CN106866993B - Compound self-healing hydrogel of a kind of macromolecule based on nano thin-layer curing molybdenum sheet and preparation method thereof - Google Patents
Compound self-healing hydrogel of a kind of macromolecule based on nano thin-layer curing molybdenum sheet and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to polymeric biomaterial technical field, a kind of compound self-healing hydrogel of the macromolecule based on nano molybdenum disulfide piece and preparation method thereof is provided.The composite hydrogel is formed and light-initiated click-reaction occurs in nano thin-layer curing molybdenum sheet aqueous solution.The click-reaction is that the unsaturated double-bond in methacrylic acid anhydridization gelatin occurs under ultraviolet radiation with the sulfydryl in four arm sulfydryl polyvinyl alcohol.The self-healing performance is that material realizes self-healing purpose and making hydrogel heat up using the photothermal conversion characteristic of nano thin-layer curing molybdenum sheet under near infrared light.Nanometer two-dimensional material curing molybdenum sheet is applied to self-healing material field by the present invention, and assigns the quick healing properties under the conditions of material light stimulus.
Description
Technical field
The invention belongs to polymeric biomaterial technical fields more particularly to a kind of based on nano thin-layer curing molybdenum sheet
Compound self-healing hydrogel of macromolecule and preparation method thereof.
Background technique
Self-healing material is the inspiration by the Nature, and the healing of mimic biology bulk damage is mended by substance supply or energy
To mechanism, a kind of emerging biomimetic material for enabling the micro-damage of material to be able to heal automatically.
Currently, composite hydrogel, Nanometer composite hydrogel have had very big progress in self-healing field, usually by
Unmixing organic (polymer) and inorganic constituents (clay/particle) and complicated (nanoscale) structural body form.McKee etc.
(Adv.Funct.Mater.2014,24,2706) a kind of Nanometer composite hydrogel is prepared for by host-guest interaction and had
There is excellent self-healing performance (the self-healing time is less than 10s).Spoljaric etc. (Eur.Polym.J.2014,56,105) is logical
It crosses mixing nanofibrillated cellulose (NFC), polyvinyl alcohol (PVA), borax and has synthesized Nanometer composite hydrogel, have excellent
Self-healing performance, self-healing performance are to be caused by the recombination of hydrogen bond, and hydrogel will be also substantially improved in the presence of hydrogen bond
Mechanical performance.In addition, Duan etc. (J.Nanomater.2015,10,1155) is by one kind by Cellulose nanocrystal palpus, acryloyl
The hydrogel of the compositions such as amine, octadecyl methacrylate can realize the self-healing of gel by the dissociation and recombination of hydrophobicity micella
Close performance.But these self-healing hydrogels have certain bio-toxicity, and mechanical performance is unable to satisfy actual use and needs
It asks.
In recent years, two-dimension nano materials are gradually shown up prominently in self-healing material preparation field, especially graphene conduct
Important component constructs the extensive concern that nano combined self-healing material causes people, Cui etc. (J.Mater.Chem.A.2015,
3,17445) by graphene oxide layer by with the method that polyacrylamide is physical crosslinking be prepared for it is a kind of mix hydrogel,
The maximum stretching force born can achieve 243kPa, and draw ratio can reach 199 times, and can be in no any extraneous item
Part completes self-healing in the case where exciting.Its self-healing effect is by macromolecular chain in broken interface phase counterdiffusion and high score
Subchain passes through broken interface and is mutually wound, then between acrylamide chain and chain, acrylamide and graphene oxide it
Between re-form hydrogen bond and complete.Zhong etc. (J.Mater.Chem.B.2015,3,4001) is by stannic oxide/graphene nano piece
The composite hydrogel and Fe that layer is formed with polyacrylamide3+Crosslinking, makes material be provided with self-healing characteristics.But graphite at present
Alkene is realized there are no method and is mass produced, therefore the higher cost of the self-healing hydrogel based on graphene, is not suitable for big rule
Mould production and popularization.
