of one kind of anticipating, is then soaked in the ion for removing extra uncrosslinked coordination in water, and it is flat to reach swelling
It weighs to get the Thermo-sensitive conductive hydrogel of metallic ion coordination.
2. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
Suddenly in (1), the crosslinking agent is N, N '-methylene-bisacrylamide；The initiator ammonium persulfate；The accelerator be N, N,
N', N'- tetramethylethylenediamine.
3. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
Suddenly in (1), the monomer vinyl imidazoles: the mass ratio of n-isopropyl acrylamide be 1-5:1-2, solid content 20-40%,
Chemical crosslinking degree is 0.2-0.4%.
4. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
Suddenly in (1), the molar fraction of the initiator and accelerator is the 0.2-3% of monomer vinyl imidazoles total amount.
5. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
Suddenly in (1), the reaction temperature is 20-30 DEG C, and the reaction time is 20-28 hours.
6. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
Suddenly in (2), the divalent metal zinc, copper, cobalt, nickel ion can be sulfate, nitrate or villaumite etc.；Further preferably sulphur
Hydrochlorate, concentration 10-90mol/L.
7. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
It is rapid 1) in, the method for purification of n-isopropyl acrylamide are as follows:
1) n-isopropyl acrylamide is added in toluene, n-hexane is added after heating for dissolving；
2) filtrate is rested on to cooling 2h in -20 DEG C of environment after filtering, then filters and obtains white crystal；
3) it repeats step 2) three times, obtained product is sealed after 30 DEG C of vacuum drying and is put into refrigerator in 5 DEG C of environment, it is standby
With.
8. the preparation method of the Thermo-sensitive conductive hydrogel of metallic ion coordination as described in claim 1, it is characterised in that: step
Suddenly in (2), the soaking time twice is 6-12 hours；Preferably, in step (2), it is described twice impregnate when temperature it is equal
It is 20-30 DEG C.
9. the Thermo-sensitive conductive hydrogel of the metallic ion coordination of the method according to claim 1 preparation.
10. the Thermo-sensitive conductive hydrogel of metallic ion coordination as claimed in claim 9 is in material, biology, field of medicaments
Application.
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