CN107759734A - High intensity supermolecule conducting hydrogel based on acryloyl group glycine amide and preparation method thereof - Google Patents
High intensity supermolecule conducting hydrogel based on acryloyl group glycine amide and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide and preparation method thereof, using monomer propylene acyl group glycine amide and the methyl propane sulfonic acid of 2 acrylamide of monomer 2 as comonomer, with poly- (3, 4 Ethylenedioxy Thiophenes) poly- (styrene sulfonic acid) be blend components, the carbon-carbon double bond on two kinds of monomers is triggered to carry out radical polymerization by initiator, and the synergy of hydrogen bond forms the hydrogel of physical crosslinking between the bisamide key carried with acryloyl group glycine amide side chain, make poly- (3, 4 Ethylenedioxy Thiophenes) poly- (styrene sulfonic acid) is entrained in gel network structure.The high intensity supramolecular hydrogel of the present invention, due to the synergy of hydrogen bond, not only preparation method is simple for this gel, and has very strong stretching and compression performance, selfreparing and thermoplastic function can be realized at higher temperatures, and have preferable electric conductivity and good biocompatibility.
Description
Technical field
The invention belongs to hydrogel direction in biological technical field, more specifically, is related to a kind of sweet with acryloyl group
Glutamine is hydrogel of matrix and preparation method thereof.
Background technology
Conductive hydrogel is a kind of functional form material for combining to form both conducting polymer and hydrogel, and it not only has
There is the soft moisture performance of hydrogel, and there is conducting function.Therefore, conductive hydrogel is in ultracapacitor, fuel cell, lithium electricity
The field such as pond and biology sensor has a wide range of applications.But the mechanical property of conductive hydrogel is poor, it is mainly reflected in weak
And crisp characteristic.In addition, in order that hydrogel conducting polymer be combined with each other, the preparation process of conductive hydrogel often compared with
For complexity.Therefore, above mentioned problem significantly limit application of the conductive hydrogel in the fields such as biomedical and electrochemistry.
At present, high-strength conductive hydrogel mainly has composite conducting hydrogel and dual network conductive hydrogel two types.
Composite conducting hydrogel refers to electrical-conductive nanometer material such as conductive-nano-fibers, CNT and graphene etc. being added to water-setting
Strengthen the mechanical property of conductive hydrogel in the network structure of glue.Dual network conductive hydrogel refers to hydrogel being immersed in and contained
Have in the solution of conductive elements, after reaching swelling equilibrium, trigger conductive elements to carry out oxidation polymerization, so as to be formed with gel-in-matrix
Dual network conductive hydrogel.Although composite conducting hydrogel and dual network conductive hydrogel can strengthen conduction to a certain extent
The mechanical property of hydrogel, but the preparation method of both conductive hydrogels relatively complicated (Qu B, Li J, Xiao H, et
al.Facile preparation and characterization of sodium alginate/graphite
conductive composite hydrogel[J].Polymer Composites,2015.).In addition, led for dual network
For electric hydrogel, because most of conducting polymer is insoluble in solvent, so causing working process difficult, while also can
Cause conductive component (Kishi R, Kubota K, Miura T, et the problem of distributing inhomogeneity in gel-in-matrix
al.Mechanically tough double-network hydrogels with high electronic
conductivity[J].Journal of Materials Chemistry C,2014,2(4):736-743.).Due to material
Self-repairability can help to extend material service life, therefore prepare with self-repairability conductive hydrogel also constantly by
To the favor of scholar.But it is still a kind of challenge to prepare the higher high-strength conductive hydrogel of self-repair efficiency.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide acryloyl group glycine amide/2- acrylamides -2-
Methyl propane sulfonic acid copolymer hydrogel and preparation method thereof, there is high intensity, selfreparing, thermoplasticity, biocompatibility and electric conductivity
Performance.
The technical purpose of the present invention is achieved by following technical proposals：
Acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels, with the sweet ammonia of monomer propylene acyl group
Acid amides and monomer 2- acrylamide-2-methyl propane sulfonics are comonomer, trigger the carbon carbon on two kinds of monomers double by initiator
Key to carry out radical polymerization, and between the bisamide key carried with acryloyl group glycine amide side chain hydrogen bond synergy shape
Into the hydrogel of physical crosslinking.
