CN106866993A - 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, there is provided compound self-healing hydrogel of a kind of macromolecule based on nano molybdenum disulfide piece and preparation method thereof.The composite aquogel is formed by there is light-initiated click-reaction in the nano thin-layer curing molybdenum sheet aqueous solution.The click-reaction is that the sulfydryl in unsaturated double-bond and four arm sulfydryl polyvinyl alcohol in methacrylic acid anhydridization gelatin occurs under ultraviolet radiation.The self-healing performance be material by under near infrared light using the photothermal conversion characteristic of nano thin-layer curing molybdenum sheet so that hydrogel heats up and realizes self-healing purpose.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
It is the invention belongs to polymeric biomaterial technical field 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 technology
Self-healing material is inspired by the Nature, the healing of mimic biology bulk damage, is fed by material or energy is mended
To mechanism, the micro-damage of material is set to be able to a kind of emerging biomimetic material for healing automatically.
At present, composite aquogel, Nanometer composite hydrogel have had very big progress in self-healing field, usually by
Unmixing organic (polymer) and inorganic constituents (clay/particle) are constituted with (nanoscale) structure of complexity.McKee etc.
(Adv.Funct.Mater.2014,24,2706) a kind of Nanometer composite hydrogel is prepared for by host-guest interaction and is had
There is excellent self-healing performance (the self-healing time is less than 10s).Spoljaric etc. (Eur.Polym.J.2014,56,105) leads to
Cross mixing nanometer fibrillating fibre element (NFC), polyvinyl alcohol (PVA), borax and synthesized Nanometer composite hydrogel, with excellent
Self-healing performance, its self-healing performance is triggered by the restructuring of hydrogen bond, and the presence of hydrogen bond will also be substantially improved hydrogel
Mechanical performance.Additionally, Duan etc. (J.Nanomater.2015,10,1155) by one kind by Cellulose nanocrystal must, acryloyl
The hydrogel of the compositions such as amine, octadecyl methacrylate can realize the self-healing of gel by the dissociation of hydrophobicity micella and restructuring
Close performance.But, these self-healing hydrogels have certain bio-toxicity, and mechanical performance cannot meet actually used need
Ask.
In recent years, two-dimension nano materials are gradually shown up prominently in self-healing material preparation field, particularly Graphene conduct
Important component build the extensive concern that nano combined self-healing material causes people, Cui etc. (J.Mater.Chem.A.2015,
3,17445) graphene oxide layer is mixed into hydrogel by being prepared for one kind with the method that polyacrylamide is physical crosslinking, its
The maximum stretching force for being born can reach 243kPa, and draw ratio can reach 199 times, and can be without any extraneous bar
Part completes self-healing in the case of exciting.Its self-healing effect is in broken interface phase counterdiffusion and high score by macromolecular chain
Subchain passes through broken interface mutually to be 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
Composite aquogel and Fe that layer is formed with polyacrylamide3+Crosslinking, makes material be provided with self-healing characteristics.But, current graphite
Alkene also has no idea to realize large-scale production, therefore the self-healing hydrogel based on Graphene is relatively costly, is not suitable for big rule
Mould is produced and promoted.
Nano thin-layer curing molybdenum sheet has very strong suction as a kind of two-dimensional material of class Graphene in solar spectrum region
Receipts ability, has a good application prospect in photocatalysis and photovoltaic art.In numerous stratified materials, MoS2(molybdenum bisuphide) is
Very special, it has the excellent properties of uniqueness in terms of heat, power, light, electricity.MoS2There is good light absorbs and photoluminescent property,
And its luminescence generated by light can become strong with the reduction of its number of plies, work as MoS2Luminous most strong (Nano when nanometer sheet is individual layer
Lett.2010,10,1271).In order to solve prior art presence it is biological incompatible, mechanical strength is low, cost is high etc., and technology is asked
Topic, the present invention is based on the excellent photothermal conversion effect of nano thin-layer curing molybdenum sheet, good electric conductivity and larger specific surface
The features such as product, the nano molybdenum disulfide piece-macromolecule composite aquogel of self-healing function admirable is built, realize it in self-healing material
Expect the popularization and application of preparation field.
