CN109749024A - A kind of conductive porous hydrogel and preparation method thereof - Google Patents
A kind of conductive porous hydrogel and preparation method thereof Download PDFInfo
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- CN109749024A CN109749024A CN201910072582.7A CN201910072582A CN109749024A CN 109749024 A CN109749024 A CN 109749024A CN 201910072582 A CN201910072582 A CN 201910072582A CN 109749024 A CN109749024 A CN 109749024A
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Abstract
The invention belongs to the technical field of hydrogel, a kind of conductive porous hydrogel and preparation method thereof is disclosed.The method: 1) carrying out high-speed stirred for methacrylic anhydride modified gelatin, carbon nanotube, acrylamide and initiator in PBS solution, obtains lotion；2) it is added into lotion and causes promotor, polymerization reaction obtains conductive porous hydrogel；The methacrylic anhydride modified gelatin: carbon nanotube: the mass ratio of acrylamide is (5~10): (0.5~3): (9~11).Method of the invention is simple, and any chemical cross-linking agent and organic solvent is not used in environmental protection, is conducive to the safety for improving material, hydrogel has good biocompatibility, and has excellent electric conductivity and good mechanical property；And the GelMA emulsion template that the present invention uses has extremely strong stability, can maintain the basic structure of lotion, in the polymerization conducive to the formation of porous aquagel.
Description
Technical field
The invention belongs to the technical fields of hydrogel, and in particular to a kind of conductive porous hydrogel and preparation method thereof.
Background technique
It forms stable lotion and is typically necessary addition surfactant, but these surfactants are certain often with having
Bio-toxicity limits application of the hydrogel of emulsion template preparation in field of biomedicine.To solve this problem, having must
Designing a kind of can realize the template of stable emulsion without adding auxiliary agent.Therefore, start to have developed many differences in recent years
The emulsion preparation method of mechanism, including freeze-drying, pore-foaming agent method, phase separation method and template.Template is divided into surface again
Surfactant templating method and emulsion template method.
Emulsion template method is similar with surfactant method, first prepares interphase emulsion template, after polymerizeing successfully and continuously
It is mutually separated with dispersed phase, then carries out processing removing template and obtain porous aquagel.By change the type of emulsion template, size,
The correlative factors such as shape, which are realized, controls the duct of porous material.However conventional emulsion method needed when preparing porous aquagel using
Organic solvent makees dispersed phase, not environmentally.
Make lotion no biotoxicity to realize, the present invention selects modified gelatin GelMA to prepare water packet sky as stabilizer
Gas (air-in-water) emulsion template, and enhance the mechanical property of gel by adding carbon nanotube (CNTs) and assign it
Electric conductivity.Any chemical cross-linking agent and organic solvent is not used in method of the invention, safety, environmental protection, the conductive porous water of preparation
Gel has excellent electric conductivity and good mechanical property.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of conductive porous hydrogel and
Preparation method.The present invention is stabilizer as emulsion template using methacrylic anhydride modified gelatin, passes through addition carbon nanotube
It polymerize to form a kind of compound porous conductive hydrogel material with biocompatibility with polymerizable function monomer.The present invention uses
Modified gelatin stablize water packet air lotion, prepare porous aquagel, can effectively solve conventional emulsion method prepare porous aquagel must
The problem of organic solvent must being used to make dispersed phase, and carbon nanotube enhances the mechanical property of gel and assigns its electric conductivity.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of conductive porous hydrogel, comprising the following steps:
1) methacrylic anhydride modified gelatin, carbon nanotube, acrylamide and initiator are carried out to high speed in PBS solution
Stirring obtains lotion；
2) it is added into lotion and causes promotor, polymerization reaction obtains conductive porous hydrogel.
Concentration of the carbon nanotube in PBS solution is 0.5%~3% (w/v), i.e., contains in the PBS solution of every 100mL
There is the carbon nanotube of 0.5~3g；
The methacrylic anhydride modified gelatin: carbon nanotube: the mass ratio of acrylamide is (5~10): (0.5~3):
(9~11)；
The dosage of the initiator is the 1~10% of acrylamide quality.
The promotor and the mass ratio of acrylamide of causing is (0.1~0.3): (9~11).