Moreover, the mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics for (15-
50)：1, preferably (16-49)：1.
The preparation method of acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels, by monomer third
Enoyl- glycine amide and monomer 2- acrylamide-2-methyl propane sulfonics dissolve under the conditions of aqueous phase, initiator are added, in anoxybiotic
Under the conditions of by initiator trigger monomer carbon-carbon double bond carry out radical polymerization.
Moreover, the mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics for (15-
50)：1, preferably (16-49)：1.
Moreover, the aqueous phase selection deionized water, or running water.
Moreover, the quality sum of two kinds of monomers and the ratio of aqueous phase quality are (1-1.5)：5.
Moreover, the dosage of the initiator is 3%-the 5% of two kinds of monomer mass sums.In actual use, can basis
Trigger effect selection two-component initiator, the dosage of each component initiator is 3%-the 5% of two kinds of monomer mass sums.
The free radical provided using initiator triggers two kinds of monomers to react.Wherein initiator can be selected in field of macromolecule polymerization
Thermal initiator under the conditions of conventional aqueous phase, such as ammonium persulfate (APS), potassium peroxydisulfate (KPS), tetramethylethylenediamine, Huo Zheguang
Initiator, such as 2- hydroxy-2-methyl -1- phenyl -1- acetone (Irgacure 1173).If selecting thermal initiator, head is needed
The oxygen in reaction system is excluded first with inert gas (such as nitrogen, argon gas or helium), to avoid its inhibition, then
According to the activity and dosage of initiator, reaction system is heated on the initiation temperature of initiator used and keeps considerably long
Time, such as more than 1h or longer (such as 1-48h, preferably 20-40 hours), to promote initiator to produce for a long time enough
Raolical polymerizable persistently occurs for more free radicals, initiation reaction system, the final hydrogel for preparing the present invention.If selection
Light trigger, wherein initiator have selected light trigger 2- hydroxy-2-methyl -1- phenyl -1- acetone (Irgacure 1173).
Transparent closed reaction vessel can have been selected, has triggered radical polymerization under conditions of ultraviolet light, due to light-initiated effect
Rate is higher than thermal initiation, because when the activity of initiator and dosage adjust irradiation time selected by, irradiation time can be shorter than thermal initiation
Heat time, such as 20 minutes or longer (30min-1h), so experimental period can be caused to subtract significantly relative to thermal initiation
It is few.
Moreover, the temperature for triggering polymerization is 20-25 DEG C of room temperature, polymerization reaction time is 24-30 hours.
In preparation scheme, after the completion of reaction, copolymer is taken out from reaction vessel, remove the list for not participating in reaction
After body, initiator, crosslinking agent and solvent, it is immersed in water until reaching swelling equilibrium and (such as immersion 7 days, is changed once every 12h
Water, reach swelling equilibrium).
High intensity supermolecule conducting hydrogel based on acryloyl group glycine amide, with monomer propylene acyl group glycine amide and
Monomer 2- acrylamide-2-methyl propane sulfonics are comonomer, with poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid)
For blend components, the carbon-carbon double bond on two kinds of monomers is triggered to carry out radical polymerization by initiator, and it is sweet with acryloyl group
The synergy of hydrogen bond forms the hydrogel of physical crosslinking between the bisamide key that aminoacyl amine side chain carries, and makes poly- (3,4- Asia second
Propylenedioxythiophene)-poly- (styrene sulfonic acid) is entrained in gel network structure.
Moreover, the mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics for (15-
50)：1, preferably (16-49)：1.
Moreover, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) is a kind of navy blue aqueous solution, city is selected
Purchase, viscosity is 120000-180000mPa.S, and solid content is 1-5% (i.e. purity), can be directly and dissolved with the water-soluble of monomer
Liquid uniformly mixes.
The preparation method of high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide, by monomer propylene acyl group
Glycine amide and monomer 2- acrylamide-2-methyl propane sulfonics dissolve under the conditions of aqueous phase, and with poly- (3,4- ethylenedioxy thiophenes
Fen)-poly- (styrene sulfonic acid) uniformly mixing, initiator is added, triggers the carbon-carbon double bond of monomer by initiator under anoxic condition
Radical polymerization is carried out, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) is entrained in gel network structure.