The content of the invention
In view of there is above-mentioned technical problem in the prior art, the present invention provides a kind of based on nano thin-layer curing molybdenum sheet
, be applied to for two-dimensional material nano material thin layer curing molybdenum sheet first by compound self-healing hydrogel of macromolecule and preparation method thereof
Self-healing material field, makes material through near infrared light so that water using the photothermal conversion characteristic of nano thin-layer curing molybdenum sheet
Hydrogel warms, the methacrylic acid glycosidation gelatin chains of its internal Thermo-sensitive are caused to produce mobility, so as to realize self-healing
Purpose.Because material therefor of the present invention all has good biocompatibility and hypotoxicity, this material is expected to good
Biologic applications prospect.Technical scheme is as described below：
The present invention provides a kind of macromolecule based on nano thin-layer curing molybdenum sheet compound self-healing hydrogel, 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 reacts with methacrylic acid anhydridization gelatin in the curing molybdenum sheet aqueous solution, and four arm sulfydryl polyethylene
The part end sulfydryl of alcohol there occurs light-initiated click-reaction and is bound up, joins with the strand of methacrylic acid anhydridization gelatin
Knot strand together is wound with equally distributed nano thin-layer curing molybdenum sheet.The self-healing performance is utilized and received
The photothermal conversion characteristic of rice thin layer curing molybdenum sheet is realized.
Present invention also offers the preparation method of the above-mentioned macromolecule composite aquogel with self-healing property, the method bag
Include following steps：
Step 1：Four arm sulfydryl polyvinyl alcohol and the nano thin-layer curing molybdenum sheet aqueous solution, stirring mixing are added in a reservoir
Solution 30min；
Step 2：Methacrylic acid anhydridization gelatin solid is added in mixed solution in above-mentioned steps 1, stirring makes its complete
CL；
Step 3：Add light trigger to wait to be completely dissolved in mixed solution in step 2 above, lead to inert gas removal
Oxygen；
Step 4：Mixed solution in above-mentioned steps 3 is reacted into 10~180min under ultraviolet radiation, macromolecule is obtained
Composite aquogel；
Step 5：Obtained macromolecule composite aquogel is put into insulating box and preserves ageing, you can 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 anhydride, and the molecular weight of the four arms sulfydryl polyvinyl alcohol is
5K。
The mass volume ratio of four arm sulfydryl polyvinyl alcohol and the 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 of solution stirring is 20 DEG C in above-mentioned steps 2.
The mass volume ratio of methacrylic acid anhydridization gelatin and the nano thin-layer curing molybdenum sheet aqueous solution is in above-mentioned steps 3
15%, the light trigger is Irg 2959, and itself and nano thin-layer curing molybdenum sheet aqueous solution mass volume ratio are 0.5%.On
The logical nitrogen deoxygenation time in step 3 is stated for 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, comprises the following steps：
Step 1：Under nitrogen protection, molybdenum disulfide powder is mixed into 30min with n-butyllithium solution under ultrasound environments；
Step 2：Deionized water is added, ultrasound, stripping obtains crude product；
Step 3：A certain amount of ethanol is added, is added to and suspension is formed in crude product, centrifugation removal supernatant, deionization
Water is added in the product of removal supernatant, centrifugation removal supernatant, obtains final product.
Wherein, nano thin-layer curing molybdenum sheet powder is with n-BuLi mol ratio in above-mentioned steps 1：1:1~12.Step
Nano thin-layer curing molybdenum sheet powder crude product is made into the suspension of 4~15mg/mL with ethanol in 3.Nano thin-layer two in step 3
Vulcanization molybdenum sheet powder crude product is made into the suspension of 1~5mg/mL with deionized water.
The methacrylic acid anhydridization gelatin is synthesized by gelatin with methacrylic anhydride, is comprised the following steps：
Step 1：Until being completely dissolved during gelatin (coming from pigskin) is dissolved in into PBS under 50 DEG C of environment；
Step 2：Methacrylic anhydride is added dropwise into reaction bulb, is reacted 2 hours；
Step 3：Dialysed, freezed, being vacuum dried and to be obtained final product.
Wherein, in step 1 gelatin mass fraction for 10%, PBS concentration be 0.1mol/L.Metering system in step 2
The mass fraction of acid anhydrides is 8%.Bag filter molecular weight cut-off value used by dialysis procedure is 14KD in step 3.Freezing environment is -80
℃。
The compound self-healing hydrogel of macromolecule that the present invention is provided has nanoscale structures, and nano molybdenum disulfide piece uniformly divides
It is dispersed in hydrogel, and the light-initiated click-reaction institute 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, compound hydrogel material is eventually become structure homogeneous
Product.The compound self-healing hydrogel of the macromolecule make use of the photothermal deformation conversion characteristic of curing molybdenum sheet, molybdenum bisuphide
Piece gradually heats up after near infrared light, because curing molybdenum sheet is dispersed so that compound hydrogel material integrally heats up.