The initiation promotor is NaHSO3Or TEMED；NaHSO3It is added as a solution, NaHSO3In PBS solution
Concentration be 0.5%~1.5% (w/v).
The temperature of the polymerization reaction is 15~30 DEG C, and the time of polymerization reaction is 16~32h.
The rate of the high-speed stirred is 10000~16000rpm.
The initiator is potassium peroxydisulfate (K2S2O8)。
The pH of the PBS solution is 7.2~7.4.
The grafting rate of methacrylic anhydride modified gelatin (GelMA) is 50%~85%.
Methacrylic anhydride modified gelatin is to be modified to obtain to gelatin by methacrylic anhydride.
Methacrylic anhydride modified gelatin is prepared especially by following methods:
(S1) Gelatin is obtained by gelatin solution using PBS solution；(S2) methyl-prop is slowly added into gelatin solution
Olefin(e) acid acid anhydride, reaction, subsequent processing obtain methacrylic anhydride modified gelatin.
The amount ratio of the gelatin and methacrylic anhydride is (2~10) g:(5~20) mL.The gelatin and PBS solution
Amount ratio be (2~10) g:(20~100) mL.
The methacrylic anhydride is added in a manner of being added dropwise, and the speed of dropwise addition is 1-3mL/min；The temperature of the reaction
It is 40~60 DEG C, the time of reaction is 4~10h.After reaction, with PBS diluting reaction to terminate reaction.The subsequent processing
Refer to and the solution after reaction is dialysed, be centrifuged, take upper liquid, is freeze-dried.The bag filter of dialysis is bag filter (8-
14KDa), it is dialysed with water.The revolving speed of centrifugation is 3000~6000rpm.
The preparation method of the conductive porous hydrogel, specifically includes the following steps:
A) by carbon nanotube ultrasonic disperse in PBS solution, carbon nano tube dispersion liquid is obtained；
B) methacrylic anhydride modified gelatin is mixed, high speed homogenization with carbon nano tube dispersion liquid, obtains lotion；
C) acrylamide and initiator are added into lotion, is uniformly mixed, obtains mixed solution；
D) it is added into mixed solution and causes promotor, polymerization reaction obtains conductive porous hydrogel.
Methacrylic anhydride modified gelatin can be added as a solution in step b), when methacrylic acid anhydride modification is bright
When glue is added as a solution, solvent is PBS solution；Causing promotor in step c) can be added as a solution, when
When initiation promotor is added as a solution, solvent is PBS solution；
V (amount of PBS in methacrylic anhydride modified gelatin solution)+V (amount of PBS in carbon nano tube dispersion liquid)=VAlways, V
(amount of PBS in methacrylic anhydride modified gelatin solution) >=0, VAlwaysIndicate the volumetric usage of total PBS solution.
The revolving speed of step b) high speed homogeneous is 10000~16000rpm, and the time of high speed homogenization is 2~4min.
The conductive porous hydrogel is prepared by the above method.
Compared with prior art, the present invention has the advantage that
(1) any chemical cross-linking agent and organic solvent is not used in method of the invention, is conducive to the safety for improving material,
Hydrogel has good biocompatibility；
(2) the GelMA emulsion template that the present invention uses has extremely strong stability, can maintain lotion in the polymerization
Basic structure, conducive to the formation of porous aquagel；
(3) conductive porous hydrogel prepared by the present invention has excellent electric conductivity and good mechanical property；
(4) the interconnected degree of porous structure is high in hydrogel of the invention, is conducive to medium rapid dispersion, can be enhanced
The electrical property that carbon nanotube assigns, while there is certain mechanical stability.
There is conductive porous hydrogel prepared by the present invention open macroporous structure and higher porosity to be conducive to the expansion of substance
It dissipates and permeates.