Moreover, the mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics for (15-
50)：1, preferably (16-49)：1.
Moreover, the aqueous phase selection deionized water, or running water.
Moreover, the quality sum of two kinds of monomers and the ratio of aqueous phase quality are (1-1.5)：5.
Moreover, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) addition is the 1%-10% of aqueous phase volume,
It is preferred that 5-8%.
Moreover, the dosage of the initiator is 3%-the 5% of two kinds of monomer mass sums.In actual use, can basis
Trigger effect selection two-component initiator, the dosage of each component initiator is 3%-the 5% of two kinds of monomer mass sums.
The free radical provided using initiator triggers two kinds of monomers to react.Wherein initiator can be selected in field of macromolecule polymerization
Thermal initiator under the conditions of conventional aqueous phase, such as ammonium persulfate (APS), potassium peroxydisulfate (KPS), tetramethylethylenediamine, Huo Zheguang
Initiator, such as 2- hydroxy-2-methyl -1- phenyl -1- acetone (Irgacure 1173).If selecting thermal initiator, head is needed
The oxygen in reaction system is excluded first with inert gas (such as nitrogen, argon gas or helium), to avoid its inhibition, then
According to the activity and dosage of initiator, reaction system is heated on the initiation temperature of initiator used and keeps considerably long
Time, such as more than 1h or longer (such as 1-48h, preferably 20-40 hours), to promote initiator to produce for a long time enough
Raolical polymerizable persistently occurs for more free radicals, initiation reaction system, the final hydrogel for preparing the present invention.If selection
Light trigger, wherein initiator have selected light trigger 2- hydroxy-2-methyl -1- phenyl -1- acetone (Irgacure 1173).
Transparent closed reaction vessel can have been selected, has triggered radical polymerization under conditions of ultraviolet light, due to light-initiated effect
Rate is higher than thermal initiation, because when the activity of initiator and dosage adjust irradiation time selected by, irradiation time can be shorter than thermal initiation
Heat time, such as 20 minutes or longer (30min-1h), so experimental period can be caused to subtract significantly relative to thermal initiation
It is few.
Moreover, the temperature for triggering polymerization is 20-25 DEG C of room temperature, polymerization reaction time is 24-30 hours.
In preparation scheme, after the completion of reaction, copolymer is taken out from reaction vessel, remove the list for not participating in reaction
After body, initiator, crosslinking agent and solvent, it is immersed in water until reaching swelling equilibrium and (such as immersion 7 days, is changed once every 12h
Water, reach swelling equilibrium).
After poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) uniformly mixes with two kinds of monomers, by drawing
Sending out agent triggers the unsaturated bond of acryloyl group glycine amide and 2- acrylamide-2-methyl propane sulfonics to carry out radical copolymerization,
Poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) is set successfully to be doped in gel three-dimensional network structure.Doping is different
The conductive hydrogel of poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) of volume is in neutral buffer (pH=
7.4) after reaching swelling equilibrium in, its electrical conductivity is average up to 0.749S/m~2.212S/m.
Application based on the supermolecule composite aquogel of acryloyl group glycine amide in 3D printing, it is sweet based on acryloyl group
The supermolecule composite aquogel of glutamine is acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels,
Or the high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide is (i.e. using poly- (3,4- ethylenedioxy thiophenes
Fen)-poly- (styrene sulfonic acid) carry out acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonics copolymerization of doping in situ
Hydrogel).
In the inventive solutions, after acryloyl group glycine amide and 2- acrylamide-2-methyl propane sulfonics are copolymerized
The intermolecular hydrogen bonding formed, destruction can be realized with restructuring so that two kinds of gels embody self-repairability and heat at high temperature
Plasticity., can be real at 80 DEG C~90 DEG C after the hydrogel of preparation reaches swelling equilibrium in neutral buffer (pH=7.4)
Existing Signa Gel selfreparing.