A kind of two-dimensional material of the nano thin-layer curing molybdenum sheet as class graphene has very strong suction in solar spectrum region
Receipts ability has a good application prospect in photocatalysis and photovoltaic art.In numerous stratified materials, MoS2(molybdenum disulfide) is
Very special, it has unique excellent properties in terms of heat, power, light, electricity.MoS2There are good light absorption and photoluminescent property,
And its luminescence generated by light can become by force with the reduction of its number of plies, work as MoS2Shine most strong (Nano when nanometer sheet is single layer
Lett.2010,10,1271).In order to solve, biology of the existing technology is incompatible, mechanical strength is low, the technologies such as at high cost are asked
Topic, the present invention is based on the excellent photothermal conversion effect of nano thin-layer curing molybdenum sheet, good electric conductivity and biggish specific surfaces
The features such as product, constructs nano molybdenum disulfide piece-macromolecule composite hydrogel of self-healing function admirable, realizes it in self-healing material
Expect the popularization and application of preparation field.
Summary of the invention
In view of the above technical problems existing in the prior art, the present invention provides a kind of based on nano thin-layer curing molybdenum sheet
Two-dimensional material nano material thin layer curing molybdenum sheet is applied to by compound self-healing hydrogel of macromolecule and preparation method thereof for the first time
Self-healing material field, the photothermal conversion characteristic using nano thin-layer curing molybdenum sheet make material make water through near infrared light
Hydrogel warms cause the methacrylic acid glycosidation gelatin chains of its internal Thermo-sensitive to generate mobility, to realize self-healing
Purpose.Since material therefor of the present invention all has good biocompatibility and hypotoxicity, this material is expected to have good
Biologic applications prospect.It is described that technical scheme is as follows:
The present invention provides a kind of compound self-healing hydrogel of the macromolecule based on nano thin-layer curing molybdenum sheet, the high score
Sub- hydrogel is synthesized by nano thin-layer curing molybdenum sheet, methacrylic acid anhydridization gelatin, four arm sulfydryl polyvinyl alcohol, four arm sulfydryls
Polyvinyl alcohol and methacrylic acid anhydridization gelatin are reacted in curing molybdenum sheet aqueous solution, and four arm sulfydryl polyethylene
The strand of the part end sulfydryl of alcohol and methacrylic acid anhydridization gelatin has occurred light-initiated click-reaction and is bound up, connection
The strand of knot together is wound with equally distributed nano thin-layer curing molybdenum sheet.The self-healing performance is utilized and is received
The photothermal conversion characteristic of rice thin layer curing molybdenum sheet is realized.
The present invention also provides the preparation method of the above-mentioned macromolecule composite hydrogel with self-healing property, this method packets
Include following steps:
Step 1: four arm sulfydryl polyvinyl alcohol and nano thin-layer curing molybdenum sheet aqueous solution being added in a reservoir, are stirred
Solution 30min；
Step 2: methacrylic acid anhydridization gelatin solid being added in the mixed solution in above-mentioned steps 1, stirring keeps its complete
Fully dissolved；
Step 3: photoinitiator being added in mixed solution in step 2 above and waits being completely dissolved, leads to inert gas removal
Oxygen；
Step 4: the mixed solution in above-mentioned steps 3 being reacted into 10~180min under ultraviolet radiation, obtains macromolecule
Composite hydrogel；
Step 5: macromolecule composite hydrogel obtained being put into insulating box and saves ageing, can be obtained based on nanometer thin
The compound self-healing hydrogel of macromolecule of layer curing molybdenum sheet.
In above-mentioned preparation method, the nano thin-layer curing molybdenum sheet is synthesized by ultrasonic wave added graft process, the methyl
Acrylic acid anhydridization gelatin is synthesized by gelatin with methacrylic acid anhydride reactant, and the molecular weight of the four arms sulfydryl polyvinyl alcohol is
5K。
The mass volume ratio of four arm sulfydryl polyvinyl alcohol and nano thin-layer curing molybdenum sheet aqueous solution in above-mentioned steps 1 is
26.8%, the concentration of nano thin-layer curing molybdenum sheet solution is 0.5mg/ml.