With the rising of composite aquogel temperature, the gelatin chains of its internal Thermo-sensitive are caused to produce mobility, by gelatin high score
Subchain passes through broken interface mutually to be wound in broken interface phase counterdiffusion and macromolecular chain, finally realizes the mesh of self-healing
's.
The compound self-healing hydrogel of macromolecule that the present invention is provided by 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 is carried out to the self-healing efficiency test of the compound self-healing hydrogel of macromolecule by following methods, including with
Lower step：
Step 1：It is diameter 9.8mm, the cylinder nano thin-layer curing molybdenum sheet high score of 2.5~3.4mm of thickness by specification
Sub- composite aquogel cuts turns into two parts, two parts hydrogel plane of disruption is contacted and is placed, and in near-infrared laser transmitter
Lower irradiation certain hour, makes it heal；Wherein, laser intensity is 0.6W/cm2, generating laser pops one's head in the distance of material and is
11cm, irradiation time is 30s~300s；
Step 2：Mechanical performance compression verification is carried out to the hydrogel after healing, healing efficiency is calculated；Healing efficiency
Computational methods are as follows：Modulus of compressibility/hydrogel initial compression modulus × 100% after healing efficiency=hydrogel healing.
The present invention has the advantages that：
1st, the compound self-healing hydrogel of the macromolecule has good healing efficiency, up to 89.3%；
2nd, self-healing hydrogel material structure design of the invention is simple, wide material sources, with low cost；
3rd, the characteristics of used material of the invention has hypotoxicity, good biocompatibility, in biologic applications field tool
There is application prospect.
Brief description of the drawings
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 proton nmr spectra of synthesis material methacrylic acid anhydridization gelatin in embodiments of the invention 1；
Fig. 3 is the scanning electron microscope diagram piece of composite aquogel in embodiments of the invention 1；
Fig. 4 be embodiments of the invention 1 under near infrared light, using nano thin-layer curing molybdenum sheet (0.5mg/
Ml the heating curve of the composite aquogel of nano thin-layer curing molybdenum sheet solution synthesis) and is not used；
Fig. 5 is using nano thin-layer curing molybdenum sheet (0.5mg/ml) and not using nanometer thin in embodiments of the invention 1
The healing efficiency of the composite aquogel of layer curing molybdenum sheet solution synthesis compares figure.
Specific embodiment
Technical scheme is further described with reference to Figure of description and specific embodiment.
Embodiment 1
The present invention provides a kind of macromolecule based on nano thin-layer curing molybdenum sheet compound self-healing hydrogel, 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 reacts with methacrylic acid anhydridization gelatin in the curing molybdenum sheet aqueous solution, and four arm sulfydryl polyethylene
The part end sulfydryl of alcohol there occurs light-initiated click-reaction and is bound up attached with the strand of methacrylic acid anhydridization gelatin
Fig. 1 is the structure and synthesis schematic diagram of the compound self-healing hydrogel of macromolecule of the present invention.
, it is necessary to first prepare nano thin-layer curing molybdenum sheet and metering system before the compound self-healing hydrogel of macromolecule is prepared
Acid anhydrides gelatin.Fig. 2 is the proton nmr spectra of synthesis material methacrylic acid anhydridization gelatin in the present embodiment 1, metering system
Acid anhydrides gelatin is compared to gelatin, and two substance absworption peaks are generated at chemical shift 5.26 and 5.51ppm, thus judges
Methacrylic acid anhydridization gelatin synthesizes successfully.