Prepare two kinds of hydrogels (acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels,
Or the high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide) reach swelling equilibrium in deionized water after,
It can be achieved at 80 DEG C-90 DEG C from gel to the transformation of colloidal sol, after colloidal sol is positioned over into 20-25 degrees Celsius of coolings of room temperature
It can again be molded, the effigurate gel of tool is can print into (i.e. using 3D printer using colloidal sol as original using 3D printer
Material is printed, and is then naturally cooled to room temperature and is realized gelation).Activated carbon is added in two kinds of hydrogels of collosol state simultaneously
Uniformly mixing, you can printed using 3D printer, then naturally cool to room temperature and realize gelation.The dosage of activated carbon is
1-the 10% of hydrogel quality, preferably 5-8%.
Compared with prior art, high intensity supramolecular hydrogel provided by the invention, with acryloyl group glycine amide and 2-
Acrylamide-2-methyl propane sulfonic is raw material, is triggered using ammonium persulfate and tetramethylethylenediamine and is prepared, due to hydrogen bond
Synergy, not only preparation method is simple for this gel, and has very strong stretching and compression performance, at higher temperatures can
Selfreparing and thermoplastic function are realized, and has preferable electric conductivity and good biocompatibility.Adulterating poly- (3,4- Asias
Ethylenedioxy thiophene)-poly- (styrene sulfonic acid) after, overall performance does not decline, and embodies more preferable electric conductivity, performance
Go out the premium properties for 3D printing.
Brief description of the drawings
Fig. 1 is the structural representation for the monomer propylene acyl group glycine amide (NAGA) that the present invention uses.
Fig. 2 is the acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels prepared in the present invention
Hydrogen nuclear magnetic resonance spectrogram.
Fig. 3 is the acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels prepared in the present invention
(undoped with curve 1) and doped acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogel (curves
2) thermoelectricity DXR laser capture microdissection Raman spectroscopy.
Fig. 4 is the acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels prepared in the present invention
The change in shape design sketch of (undoped with), wherein A represent stretching, and B represents compression, and C represents winding, and D, which is represented, to knot.
Fig. 5 is doped acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels in the present invention
Change in shape design sketch, wherein A represent stretching, B represent compression, C represent winding, D represent knot.
Fig. 6 is the acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels prepared in the present invention
It is to cut gel with scalpel that the schematic diagram of the selfreparing of (undoped with), wherein a, which represent,；It is that the gel being cut open exists that b, which is represented,
Selfreparing is realized under 90 degrees Celsius；It is that the later gel of selfreparing can be stretched that c, which is represented,；D represents later solidifying of selfreparing
Glue can be bent.
Fig. 7 is doped acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels in the present invention
Selfreparing schematic diagram, wherein a represent be to cut gel with scalpel；B representatives are the gels being cut open at 90 degrees Celsius
Under realize selfreparing；It is that the later gel of selfreparing can be stretched that c, which is represented,；D represents the later gel of selfreparing can be with curved
It is bent.Fig. 8 is to reach to be printed as TJU using 3D printer after swelling equilibrium in deionized water using the hydrogel for preparing of the present invention
The gel photograph of shape.
Fig. 9 is the hydrogel prepared using the present invention and reaches swelling equilibrium in deionized water, then is realized at 90 DEG C
After sol-gel transformation, it is blended with activated carbon, then reuses 3D printer and print the gel photograph with TJU shapes.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.In the embodiment of the present invention using medicine and
The conventional medication and equipment that instrument is commercially available or laboratory uses, monomer propylene acyl group glycine amide is with glycine amide hydrochloric acid
Salt and acryloyl chloride are raw material according to bibliography (Boustta M, Colombo P E, Lenglet S, et
al.VersatileUCST-based thermoresponsive hydrogels for loco-regional sustained
drug delivery[J].Journalof Controlled Release,2014,174:1-6) prepare and carried two acyls
The monomer propylene acyl group glycine amide (NAGA) of amine groups, and through nuclear-magnetism and it is infrared determined structure as shown in Figure 1, herein
Repeat no more.