The environment temperature that solution stirs in above-mentioned steps 2 is 20 DEG C.
The mass volume ratio of methacrylic acid anhydridization gelatin and nano thin-layer curing molybdenum sheet aqueous solution is in above-mentioned steps 3
15%, the photoinitiator is Irg 2959, and nano thin-layer curing molybdenum sheet aqueous solution mass volume ratio is 0.5%.On
Stating the logical nitrogen deoxygenation time in step 3 is 1min.
Ultraviolet radiation process in above-mentioned steps 4 realizes that reaction temperature is by the UV illumination 1h of 365nm wavelength
60℃。
Storage temperature is 25 DEG C in insulating box in above-mentioned steps 5.
The ultrasonic wave added graft process synthesizes nano thin-layer curing molybdenum sheet, comprising the following steps:
Step 1: under nitrogen protection, molybdenum disulfide powder being mixed into 30min under ultrasound environments with n-butyllithium solution；
Step 2: deionized water, ultrasound is added, removing obtains crude product；
Step 3: a certain amount of ethyl alcohol is added, is added in crude product and forms suspension, centrifugation removal supernatant, deionization
Water is added in the product of removal supernatant, and centrifugation removal supernatant obtains final product.
Wherein, nano thin-layer curing molybdenum sheet powder and n-BuLi molar ratio in above-mentioned steps 1 are as follows: 1:1~12.Step
Nano thin-layer curing molybdenum sheet powder crude product and ethyl alcohol are made into the suspension of 4~15mg/mL in 3.Nano thin-layer two in step 3
Vulcanization molybdenum sheet powder crude product and deionized water are made into the suspension of 1~5mg/mL.
The methacrylic acid anhydridization gelatin is synthesized by gelatin with methacrylic acid anhydride reactant, comprising the following steps:
Step 1: gelatin (coming from pigskin) is dissolved in PBS until being completely dissolved under 50 DEG C of environment；
Step 2: methacrylic anhydride being added dropwise into reaction flask, is reacted 2 hours；
Step 3: dialysed, freezed, is dried in vacuo and to obtain final product.
Wherein, the concentration that the mass fraction of gelatin is 10%, PBS in step 1 is 0.1mol/L.Metering system in step 2
The mass fraction of acid anhydrides is 8%.Bag filter molecular weight cut-off value used in dialysis procedure is 14KD in step 3.Freezing environment is -80
℃。
The compound self-healing hydrogel of macromolecule provided by the invention has nanoscale structures, and nano molybdenum disulfide piece uniformly divides
The light-initiated click-reaction institute for being dispersed in hydrogel, and being occurred by four arm sulfydryl polyvinyl alcohol and methacrylic acid anhydridization gelatin
The polymer chain structure of formation is mutually intertwined with curing molybdenum sheet, so that compound hydrogel material is eventually become structure uniform
Product.The photothermal conversion conversion characteristic of curing molybdenum sheet, molybdenum disulfide is utilized in the compound self-healing hydrogel of macromolecule
Piece is gradually warmed up after near infrared light, since curing molybdenum sheet is evenly dispersed, so that compound hydrogel material integrally heats up.
With the raising of composite hydrogel temperature, causes the gelatin chains of its internal Thermo-sensitive to generate mobility, pass through gelatin high score
Subchain passes through broken interface in broken interface phase counterdiffusion and macromolecular chain and is mutually wound, the final mesh for realizing self-healing
's.
