CN109851725A - The gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, preparation method and application - Google Patents

The gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, preparation method and application Download PDF

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CN109851725A
CN109851725A CN201811640605.1A CN201811640605A CN109851725A CN 109851725 A CN109851725 A CN 109851725A CN 201811640605 A CN201811640605 A CN 201811640605A CN 109851725 A CN109851725 A CN 109851725A
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cellulose
nano
gelatin
hydrogel
preparation
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陈广学
李楠
田君飞
陈奇峰
何明辉
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention discloses the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, preparation method and applications, are related to technical field of composite materials.The gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, forms double-network hydrogel by acrylamide crosspolymer network and gelatin cross-linked network, and load has the nano-cellulose after oxidation in double-network hydrogel.The preparation method of the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-includes: after aoxidizing cellulose in oxidation system, then carries out homogeneous and obtain nano-cellulose, and nano-cellulose and water are mixed to get nano-cellulose solution;Mixed solution is obtained after nano-cellulose solution is mixed with gelatin aqueous dispersions, acrylamide, initiator, crosslinking agent and catalyst;Mixed solution is injected in mold and reacts 10-15h.The composite hydrogel being prepared has good mechanical strength, while improving the biocompatibility and biological degradability of hydrogel.

Description

The gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, preparation method and Using
Technical field
The present invention relates to technical field of composite materials, and the in particular to gelatin-compounded water of nano-cellulose-polyacrylamide- Gel, preparation method and application.
Background technique
Hydrogel (Hydrogel) be it is a kind of can absorb a large amount of water and not dissolve, and keep the macromolecule of certain shape The network system, shape memory gel shape memory and can restore in certain circumstances under the action of environmental stimuli.However, The gel strength of traditional chemical crosslinking preparation is relatively weak, and this greatly limits their applications as soft material.
Composite hydrogel and double-network hydrogel are considered as the common approach for improving gel mechanical performance all the time.It is multiple Heshui gel introduces enhancing organic/inorganic filler, such as montmorillonite, nanofiber in the polymer network structure of hydrogel Element, carbon nanotube etc., to improve the mechanical performance of hydrogel.But existing hydrogel there is shape memory rates low, machine The problem of tool intensity cannot be met the requirements.
Summary of the invention
The purpose of the present invention is to provide a kind of gelatin-compounded hydrogels of nano-cellulose-polyacrylamide-, it is intended to be promoted The mechanical strength of hydrogel.
Another object of the present invention is to provide a kind of systems of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide- Preparation Method, simple process, condition is easy to control, the high mechanical strength for the hydrogel being prepared.
The third object of the present invention is to provide a meter application for the gelatin-compounded hydrogel of cellulose-polyacrylamide-, widen The application field of material.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The invention proposes a kind of gelatin-compounded hydrogels of nano-cellulose-polyacrylamide-, by acrylamide crosspolymer net Network and gelatin cross-linked network form double-network hydrogel, and load has the nano-cellulose after oxidation in double-network hydrogel.
The invention also provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, including Following steps:
After cellulose is aoxidized in oxidation system, then carry out homogeneous and obtain nano-cellulose, and by nano-cellulose with Water is mixed to get nano-cellulose solution;
After nano-cellulose solution is mixed with gelatin aqueous dispersions, acrylamide, initiator, crosslinking agent and catalyst To mixed solution;
Mixed solution is injected in mold and reacts 10-15h.
It is slow in organizational project, drug that the invention also provides the gelatin-compounded hydrogels of nano-cellulose-polyacrylamide- It releases, the application in the driving of cell culturing bracket and soft substance.
A kind of beneficial effect of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-provided in an embodiment of the present invention Be: it is by forming the Nanowire in double-network hydrogel after load oxidation in acrylamide crosspolymer network and gelatin cross-linked network Dimension element forms composite hydrogel, has good mechanical strength, while improving biocompatibility and the biodegrade of hydrogel Property.
The present invention also provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, lead to It crosses after cellulose to be carried out to oxidation and homogeneous in oxidation system and obtains nano-cellulose, to be obtained after nanofiber and water mixing Nano-cellulose solution materials, after it is mixed with gelatin aqueous dispersions, acrylamide, initiator, crosslinking agent and catalyst Mixed solution is obtained, composite hydrogel is prepared after mixed solution is reacted in molding die.Simple process is easy, condition It is easy to control, the composite hydrogel being prepared has good mechanical performance, can be in organizational project, medicament slow release, cell It is used widely in the fields such as culture bracket and the driving of soft substance.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the test result of the shape memory function of plural gel in the embodiment of the present invention;
Fig. 2 is the test result of plural gel tensile property in the embodiment of the present invention;
Fig. 3 is the test result of plural gel tensile property in the embodiment of the present invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.
Below to the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-provided in an embodiment of the present invention, its preparation side Method and application are specifically described.
The embodiment of the invention provides a kind of gelatin-compounded hydrogels of nano-cellulose-polyacrylamide-, by acrylamide Cross-linked network and gelatin cross-linked network form double-network hydrogel, and load has the nanofiber after oxidation in double-network hydrogel Element.