Detailed description of the invention
Fig. 1 is the photo that embodiment 2 prepares CNT dispersion Yu CNT-GelMA lotion；
Fig. 2 is the swelling curve of conductive porous hydrogel prepared by embodiment 2,4 and 6；
Fig. 3 is the scanning electron microscope (SEM) photograph of conductive porous hydrogel inner porosity prepared by embodiment 2,4 and 6, wherein a1
~a3 is the SEM figure of hydrogel different amplification prepared by embodiment 6, and b1~b3 is conductive hydrogel prepared by embodiment 2
The SEM of different amplification schemes, and c1~c3 is the SEM figure of hydrogel different amplification prepared by embodiment 4；
Fig. 4 is the Mechanics Performance Testing curve of conductive porous hydrogel prepared by embodiment 2,4 and 6, and wherein a is stress-
Strain curve, b are compression modulus histogram.
Specific embodiment
The present invention is specifically described below with reference to embodiment, but protection scope of the present invention is not limited to following implementation
Example.
GelMA in each embodiment: the gelatin (Gelatin) for weighing 5g is added in PBS (pH=7.4) solution of 50mL,
The heating stirring half an hour at 50 DEG C, until gelatin is completely dissolved；It is slowly added to the methacrylic anhydride (MA) of 10mL, speed is added dropwise
Spend 1mL/min；Continue to be stirred to react 4h at 50 DEG C, after reaction, with the PBS diluting reaction of 200mL to terminate reaction；By institute
It obtains liquid to be placed in bag filter (8-14KDa), is used deionized water dialysis 7 days at 40 DEG C, change water daily twice, it is molten after dialysis
Liquid pours into centrifuge tube, is centrifuged 10min at 3,000 rpm, takes supernatant liquor, is lyophilized with freeze drier to get production is arrived
Object GelMA, yield 91%, acid anhydrides grafting rate 83%.
Embodiment 1
A kind of preparation method of porous, electrically conductive hydrogel, includes the following steps:
(1) by 0.025g carbon nanotube (CNTs) ultrasonic disperse in the PBS solution (PH=7.4) of 5mL, ultrasonic time is
1h obtains carbon nano tube dispersion liquid；
(2) GelMA, the high speed homogenization 4min at 16000rpm of 0.5g are added into carbon nano tube dispersion liquid, obtains steady
Determine lotion；
(3) 0.5g acrylamide monomer and 0.005gKPS are added into stable emulsion, stirs and evenly mixs, obtains mixed solution；
(4) 0.01g is added in step (3) resulting mixed solution and causes accelerant N aHSO3, seal, room temperature reaction is poly-
It closes 24 hours, obtains conductive porous hydrogel.
Embodiment 2
A kind of preparation method of porous, electrically conductive hydrogel, includes the following steps:
(1) by 0.05g carbon nanotube (CNTs) ultrasonic disperse in the PBS solution (PH=7.4) of 5mL, ultrasonic time is
1h obtains carbon nano tube dispersion liquid；
(2) GelMA, the high speed homogenization 4min at 16000rpm of 0.5g are added into carbon nano tube dispersion liquid, obtains steady
Determine lotion (CNT-GelMA lotion)；
(3) 0.5g acrylamide monomer and 0.005gKPS are added into stable emulsion, stirs and evenly mixs, obtains mixed solution；
(4) it is added in step (3) resulting mixed solution and causes accelerant N aHSO3(solvent is PBS solution to solution, should
Solution is by the PBS solution of 1mL and the NaHSO of 0.01g3Configure), it is more to obtain conduction for sealing, room temperature reaction polymerization 24 hours
Hole hydrogel.
Embodiment 3
A kind of preparation method of porous, electrically conductive hydrogel, includes the following steps:
(1) by 0.1g carbon nanotube (CNTs) ultrasonic disperse in the PBS solution (PH=7.4) of 5mL, ultrasonic time is
1h obtains carbon nano tube dispersion liquid；
(2) GelMA, the high speed homogenization 4min at 16000rpm of 0.5g are added into carbon nano tube dispersion liquid, obtains steady
Determine lotion；
(3) 0.5g acrylamide monomer and 0.005gKPS are added into stable emulsion, stirs and evenly mixs, obtains mixed solution；
(4) it is added in step (3) resulting mixed solution and causes accelerant N aHSO3(solvent is PBS solution to solution, should
Solution is by the PBS solution of 1mL and the NaHSO of 0.01g3Configure), it is more to obtain conduction for sealing, room temperature reaction polymerization 24 hours
Hole hydrogel.