The compound self-healing hydrogel of macromolecule provided by the invention passes through near infrared light 90s, hydrogel temperature energy
38.7 DEG C are risen to from 15.8 DEG C, hydrogel healing efficiency is 89.3%.
The present invention carries out the self-healing efficiency test of the compound self-healing hydrogel of macromolecule by following methods, including with
Lower step:
Step 1: being diameter 9.8mm, the cylindrical body nano thin-layer curing molybdenum sheet high score of 2.5~3.4mm of thickness by specification
Sub- composite hydrogel, which is cut, becomes two parts, two parts hydrogel fracture face contact is placed, and in near-infrared laser transmitter
Lower irradiation certain time, makes its healing；Wherein, laser intensity 0.6W/cm2, laser emitter is popped one's head in is to the distance of material
11cm, irradiation time are 30s~300s；
Step 2: mechanical performance compression verification being carried out to the hydrogel after healing, healing efficiency is calculated；Healing efficiency
Calculation method is as follows: compression modulus/hydrogel initial compression modulus × 100% after healing efficiency=hydrogel healing.
The invention has the following beneficial effects:
1, the compound self-healing hydrogel of the macromolecule have good healing efficiency, up to 89.3%；
2, self-healing hydrogel material structure of the invention design is simple, from a wealth of sources, low in cost；
3, the material used of the invention has the characteristics of hypotoxicity, good biocompatibility, has in biologic applications field
There is application prospect.
Detailed description of the invention
Fig. 1 is the structure and synthesis schematic diagram of the compound self-healing hydrogel of macromolecule of the present invention；
Fig. 2 is the nuclear magnetic resonance spectroscopy of synthesis material methacrylic acid anhydridization gelatin in the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope diagram piece of composite hydrogel in the embodiment of the present invention 1；
Fig. 4 is in the embodiment of the present invention 1 under near infrared light, using nano thin-layer curing molybdenum sheet (0.5mg/
Ml the heating curve for the composite hydrogel for) and not using nano thin-layer curing molybdenum sheet solution to synthesize；
Fig. 5 is using nano thin-layer curing molybdenum sheet (0.5mg/ml) and not use nanometer thin in the embodiment of the present invention 1
The healing efficiency of the composite hydrogel of layer curing molybdenum sheet solution synthesis compares figure.
Specific embodiment
Further description of the technical solution of the present invention with specific embodiment with reference to the accompanying drawings of the specification.
Embodiment 1
The present invention provides a kind of compound self-healing hydrogel of the macromolecule based on nano thin-layer curing molybdenum sheet, the high score
Sub- hydrogel is synthesized by nano molybdenum disulfide piece, methacrylic acid anhydridization gelatin, four arm sulfydryl polyvinyl alcohol, the four arms sulfydryl
Polyvinyl alcohol and methacrylic acid anhydridization gelatin are reacted in curing molybdenum sheet aqueous solution, and four arm sulfydryl polyethylene
The strand of the part end sulfydryl of alcohol and methacrylic acid anhydridization gelatin has occurred light-initiated click-reaction and is bound up attached
Fig. 1 is the structure and synthesis schematic diagram of the compound self-healing hydrogel of macromolecule of the present invention.
Before preparing the compound self-healing hydrogel of macromolecule, need first to prepare nano thin-layer curing molybdenum sheet and metering system
Acid anhydrides gelatin.Fig. 2 is the nuclear magnetic resonance spectroscopy of synthesis material methacrylic acid anhydridization gelatin in the present embodiment 1, metering system
Acid anhydrides gelatin is compared to gelatin, produces two substance absorption peaks at chemical shift 5.26 and 5.51ppm, thus determines
Methacrylic acid anhydridization gelatin synthesizes successfully.