The present embodiment provide it is a kind of based on nano thin-layer curing molybdenum sheet have self-healing performance composite aquogel and its
The method for preparing and verifying self-healing performance, comprises the steps of：
Step 1：Four arm sulfydryls polyvinyl alcohol (53.6mg) and 0.2mL nano thin-layer curing molybdenum sheets are 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
It is 5K；
Step 2：By the mixing in above-mentioned steps 1；
Methacrylic acid anhydridization gelatin (0.03g) is added in solution, stirring is completely dissolved it,
Step 3：Irg 2959 (1mg) is added in mixed solution in step 2 above, waits to be completely dissolved, lead to nitrogen
Removal oxygen, leads to the nitrogen deoxygenation time for 1min；
Step 4：Height is obtained by ultraviolet radiation 10~180min initiation reactions in mixed solution in step 2 above
Molecule composite aquogel；
Step 5：Obtained macromolecule composite aquogel is put into insulating box and is preserved 6 hours, storage temperature in insulating box
It is 25 DEG C；
Step 6：Composite aquogel is taken out, specification is made for diameter 9.8mm, the cylinder nanometer of 2.5~3.4mm of thickness
Thin layer curing molybdenum sheet macromolecule composite aquogel, is cut as two parts from top to bottom along cylinder diameter；
Two parts hydrogel plane of disruption is contacted and is placed, and the 11cm under near-infrared laser transmitter probe, 90s is irradiated,
Laser intensity is 0.6W/cm2；
Step 8：By through the compression mould of the material after universal testing machine is tested and healed of the hydrogel after irradiation healing
Amount, as shown in Figure 5.
Wherein, the preparation of the nano thin-layer curing molybdenum sheet aqueous solution, comprises the following steps：
Step 1：Under nitrogen protection, molybdenum disulfide powder is mixed into 30min with n-butyllithium solution under ultrasound environments,
Nano thin-layer curing molybdenum sheet powder is with n-BuLi mol ratio：1:1~12；
Step 2：Deionized water is added, ultrasound, stripping obtains crude product；
Step 3：A certain amount of ethanol is added, the suspension for being formed in crude product and being made into 4~15mg/mL is added to, centrifugation is gone
Except supernatant, deionized water is added in the product of removal supernatant the suspension for being made into 1~5mg/mL, centrifugation removal supernatant
Liquid, obtains nano thin-layer curing molybdenum sheet.
Step 4：Obtained nano thin-layer curing molybdenum sheet 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 anhydride, including following step
Suddenly：
Step 1：Until being completely dissolved during gelatin (coming from pigskin) is dissolved in into PBS under 50 DEG C of environment, the quality point of gelatin
Number is 0.1mol/L for the concentration of 10%, PBS；
Step 2：The methacrylic anhydride that mass fraction is 8% is added dropwise into reaction bulb, is reacted 2 hours；
Step 3：Dialysed, freezed, being vacuum dried and to be obtained methacrylic acid anhydridization gelatin；Wherein, used by dialysis procedure thoroughly
Analysis bag molecular weight cut-off value is 14KD, and freezing environment is -80 DEG C.
In addition, during test hydrogel self-healing performance, the time of laser irradiation should determine according to actual conditions, can be with
It is 30s, 90s, 150s, 300s etc..
In order to better illustrate the performance of self-healing hydrogel obtained in the present embodiment, be also prepared for not comprising molybdenum dioxide
The hydrogel of piece, is contrasted.
All of test result shows, the macromolecule Compound Water based on nano thin-layer curing molybdenum sheet involved in the present invention
Gel self-healing result is excellent (Fig. 5).Click-reaction is triggered to prepare compound self-healing hydrogel, process operation letter using ultraviolet light
Just, it is with low cost, energy saving, beneficial to large-scale promotion research.Additionally, 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 macromolecule based on nano thin-layer curing molybdenum sheet is combined self-healing hydrogel, it is characterised 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 reacts with methacrylic acid anhydridization gelatin in the curing molybdenum sheet aqueous solution, and four arm sulfydryls are poly-
The part end sulfydryl of vinyl alcohol there occurs light-initiated click-reaction and be bound up on one with the strand of methacrylic acid anhydridization gelatin
Rise, the strand being bound up is wound with equally distributed nano thin-layer curing molybdenum sheet；The self-healing performance
Realized using the photothermal conversion characteristic of nano thin-layer curing molybdenum sheet.