Embodiment 1 prepares acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels
196mg acryloyl groups glycine amide and 4mg 2- acrylamide-2-methyl propane sulfonics are dissolved in going for 1000 μ L
In ionized water, then add 6mg ammonium persulfates and make its dissolving, finally add 6 μ L tetramethylethylenediamines.Mixed liquor is injected
In closed mould, 24h is maintained to ensure fully to trigger polymerization.Then turn on mould and take out gel, it is molten to be immersed in neutral buffered
In liquid PBS (pH=7.4) or deionized water reaches swelling equilibrium and (such as immersion 7 days, changes a water every 12h, reach molten
Swollen balance).Acryloyl group glycine amide be a kind of side chain carry bisamide key monomer, with 2- acrylamide -2- methyl-props
When sulfonic acid carries out radical copolymerization, acting synergistically for hydrogen bond forms the water of physical crosslinking between utilizing the bisamide key of side chain
Gel.Using hydrogen nuclear magnetic resonance spectrogram (1H NMR, 500MHz) demonstrate two kinds of monomers and realize copolymerization (PNAGA-co-
PAMPS), Figure of description 2 is referred to.
1H NMR spectras (hydrogen nuclear magnetic resonance spectrum) are to utilize deuterated water (D2O, also cry：Deuterium oxide；Deuterium-oxide；Heavy water) it is used as deuterium
For reagent, copolymer sample is dissolved in deuterated reagent, utilizes 500MHz Liquid NMR spectrometer (models：Varian
INOVA, VARIAN Oncology Systems's production) detected.Deuterium-oxide (D2O) specification is as follows：No. CAS：7789-20-0；Manufacturer：
(agent is by French CIL：Shanghai Bai Li bio tech ltd)；The sale producer of deuterated reagent：Beijing is permanent to think sharp science and trade
Co., Ltd.A, b, c in above-mentioned spectrogram spectrogram, d, e order are to turn left to mark successively from the right side：Chemical shift δ=1.7ppm
(Ha,-CH3)；- 2.1ppm (the H of δ=1.8b,-CH2-)；- 2.6ppm (the H of δ=2.4c,-CH-)；δ=3.3ppm (Hd,-CH2-
SO3H)；- 4.4ppm (the H of δ=4.1e,-NH-CH2-CONH2) ppm. can prove from the above analysis two kinds of monomers realize altogether
It is poly-.
Embodiment 2 prepares doped acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels
196mg acryloyl groups glycine amide and 4mg 2- acrylamide-2-methyl propane sulfonics are dissolved in going for 1000 μ L
In ionized water, 30 μ L poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) is added.Then 6mg persulfuric acid is added
Ammonium simultaneously makes its dissolving, finally adds 6 μ L tetramethylethylenediamines.Mixed liquor is injected in closed mould, maintain 24h to ensure
Fully trigger polymerization.Then turn on mould and take out gel, be immersed in neutral buffer PBS (pH=7.4) or deionized water
Reach swelling equilibrium (such as immersion 7 days, change a water every 12h, reach swelling equilibrium).Acryloyl group glycine amide is
A kind of side chain carries the monomer of bisamide key, can profit when carrying out radical copolymerization with 2- acrylamide-2-methyl propane sulfonics
The hydrogel of physical crosslinking is formed with the synergy of hydrogen bond between the bisamide key of side chain.
Poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) CAS：155090-83-8, Poly (3,4-
Ethylenedioxythiophene)-poly (styrenesulfonate), producer is sold：Tianjin Skien Si Aopu Deco skills
Co., Ltd, purity：1.3wt% (purity：1.3wt%dispersion in H2O).Poly- (3,4- Ethylenedioxy Thiophenes)-
Poly- (styrene sulfonic acid) is a kind of navy blue aqueous solution, mass fraction 1.3%, have high conductivity and can directly with it is molten
The aqueous solution for having monomer uniformly mixes, and triggers acryloyl group glycine amide and 2- acrylamide -2- methyl-prop sulphurs by initiator
The unsaturated bond of acid carries out radical copolymerization, it is successfully doped in gel three-dimensional network structure.