The present embodiment provides it is a kind of based on nano thin-layer curing molybdenum sheet have self-healing performance composite hydrogel and its
The method of preparation and verifying self-healing performance comprising the steps of:
Step 1: four arm sulfydryl polyvinyl alcohol (53.6mg) and 0.2mL nano thin-layer curing molybdenum sheet being added in a reservoir
(0.5mg/mL) solution, and 30min is stirred, the environment temperature of stirring is 20 DEG C, the molecular weight of the four arms sulfydryl polyvinyl alcohol
For 5K；
Step 2: by the mixing in above-mentioned steps 1；
Methacrylic acid anhydridization gelatin (0.03g) is added in solution, stirring makes it completely dissolved,
Step 3: adding Irg 2959 (1mg) in mixed solution in step 2 above, wait be completely dissolved, lead to nitrogen
Oxygen is removed, leading to the nitrogen deoxygenation time is 1min；
Step 4: height being obtained by ultraviolet radiation 10~180min initiation reaction in mixed solution in step 2 above
Molecule composite hydrogel；
Step 5: macromolecule composite hydrogel obtained is put into insulating box and is saved 6 hours, storage temperature in insulating box
It is 25 DEG C；
Step 6: composite hydrogel being taken out, it is diameter 9.8mm, the cylindrical body nanometer of 2.5~3.4mm of thickness that specification, which is made,
Thin layer curing molybdenum sheet macromolecule composite hydrogel, being cut from top to bottom along cylinder diameter becomes two parts；
Two parts hydrogel fracture face contact is placed, and the 11cm under near-infrared laser transmitter probe, irradiates 90s,
Laser intensity is 0.6W/cm2；
Step 8: the hydrogel after irradiation healing is tested by universal testing machine to the compression mould of material after being healed
Amount, as shown in Figure 5.
Wherein, the preparation of the nano thin-layer curing molybdenum sheet aqueous solution, comprising the following steps:
Step 1: under nitrogen protection, molybdenum disulfide powder is mixed into 30min under ultrasound environments with n-butyllithium solution,
Nano thin-layer curing molybdenum sheet powder and n-BuLi molar ratio are as follows: 1:1~12；
Step 2: deionized water, ultrasound is added, removing obtains crude product；
Step 3: a certain amount of ethyl alcohol is added, is added to the suspension for being formed in crude product and being made into 4~15mg/mL, centrifugation is gone
Except supernatant, deionized water is added to the suspension that 1~5mg/mL is made into the product of removal supernatant, centrifugation removal supernatant
Liquid obtains nano thin-layer curing molybdenum sheet.
Step 4: nano thin-layer curing molybdenum sheet obtained and water ion are made into the aqueous solution that concentration is 0.5mg/mL.
Wherein, the methacrylic acid anhydridization gelatin is synthesized by gelatin with methacrylic acid anhydride reactant, including following step
It is rapid:
Step 1: gelatin (coming from pigskin) is dissolved in PBS under 50 DEG C of environment until being completely dissolved, the quality point of gelatin
The concentration that number is 10%, PBS is 0.1mol/L；
Step 2: the methacrylic anhydride that mass fraction is 8% being added dropwise into reaction flask, is reacted 2 hours；
Step 3: dialysed, freezed, is dried in vacuo and to obtain methacrylic acid anhydridization gelatin；Wherein, used in dialysis procedure thoroughly
Analysis bag molecular weight cut-off value is 14KD, and freezing environment is -80 DEG C.
In addition, the time of laser irradiation should determine according to the actual situation, can be with when test hydrogel self-healing performance
It is 30s, 90s, 150s, 300s etc..
In order to better illustrate the performance of self-healing hydrogel made from the present embodiment, what is be also prepared for does not include molybdenum dioxide
The hydrogel of piece, compares.
All test results show the macromolecule Compound Water according to the present invention based on nano thin-layer curing molybdenum sheet
Gel self-healing result is excellent (Fig. 5).Click-reaction is caused using ultraviolet light and prepares compound self-healing hydrogel, process operation letter
Just, low in cost, it is energy saving, it is conducive to large-scale promotion research.In addition, for research nano thin-layer curing molybdenum sheet in self-healing
Condensation material preparation field has important research meaning.
Claims (10)
1. a kind of compound self-healing hydrogel of macromolecule based on nano thin-layer curing molybdenum sheet, which is characterized in that the high score
Sub- hydrogel is synthesized by nano thin-layer curing molybdenum sheet, methacrylic acid anhydridization gelatin, four arm sulfydryl polyvinyl alcohol, four arm
Sulfydryl polyvinyl alcohol and methacrylic acid anhydridization gelatin are to react in curing molybdenum sheet aqueous solution, and four arm sulfydryls are poly-
The part end sulfydryl of vinyl alcohol and the strand of methacrylic acid anhydridization gelatin have occurred light-initiated click-reaction and are bound up on one
It rises, the strand being bound up is wound with equally distributed nano thin-layer curing molybdenum sheet；The self-healing performance
It is realized using the photothermal conversion characteristic of nano thin-layer curing molybdenum sheet.