2. a kind of macromolecule as claimed in claim 1 is combined the preparation method of self-healing hydrogel, it is characterised in that the system
Preparation Method comprises the following steps：
Step 1：Four arm sulfydryl polyvinyl alcohol and the nano thin-layer curing molybdenum sheet aqueous solution are added in a reservoir, stir mixed solution
30min；
Step 2：Methacrylic acid anhydridization gelatin solid is added in mixed solution in above-mentioned steps 1, stirring makes it completely molten
Solution；
Step 3：Add light trigger to wait to be completely dissolved in mixed solution in step 2 above, lead to inert gas removal oxygen；
Step 4：Mixed solution in above-mentioned steps 3 is reacted into 10min~180min under ultraviolet radiation, macromolecule is obtained and is answered
Heshui gel；
Step 5：Obtained macromolecule composite aquogel is put into insulating box and preserves ageing, you can 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, it is characterised 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 anhydride, the four arms mercapto
The molecular weight of base polyvinyl alcohol is 5K.
4. preparation method according to claim 2, it is characterised in that four arm sulfydryl polyvinyl alcohol in above-mentioned steps 1 and
The mass volume ratio of the nano thin-layer curing molybdenum sheet aqueous solution is 26.8%, and the concentration of nano thin-layer curing molybdenum sheet solution is
0.5mg/ml。
5. preparation method according to claim 2, it is characterised 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, it is characterised in that in above-mentioned steps 3 methacrylic acid anhydridization gelatin and
The mass volume ratio of the nano thin-layer curing molybdenum sheet aqueous solution is 15%, and the light trigger is Irg 2959, itself and nanometer thin
Layer curing molybdenum sheet aqueous solution mass volume ratio is 0.5%, leads to the nitrogen deoxygenation time for 1min.
7. preparation method according to claim 2, it is characterised 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, it is characterised in that the ultrasonic wave added graft process synthesizes nano thin-layer two
Vulcanization molybdenum sheet, comprises the following steps：
Step 1：Under nitrogen protection, molybdenum disulfide powder is mixed into 30min, nanometer with n-butyllithium solution under ultrasound environments
Thin layer curing molybdenum sheet powder is with n-BuLi mol ratio：1:1~12；
Step 2：Deionized water is added, ultrasound, stripping obtains crude product；
Step 3：A certain amount of ethanol is added, is added in crude product and is formed the suspension of 4~15mg/mL, centrifugation removal supernatant,
Deionized water is added in the product of removal supernatant, the suspension of 1~5mg/mL is made into, centrifugation removal supernatant is obtained most
End-product.
9. preparation method according to claim 3, it is characterised in that the methacrylic acid anhydridization gelatin by gelatin with
Methacrylic anhydride is synthesized, and comprises the following steps：
Step 1：The gelatin (coming from pigskin) that mass fraction is 10% is dissolved in the PBS that concentration is 0.1mol/L under 50 DEG C of environment
In until be completely dissolved；
Step 2：The methacrylic anhydride that mass fraction is 8% is added dropwise into reaction bulb, is reacted 2 hours；
Step 3：Dialysed, freezed, being vacuum dried and to be obtained final product, bag filter molecular weight cut-off value used by the dialysis procedure
It is 14KD, the freezing environment is -80 DEG C.
10. a kind of macromolecule as claimed in claim 1 is combined the self-healing Efficiency test method of self-healing hydrogel, its feature
It is that the method for testing is comprised the following steps：
Step 1：It is diameter 9.8mm by specification, the cylinder nano thin-layer curing molybdenum sheet macromolecule of 2.5~3.4mm of thickness is answered
Heshui gel cuts turns into two parts, two parts hydrogel plane of disruption is contacted and is placed, and shone under near-infrared laser transmitter
Certain hour is penetrated, it is healed；Wherein, laser intensity is 0.6W/cm2, the distance of generating laser probe to material is 11cm,
Irradiation time is 30s~300s；
Step 2：Mechanical performance compression verification is carried out to the hydrogel after healing, healing efficiency is calculated；Healing efficiency is calculated
Method is as follows：Modulus of compressibility/hydrogel initial compression modulus × 100% after healing efficiency=hydrogel healing.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107550921A (en) * | 2017-08-24 | 2018-01-09 | 南京邮电大学 | Double medicine-carried systems of a kind of nano particle macromolecule injectable composite aquogel and preparation method thereof |