Utilize thermoelectricity DXR laser capture microdissection Raman spectrometer (english names：ThermoFisher DXR Raman
Microscope) characterized to adulterating front and rear hydrogel, excitation wavelength is fixed as 532 nanometers, sample test be it is powdered,
As shown in Figure 3.The mass ratio (NAGA/AMPS) of two kinds of monomers is 24, adulterates poly- (3,4- Ethylenedioxy Thiophene)-poly- (benzene
Vinyl sulfonic acid) content be 5%, be PNAGA-PAMPS/PEDOT/PSS-0-24 before doping, after doping according to the name in text
For PNAGA-PAMPS/PEDOT/PSS-5-24.It is located at 990cm in figure-1The absworption peak at place is oxygen in thiphene ring in PEDOT/PSS
The deformation vibration of ethene ring, positioned at 1365cm-1The absworption peak at place is thiphene ring Cα-CαStretching vibration, positioned at 1519cm-1The suction at place
It is C in thiphene ring to receive peakβ-CβStretching vibration, positioned at 1443cm-1The absworption peak at place is C in thiphene ringα=CβStretching vibration.
It can draw PEDOT/PSS characteristic absorption peak occur after gel doping PEDOT/PSS, it is possible to prove according to spectrogram
PEDOT/PSS is successfully doped with gel.
The Mechanics Performance Testing of embodiment 3
The mechanical property of two kinds of hydrogels of above-mentioned preparation is tested with the following method.Mechanics Performance Testing is in electronics ten thousand
It can carried out on testing machine (Jinan epoch Co., Ltd), the hydrogel before test is in neutral PBS cushioning liquid (pH=7.4)
Reach swelling equilibrium.The size of the sample of stretching mechanical property testing is 20mm × 10mm, and thickness is 500 μm, and rate of extension is
50mm/min；The sample size of Compressive Mechanical Properties test is diameter 10mm, high 8mm cylinder, compression speed 10mm/min.
The stretching of the front and rear hydrogel of doping and compressive strength can reach MPa rank；In addition, in order to vivider state mechanics
Performance, two kinds of gels are stretched, compressed, are wound and knotting is handled.
Acryloyl group glycine amide/2- acrylamide-2-methyl propane sulfonic copolymer hydrogels (undoped with) of preparation are entered
Row change in shape, and shot, as shown in Figure 4, wherein A represents stretching, and B represents compression, and C represents winding, and D is represented and beaten
Knot, shows good change in shape performance.To acryloyl group glycine amide/2- acrylamide -2- methyl-prop sulphurs of preparation
Sour copolymer hydrogel (undoped with) carries out change in shape, and is shot, and as shown in Figure 5, wherein A represents stretching, and B represents pressure
Contracting, C represent winding, D represent knot, show good change in shape performance, substantially with the change in shape undoped with state
Can be consistent.
The self-healing properties of embodiment 4
Profit detects the self-healing properties of two kinds of hydrogels of the present invention with the following method.Hydrogel before test is in neutrality
Reach swelling equilibrium in cushioning liquid (pH=7.4).Conductive hydrogel will be prepared to cut in half, then coagulate the two halves of incision
Glue is put into sealing container and heated 3 hours at a temperature of 90 DEG C, the gel finally cut can be fine to upper and fully contact
Ground is bonded together, and can't see interface.As seen in figs. 6 and 7, two kinds of hydrogels (undoped with it is doped) show
Basically identical property and state, i.e. hydrogel realize selfreparing, and repair the mechanics for keeping good afterwards and deformability (drawing
Stretch and bend).
The electric conductivity of embodiment 5
Profit detects the electric conductivity of hydrogel with the following method.Electrical performance testing is in electrochemical workstation (New Zealand
PGSTAT302N types electrochemical workstation) on tested using impedance method is crosslinked, the conductive hydrogel before test is slow in neutrality
Rush in solution (pH=7.4) and reach swelling equilibrium.The sample size of electrical performance testing is diameter 10mm, high 1mm sequin.
The cytotoxicity of embodiment 6
Profit detects the cytotoxicities of different hydrogels with the following method, in order to test hydrogel applied to biomaterial can
Can property.The gel film of various different ratios is soaked into 2h in 75% alcohol makes its sterilization, then with cushioning liquid PBS (pH
=7.4) wash, then Signa Gel is put into the bottom of 48 orifice plates.L cell kind is entered to above-mentioned 48 orifice plate
In, cultivate 48 hours.Original culture medium is then replaced by the culture medium containing Thiazolyl blue (MTT), in 37 DEG C and 5% CO2
Cultivated 4 hours under environment.Finally crystallized using 300 μ L dmso solutions bluish violets, after slight concussion 15min, use 490nm
Exciting light detect that cell survival rate has reached more than 70%, do not find significant cytotoxicity, test result indicates that
Mix and be respectively provided with good biocompatibility in front and rear gel.