2. a kind of preparation method of the compound self-healing hydrogel of macromolecule as described in claim 1, which is characterized in that the system
Preparation Method includes the following steps:
Step 1: four arm sulfydryl polyvinyl alcohol and nano thin-layer curing molybdenum sheet aqueous solution being added in a reservoir, are stirred solution
30min；
Step 2: methacrylic acid anhydridization gelatin solid being added in the mixed solution in above-mentioned steps 1, stirring keeps it completely molten
Solution；
Step 3: photoinitiator being added in mixed solution in step 2 above and waits being completely dissolved, leads to inert gas and removes oxygen；
Step 4: the mixed solution in above-mentioned steps 3 being reacted into 10min~180min under ultraviolet radiation, it is multiple to obtain macromolecule
Heshui gel；
Step 5: macromolecule composite hydrogel obtained being put into insulating box and saves ageing, can be obtained based on nano thin-layer two
Vulcanize the compound self-healing hydrogel of macromolecule of molybdenum sheet.
3. preparation method according to claim 2, which is characterized in that the nano thin-layer curing molybdenum sheet is auxiliary by ultrasound
Graft process is helped to synthesize, the methacrylic acid anhydridization gelatin is synthesized by gelatin with methacrylic acid anhydride reactant, the four arms mercapto
The molecular weight of base polyvinyl alcohol is 5K.
4. preparation method according to claim 2, which is characterized in that four arm sulfydryl polyvinyl alcohol in above-mentioned steps 1 and
The mass volume ratio of nano thin-layer curing molybdenum sheet aqueous solution is 26.8%g/ml, the concentration of nano thin-layer curing molybdenum sheet solution
For 0.5mg/ml.
5. preparation method according to claim 2, which is characterized in that the environment temperature of solution stirring is in above-mentioned steps 2
20 DEG C, storage temperature is 25 DEG C in the insulating box in above-mentioned steps 5.
6. preparation method according to claim 2, which is characterized in that in above-mentioned steps 3 methacrylic acid anhydridization gelatin and
The mass volume ratio of nano thin-layer curing molybdenum sheet aqueous solution is 15%g/ml, and the photoinitiator is Irg 2959, Qi Hena
Rice thin layer curing molybdenum sheet aqueous solution mass volume ratio is 0.5%, and leading to the nitrogen deoxygenation time is 1min.
7. preparation method according to claim 2, which is characterized in that the ultraviolet radiation process in above-mentioned steps 4 passes through
The UV illumination 1h of 365nm wavelength realizes that reaction temperature is 60 DEG C.
8. preparation method according to claim 3, which is characterized in that the ultrasonic wave added graft process synthesizes nano thin-layer two
Vulcanize molybdenum sheet, comprising the following steps:
Step 1: under nitrogen protection, molybdenum disulfide powder being mixed into 30min, nanometer with n-butyllithium solution under ultrasound environments
Thin layer curing molybdenum sheet powder and n-BuLi molar ratio are as follows: 1:1~12；
Step 2: deionized water, ultrasound is added, removing obtains crude product；
Step 3: a certain amount of ethyl alcohol is added, is added to the suspension for forming 4~15mg/mL in crude product, centrifugation removes supernatant,
Deionized water is added in the product of removal supernatant, is made into the suspension of 1~5mg/mL, centrifugation removal supernatant obtains most
Final product.
9. preparation method according to claim 3, which is characterized in that the methacrylic acid anhydridization gelatin by gelatin with
The synthesis of methacrylic acid anhydride reactant, comprising the following steps:
Step 1: the gelatin that mass fraction is 10% is dissolved in the PBS that concentration is 0.1mol/L under 50 DEG C of environment until completely
Dissolution；
Step 2: the methacrylic anhydride that mass fraction is 8% being added dropwise into reaction flask, is reacted 2 hours；
Step 3: dialysed, freezed, is dried in vacuo and to obtain final product, bag filter molecular weight cut-off value used in the dialysis procedure
For 14KD, the freezing environment is -80 DEG C.