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| CN109762369A (en) * | 2019-02-28 | 2019-05-17 | 中山大学惠州研究院 | A kind of preparation method of water base high dispersancy nano molybdenum disulfide |
| CN109897314A (en) * | 2019-02-20 | 2019-06-18 | 南京邮电大学 | Self-healing polyvinyl alcohol-molybdenum disulfide composite hydrogel that a kind of near infrared light causes and preparation method thereof and test method |
| CN109970998A (en) * | 2019-03-14 | 2019-07-05 | 华南理工大学 | A kind of method and application preparing GelMA super porous hydrogel with Pickering emulsion method |
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| CN111363106A (en) * | 2020-03-24 | 2020-07-03 | 四川大学 | High-strength high-toughness nano composite hydrogel and preparation method and application thereof |
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| CN113350569A (en) * | 2021-06-18 | 2021-09-07 | 西北大学 | Preparation method of hydrogel based on carbon nanotube composite molybdenum disulfide nanosheet |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910894A (en) * | 2014-03-28 | 2014-07-09 | 西安交通大学 | Preparation method of injectable natural polysaccharide self-healing hydrogel |
| CN105268029A (en) * | 2015-09-28 | 2016-01-27 | 福州大学 | Injectable and self-healing natural polymer hydrogel used for bone restoration |
| CN105694066A (en) * | 2016-01-28 | 2016-06-22 | 湖南工业大学 | Self-healing biologically-friendly aquagel with excellent mechanical properties |
-
2017
- 2017-01-18 CN CN201710036508.0A patent/CN106866993B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910894A (en) * | 2014-03-28 | 2014-07-09 | 西安交通大学 | Preparation method of injectable natural polysaccharide self-healing hydrogel |
| CN105268029A (en) * | 2015-09-28 | 2016-01-27 | 福州大学 | Injectable and self-healing natural polymer hydrogel used for bone restoration |
| CN105694066A (en) * | 2016-01-28 | 2016-06-22 | 湖南工业大学 | Self-healing biologically-friendly aquagel with excellent mechanical properties |
Non-Patent Citations (1)
| Title |
|---|
| ZHAO WEI ETAL.: "Novel Biocompatible Polysaccharide-Based Self-Healing Hydrogel", 《ADVANCED FUNCTIONAL MATERIALS》 * |
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| CN107550921A (en) * | 2017-08-24 | 2018-01-09 | 南京邮电大学 | Double medicine-carried systems of a kind of nano particle macromolecule injectable composite aquogel and preparation method thereof |
| 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 |
| CN107583104A (en) * | 2017-10-31 | 2018-01-16 | 无锡中科光远生物材料有限公司 | A kind of gel rubber material for backbone reparation of injectable |
| 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 |
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| CN109897314A (en) * | 2019-02-20 | 2019-06-18 | 南京邮电大学 | Self-healing polyvinyl alcohol-molybdenum disulfide composite hydrogel that a kind of near infrared light causes and preparation method thereof and test method |
| 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 |
| CN109762369A (en) * | 2019-02-28 | 2019-05-17 | 中山大学惠州研究院 | A kind of preparation method of water base high dispersancy nano molybdenum disulfide |
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| CN111393675A (en) * | 2020-03-18 | 2020-07-10 | 武汉纺织大学 | Quick-forming self-healing hydrogel and preparation method thereof |
| CN111393675B (en) * | 2020-03-18 | 2022-09-27 | 武汉纺织大学 | Rapid-forming self-healing hydrogel and preparation method thereof |
| CN111253535A (en) * | 2020-03-23 | 2020-06-09 | 合肥工业大学 | Preparation method of novel photoinduced self-repairing nano composite hydrogel |
| CN111253535B (en) * | 2020-03-23 | 2022-11-08 | 合肥工业大学 | Preparation method of novel photoinduced self-repairing nano composite hydrogel |
| CN111363106A (en) * | 2020-03-24 | 2020-07-03 | 四川大学 | High-strength high-toughness nano composite hydrogel and preparation method and application thereof |
| 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 |
| CN113350569A (en) * | 2021-06-18 | 2021-09-07 | 西北大学 | Preparation method of hydrogel based on carbon nanotube composite molybdenum disulfide nanosheet |
| CN113350569B (en) * | 2021-06-18 | 2022-07-08 | 西北大学 | Preparation method of hydrogel based on carbon nanotube composite molybdenum disulfide nanosheet |
| CN114975944A (en) * | 2022-06-08 | 2022-08-30 | 陕西科技大学 | Silicon-carbon negative electrode material with high-strength carbon matrix and preparation method thereof |
| 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 |
| CN117683445A (en) * | 2024-02-04 | 2024-03-12 | 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 |
| 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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