The thermoplastic property of embodiment 7 and 3D printing
Profit detects the thermoplasticity of two kinds of hydrogels in the present invention with the following method.First by the PNAGA-PAMPS/ of preparation
PEDOT/PSS-10-24 gel samples are positioned in deionized water, reach swelling equilibrium.Then heating makes to coagulate at 90 DEG C
Glue is changed into the colloidal sol of flow regime, and the sample of TJU shapes is printed as by 3D printer, is placed under 20-25 degrees Celsius of room temperature
After cooling, plastic again, as shown in Figure 8.
In order to further give full play to the thermoplasticity of conductive hydrogel, the PNAGA-PAMPS/PEDOT/PSS- that will prepare
10-24 gel samples are positioned over reach swelling equilibrium in deionized water after, still at 90 DEG C heating make gel conversion for flowing
The colloidal sol of state, the activated carbon with electro-chemical activity that mass fraction is 10% is then added in colloidal sol, after being well mixed
The sample of TJU shapes is printed as by 3D printer again, after being placed in room temperature cooling, can plastic again, as shown in Figure 9.
3 printings are carried out after being blended according to the method described above with activated carbon using hydrogel PNAGA-PAMPS/PEDOT/PSS-0-24, can be made
Into the sample of the TJU shape consistent with shown in accompanying drawing 9.
Gel sample is named as PNAGA-PAMPS/PEDOT/PSS-X-Y, and wherein PNAGA-PAMPS represents two kinds of monomers third
Enoyl- glycine amide (NAGA) and 2- acrylamide-2-methyl propane sulfonics (AMPS) form copolymer, X represent doping it is poly- (3,
4- Ethylenedioxy Thiophenes)-the volume fraction of poly- (styrene sulfonic acid), Y represents acryloyl group glycine amide (NAGA) and 2- third
The mass ratio of acrylamide -2- methyl propane sulfonic acids (AMPS).
Following table is the various performance parameters of hydrogel sample：
Compressive strength：During measurement, gel, which is compressed to machine maximum range, can not also compress, so at using 90% strain
Stress is as intensity.
The preparation of hydrogel is carried out according to the content adjusting process parameter that the present application content part is recorded, before and after doping
Hydrogel show the property basically identical with embodiment.Exemplary description is done to the present invention above, it should explanation
It is that, in the case where not departing from the core of the present invention, any simple deformation, modification or other skilled in the art can
The equivalent substitution of creative work is not spent to each fall within protection scope of the present invention.
Claims (10)
1. the high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide, it is characterised in that with monomer propylene acyl group
Glycine amide and monomer 2- acrylamide-2-methyl propane sulfonics are comonomer, with poly- (3,4- Ethylenedioxy Thiophene)-poly-
(styrene sulfonic acid) is blend components, triggers the carbon-carbon double bond on two kinds of monomers by initiator to carry out radical polymerization, and
The synergy of hydrogen bond forms the hydrogel of physical crosslinking between the bisamide key carried with acryloyl group glycine amide side chain, makes
Poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) is entrained in gel network structure；Two kinds of monomer propylene acyl groups are sweet
The mass ratio of glutamine and 2- acrylamide-2-methyl propane sulfonics is (15-50)：1；Poly- (3,4- Ethylenedioxy Thiophenes)-it is poly-
(styrene sulfonic acid) viscosity is 120000-180000mPa.S, and solid content is 1-5%, and addition is that two are dissolved in preparation process
The 1%-10% of the aqueous phase volume of kind monomer.
2. the high intensity supermolecule conducting hydrogel according to claim 1 based on acryloyl group glycine amide, its feature
It is, the mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics is (16-49)：1；It is poly-
(3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) addition is that the aqueous phase volume of two kinds of monomers is dissolved in preparation process
5-8%.