10. a kind of self-healing Efficiency test method of the compound self-healing hydrogel of macromolecule as described in claim 1, feature
Be, the test method the following steps are included:
Step 1: being diameter 9.8mm by specification, the cylindrical body nano thin-layer curing molybdenum sheet macromolecule of 2.5~3.4mm of thickness is multiple
Heshui gel, which is cut, becomes two parts, and two parts hydrogel fracture face contact is placed, and shines under near-infrared laser transmitter
Certain time is penetrated, its healing is made；Wherein, laser intensity 0.6W/cm2, the distance of laser emitter probe to material is 11cm,
Irradiation time is 30s~300s；
Step 2: mechanical performance compression verification being carried out to the hydrogel after healing, healing efficiency is calculated；Healing efficiency calculates
Method is as follows: compression modulus/hydrogel initial compression modulus × 100% after healing efficiency=hydrogel healing.
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| CN107550921B (en) * | 2017-08-24 | 2020-04-14 | 南京邮电大学 | Nanoparticle-polymer injectable composite hydrogel double-drug-loading system and preparation method thereof |
| CN107583104B (en) * | 2017-10-31 | 2020-12-01 | 无锡中科光远生物材料有限公司 | Injectable gel material for spine repair |
| CN108219480B (en) * | 2017-12-07 | 2020-06-05 | 南京邮电大学 | Preparation and application of macromolecule-nanometer molybdenum disulfide sheet composite hydrogel based on thermally reversible Diels-Alder reaction |
| CN109897314B (en) * | 2019-02-20 | 2021-06-08 | 南京邮电大学 | Near-infrared light-initiated self-healing polyvinyl alcohol-molybdenum disulfide composite hydrogel and preparation method and testing method thereof |
| CN109762369B (en) * | 2019-02-28 | 2021-02-26 | 中山大学惠州研究院 | Preparation method of water-based high-dispersity nano molybdenum disulfide |
| CN109970998B (en) * | 2019-03-14 | 2020-04-28 | 华南理工大学 | Method for preparing GelMA macroporous hydrogel by Pickering emulsion method and application |
| CN111393675B (en) * | 2020-03-18 | 2022-09-27 | 武汉纺织大学 | Rapid-forming self-healing hydrogel and preparation method thereof |
| CN111253535B (en) * | 2020-03-23 | 2022-11-08 | 合肥工业大学 | Preparation method of novel photoinduced self-repairing nano composite hydrogel |
| CN111363106B (en) * | 2020-03-24 | 2021-04-06 | 四川大学 | High-strength high-toughness nano composite hydrogel and preparation method and application thereof |
| CN113350569B (en) * | 2021-06-18 | 2022-07-08 | 西北大学 | Preparation method of hydrogel based on carbon nanotube composite molybdenum disulfide nanosheet |
| CN114975944B (en) * | 2022-06-08 | 2023-08-29 | 陕西科技大学 | Silicon-carbon negative electrode material with high-strength carbon matrix and preparation method thereof |
| CN117683445B (en) * | 2024-02-04 | 2024-04-26 | 南京海关工业产品检测中心 | Healing material based on photo-thermal effect and preparation method and application thereof |
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| CN103910894B (en) * | 2014-03-28 | 2016-04-13 | 西安交通大学 | A kind of preparation method of injectable natural polysaccharide self-healing hydrogel |
| CN105268029B (en) * | 2015-09-28 | 2018-02-09 | 福州大学 | A kind of injectable for Bone Defect Repari and natural polymer hydrogel capable of self-healing |
| CN105694066A (en) * | 2016-01-28 | 2016-06-22 | 湖南工业大学 | Self-healing biologically-friendly aquagel with excellent mechanical properties |
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