Embodiment 4
A kind of preparation method of porous, electrically conductive hydrogel, includes the following steps:
(1) by 0.15g carbon nanotube (CNTs) ultrasonic disperse in the PBS solution (PH=7.4) of 5mL, ultrasonic time is
1h obtains carbon nano tube dispersion liquid；
(2) GelMA, the high speed homogenization 4min at 16000rpm of 0.5g are added into carbon nano tube dispersion liquid, obtains steady
Determine lotion；
(3) 0.5g acrylamide monomer and 0.005gKPS are added into stable emulsion, stirs and evenly mixs, obtains mixed solution；
(4) it is added in step (3) resulting mixed solution and causes accelerant N aHSO3(solvent is PBS solution to solution, should
Solution is by the PBS solution of 1mL and the NaHSO of 0.01g3Configure), it is more to obtain conduction for sealing, room temperature reaction polymerization 24 hours
Hole hydrogel.
Embodiment 5
A kind of preparation method of porous, electrically conductive hydrogel, includes the following steps:
(1) by 0.15g carbon nanotube (CNTs) ultrasonic disperse in the PBS solution (PH=7.4) of 5mL, ultrasonic time is
1h obtains carbon nano tube dispersion liquid；
(2) GelMA, the high speed homogenization 4min at 16000rpm of 0.25g are added into carbon nano tube dispersion liquid, obtains steady
Determine lotion；
(3) 0.5g acrylamide monomer and 0.005gKPS are added into stable emulsion, stirs and evenly mixs, obtains mixed solution；
(4) it is added in step (3) resulting mixed solution and causes accelerant N aHSO3(solvent is PBS solution (PH to solution
=7.4), the solution is by the PBS solution of 1mL and the NaHSO of 0.01g3Configure), sealing, room temperature reaction polymerization 24 hours,
Obtain conductive porous hydrogel.
Embodiment 6
A kind of preparation method of porous, electrically conductive hydrogel, includes the following steps:
(1) by the PBS solution (PH=7.4) of the GelMA of 0.5g and 5mL at 16000rpm high speed homogenization 4min, obtain
Stable emulsion；
(2) 0.5g acrylamide monomer and 0.005gKPS mixing are added in the lotion of step (1), obtains mixed solution；
(3) it is added in step (2) resulting mixed solution and causes accelerant N aHSO3(solvent is PBS solution to solution, should
Solution is by the PBS solution of 1mL and the NaHSO of 0.01g3Configure), sealing, room temperature reaction polymerization 24 hours obtains water-setting
Glue.
Performance test:
Fig. 1 is the photo that embodiment 2 prepares CNT dispersion Yu CNT-GelMA lotion；
Fig. 2 is the swelling curve of conductive porous hydrogel prepared by embodiment 2,4 and 6；
Fig. 3 is the scanning electron microscope (SEM) photograph of conductive porous hydrogel inner porosity prepared by embodiment 2,4 and 6, wherein a1
~a3 is the SEM figure of hydrogel different amplification prepared by embodiment 6, and b1~b3 is conductive hydrogel prepared by embodiment 2
The SEM of different amplification schemes, and c1~c3 is the SEM figure of hydrogel different amplification prepared by embodiment 4；
Fig. 4 is the Mechanics Performance Testing curve of conductive porous hydrogel prepared by embodiment 2,4 and 6, and wherein a is stress-
Strain curve, b are compression modulus histogram.
Claims (9)
1. a kind of preparation method of conductive porous hydrogel, it is characterised in that: the following steps are included:
1) methacrylic anhydride modified gelatin, carbon nanotube, acrylamide and initiator are subjected to high-speed stirring in PBS solution
It mixes, obtains lotion；
2) it is added into lotion and causes promotor, polymerization reaction obtains conductive porous hydrogel；
The methacrylic anhydride modified gelatin: carbon nanotube: the mass ratio of acrylamide is (5~10): (0.5~3): (9~
11)。
2. the preparation method of conductive porous hydrogel according to claim 1, it is characterised in that: the initiation promotor is
NaHSO3Or TEMED；The initiator is potassium peroxydisulfate；
The dosage of the initiator is the 1~10% of acrylamide quality；
The promotor and the mass ratio of acrylamide of causing is (0.1~0.3): (9~11).