3. the preparation method of the high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide, it is characterised in that will be single
Body acryloyl group glycine amide and monomer 2- acrylamide-2-methyl propane sulfonics dissolve under the conditions of aqueous phase, and with poly- (3,4- is sub-
Ethylenedioxy thiophene)-poly- (styrene sulfonic acid) uniformly mixing, initiator is added, monomer is triggered by initiator under anoxic condition
Carbon-carbon double bond carry out radical polymerization, poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) is entrained in gel net
In network structure；The mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics is (15-50)：
1；Poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) viscosity is 120000-180000mPa.S, solid content is 1-
5%, addition is the 1%-10% for the aqueous phase volume that two kinds of monomers are dissolved in preparation process.
4. the high intensity supermolecule conducting hydrogel according to claim 3 based on acryloyl group glycine amide, its feature
It is, the mass ratio of two kinds of monomer propylene acyl group glycine amides and 2- acrylamide-2-methyl propane sulfonics is (16-49)：1；It is poly-
(3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) addition is that the aqueous phase volume of two kinds of monomers is dissolved in preparation process
5-8%.
5. the high intensity supermolecule conducting hydrogel according to claim 3 based on acryloyl group glycine amide, its feature
It is, the aqueous phase selects deionized water, or running water.
6. the high intensity supermolecule conducting hydrogel according to claim 3 based on acryloyl group glycine amide, its feature
It is, the quality sum of two kinds of monomers and the ratio of aqueous phase quality are (1-1.5)：5.
7. the high intensity supermolecule conducting hydrogel according to claim 3 based on acryloyl group glycine amide, its feature
It is, the dosage of the initiator is 3%-the 5% of two kinds of monomer mass sums；Select two-component initiator, each component
The dosage of initiator is 3%-the 5% of two kinds of monomer mass sums.
8. the high intensity supermolecule conducting hydrogel according to claim 3 based on acryloyl group glycine amide, its feature
It is, the temperature for triggering polymerization is 20-25 DEG C of room temperature, and polymerization reaction time is 24-30 hours.
9. the high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide is as selfreparing as claimed in claim 1
The application of material.
10. the high intensity supermolecule conducting hydrogel based on acryloyl group glycine amide is as biology as claimed in claim 1
The application of material.
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| CN109880123A (en) * | 2019-01-31 | 2019-06-14 | 郑州轻工业学院 | A kind of preparation method of the stretchable conductive self-healing supramolecular hydrogel of high intensity |
| CN111320768A (en) * | 2020-03-13 | 2020-06-23 | 华南理工大学 | Preparation method of hydrogel strain sensor |
| CN114806057A (en) * | 2022-05-18 | 2022-07-29 | 东南大学 | Self-adhesion conductive organic gel and preparation method thereof |
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| CN1742056A (en) * | 2003-01-28 | 2006-03-01 | 凸版资讯股份有限公司 | Conductive polymer gel and process for producing the same, actuator, patch label for ion introduction, bioelectrode, toner, conductive functional member, antistatic sheet, printed-circuit member, cond |
| CN101602876A (en) * | 2009-06-23 | 2009-12-16 | 南京大学 | The multimeshed network compound water congealing glue material and the method for making thereof of high mechanical strength and electrochemical activity |
| CN104804115A (en) * | 2015-04-21 | 2015-07-29 | 天津大学 | High-strength supramolecular hydrogel and preparation method and application thereof |
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| CN1742056A (en) * | 2003-01-28 | 2006-03-01 | 凸版资讯股份有限公司 | Conductive polymer gel and process for producing the same, actuator, patch label for ion introduction, bioelectrode, toner, conductive functional member, antistatic sheet, printed-circuit member, cond |
| CN101602876A (en) * | 2009-06-23 | 2009-12-16 | 南京大学 | The multimeshed network compound water congealing glue material and the method for making thereof of high mechanical strength and electrochemical activity |
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| CN109880123A (en) * | 2019-01-31 | 2019-06-14 | 郑州轻工业学院 | A kind of preparation method of the stretchable conductive self-healing supramolecular hydrogel of high intensity |
| CN111320768A (en) * | 2020-03-13 | 2020-06-23 | 华南理工大学 | Preparation method of hydrogel strain sensor |
| CN114806057A (en) * | 2022-05-18 | 2022-07-29 | 东南大学 | Self-adhesion conductive organic gel and preparation method thereof |
| CN114806057B (en) * | 2022-05-18 | 2023-09-08 | 东南大学 | Self-adhesive conductive organic gel and preparation method thereof |
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