3. the preparation method of conductive porous hydrogel according to claim 1, it is characterised in that:
Concentration of the carbon nanotube in PBS solution is 0.5%~3% (w/v), i.e., contains in the PBS solution of every 100mL
The carbon nanotube of 0.5~3g；
NaHSO3It is added as a solution, solvent is PBS solution；NaHSO3Concentration in PBS solution is 0.5%~1.5%
(w/v)。
4. the preparation method of conductive porous hydrogel according to claim 1, it is characterised in that: the temperature of the polymerization reaction
It is 15~30 DEG C, the time of polymerization reaction is 16~32h；
The pH of the PBS solution is 7.2~7.4；
The rate of the high-speed stirred is 10000~16000rpm.
5. the preparation method of conductive porous hydrogel according to claim 1, it is characterised in that: methacrylic acid anhydride modification is bright
The grafting rate of glue is 50%~85%；
Methacrylic anhydride modified gelatin is to be modified to obtain to gelatin by methacrylic anhydride.
6. the preparation method of conductive porous hydrogel according to claim 5, it is characterised in that: methacrylic acid anhydride modification is bright
Glue is prepared especially by following methods:
(S1) Gelatin is obtained by gelatin solution using PBS solution；(S2) methacrylic acid is slowly added into gelatin solution
Acid anhydride, reaction, subsequent processing obtain methacrylic anhydride modified gelatin；
The amount ratio of the gelatin and methacrylic anhydride is (2~10) g:(5~20) mL；The use of the gelatin and PBS solution
Amount is than being (2~10) g:(20~100) mL.
7. the preparation method of conductive porous hydrogel according to claim 6, it is characterised in that: the methacrylic anhydride with
The mode of dropwise addition is added, and the speed of dropwise addition is 1-3mL/min；The temperature of the reaction is 40~60 DEG C, time of reaction is 4~
10h。
8. the preparation method of conductive porous hydrogel according to claim 6, it is characterised in that: the subsequent processing refer to by
Solution after reaction is dialysed, and centrifugation takes upper liquid, is freeze-dried.
9. a kind of conductive porous hydrogel obtained by any one of claim 1~8 preparation method.
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Cited By (4)
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| CN110540658A (en) * | 2019-08-08 | 2019-12-06 | 天津大学 | acrylamide/carbon oxide nanotube-based nanocomposite hydrogel sensor and preparation method thereof |
| CN112704488A (en) * | 2020-12-11 | 2021-04-27 | 西安交通大学 | Wound damage state monitoring devices based on flexible ventilative hydrogel membrane |
| CN112979998A (en) * | 2021-02-24 | 2021-06-18 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Anisotropic conductive hydrogel and preparation method and application thereof |
| CN113527605A (en) * | 2021-07-22 | 2021-10-22 | 华南理工大学 | Tissue adhesion conductive porous hydrogel and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540658A (en) * | 2019-08-08 | 2019-12-06 | 天津大学 | acrylamide/carbon oxide nanotube-based nanocomposite hydrogel sensor and preparation method thereof |
| CN110540658B (en) * | 2019-08-08 | 2022-03-15 | 天津大学 | Acrylamide/carbon oxide nanotube-based nanocomposite hydrogel sensor and preparation method thereof |
| CN112704488A (en) * | 2020-12-11 | 2021-04-27 | 西安交通大学 | Wound damage state monitoring devices based on flexible ventilative hydrogel membrane |
| CN112704488B (en) * | 2020-12-11 | 2022-06-07 | 西安交通大学 | Wound damage state monitoring devices based on flexible ventilative hydrogel membrane |
| CN112979998A (en) * | 2021-02-24 | 2021-06-18 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Anisotropic conductive hydrogel and preparation method and application thereof |
| CN112979998B (en) * | 2021-02-24 | 2023-09-05 | 中科南京绿色制造产业创新研究院 | Anisotropic conductive hydrogel and preparation method and application thereof |
| CN113527605A (en) * | 2021-07-22 | 2021-10-22 | 华南理工大学 | Tissue adhesion conductive porous hydrogel and preparation method thereof |
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