It should be noted that by being carried on the nano-cellulose after oxidation by acrylamide and gelatin cross-linked network shape At dual network system in, which has good mechanical strength, is provided simultaneously with good biocompatibility, can be again Natural disposition.
The embodiment of the invention also provides a kind of preparation sides of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide- Method, comprising the following steps:
The preparation of S1, nano-cellulose solution
After cellulose is aoxidized in oxidation system, then carry out homogeneous and obtain nano-cellulose, and by nano-cellulose with Water is mixed to get nano-cellulose solution.Homogenizing process can be to carry out in high pressure homogenizer, at elevated pressures through excessively high The effect of pressure homogenizer obtains nano-cellulose.
Preferably, the oxidation system during cellulose oxidation is TEMPO/NaBr/NaClO oxidation system.TEMPO(2, - 1 oxide radical of 2,6,6- tetramethyl piperidine)/NaBr/NaClO oxidation system, the hydroxyl on the selective C6 by cellulose Base is oxidized to carboxyl, then the nano-cellulose of TEMPO oxidation is prepared for by mechanical treatment.The nano-cellulose of TEMPO preparation With biggish specific surface area, higher mechanical strength and elasticity modulus, it can be greatly improved by being added in hydrogel Mechanical performance.
In other embodiments, it can also be aoxidized using other oxidation systems for cellulose, herein not one by one It enumerates.
Specifically, the preparation step of nano-cellulose includes: and discongests paper pulp in water, then with TEMPO, NaBr and Then NaClO hybrid reaction terminates reaction using dehydrated alcohol, using obtaining nanofiber after the homogeneous of high pressure homogenizer Element, PH remains constant during the reaction.
In general, the solid content of nano-cellulose solution is 1%-2%, the solid content in nano-cellulose solution is main React the cooperation of nano-cellulose and water consumption, solid content it is excessive or it is too small can machinery to final composite hydrogel product it is strong Degree has certain influence.
The preparation of S2, reaction system solution
After nano-cellulose solution is mixed with gelatin aqueous dispersions, acrylamide, initiator, crosslinking agent and catalyst To mixed solution.It preferably, is first by nano-cellulose solution, gelatin aqueous dispersions and third in the preparation process of mixed solution Acrylamide after mixing, then with initiator, crosslinking agent and catalyst mixes.Such order by merging can make nanofiber Element, acrylamide and gelatin are uniformly mixed, and carry out reaction more abundant.
Specifically, gelatin aqueous dispersions refer to the dispersion liquid formed after gelatin and water mixing, by gelatin and water at 40-60 DEG C Temperature under the conditions of mix, it is preferable that the incorporation time of gelatin and water be 2-3h.Pass through 2- under the conditions of 40-60 DEG C of temperature The mixing of 3h can be such that gelatin is homogeneously dispersed in water, form uniform solution.Specifically, acrylamide refers to monomer propylene acyl Amine (AM).
The used in amounts of nano-cellulose, gelatin and acrylamide will be controlled in mixed solution, otherwise will affect most End form at hydrogel mechanical strength, inventors have found that gelatin dosage and acryloyl in nano-cellulose, gelatin aqueous dispersions The mass ratio of amine is advisable for 0.01-0.05:0.1-0.5:1, can make the hydrogel mechanical strength being prepared within this range It can meet the requirements with shape memory rate.
Specifically, initiator, crosslinking agent dosage be also required to substantially be controlled, initiator, crosslinking agent and acrylamide Mass ratio be 0.005-0.006:0.004-0.005:1.The dosage of initiator and crosslinking agent is too low to make raw material reaction not fill Point, influence the formation of dual network system and the addition homogeneity question of nano-cellulose.
Preferably, initiator is potassium peroxydisulfate or ammonium persulfate, crosslinking agent N, N'- methylene-bisacrylamide, catalysis Agent is tetramethylethylenediamine.Inventors have found that the selection of initiator, crosslinking agent and catalyst mainly guarantees to keep polymerization anti- It should sufficiently carry out obtaining the good dual network system of cross-linking effect.
S3, molding reaction
Specifically, molding reaction process is to inject mixed solution in mold to react 10-15h, in some embodiments, at Pattern tool is to make water-setting while providing and reacting mold in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness Gum forming works well.
The gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-obtained by method made above organizational project, Application in medicament slow release, cell culturing bracket and the driving of soft substance.What the preparation method in the embodiment of the present invention obtained receives The rice gelatin-compounded hydrogel of cellulose-polyacrylamide-is mainly applied in field of biomedicine technology.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-comprising Following steps:
Discongested firstly, first paper pulp 20g is placed in suitable distilled water, sequentially add 0.32gTEMPO and 2.32gNaBr adds the NaClO solution of 100-284g (6.3%, effective chlorine) after mixing, is added after the reaction was completed suitable It measures dehydrated alcohol and terminates reaction, PH remains constant, completely reacted cellulose is placed in homogeneous in high pressure homogenizer and obtains nanometer Cellulose.
It is added in 30mL deionized water secondly, weighing 0.9g gelatin, uniform solution is heated at 60 DEG C, is then added 6.4g acrylamide and 0.321g nano-cellulose, stir evenly.Then 0.036g initiator potassium persulfate is added, 0.03g is handed over Join agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, is quickly uniformly mixing to obtain mixed solution.
Finally, mixed solution quickly injects in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness, 20 12h is reacted under the conditions of DEG C, obtains the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-.
Embodiment 2
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-comprising Following steps:
Discongested firstly, first paper pulp 20g is placed in suitable distilled water, sequentially add 0.32gTEMPO and 2.32gNaBr adds the NaClO solution of 100-284g (6.3%, effective chlorine) after mixing, is added after the reaction was completed suitable It measures dehydrated alcohol and terminates reaction, PH remains constant, completely reacted cellulose is placed in homogeneous in high pressure homogenizer and obtains nanometer Cellulose.
It is added in 30mL deionized water secondly, weighing 1.5g gelatin, uniform solution is heated at 60 DEG C, is then added 6.4g acrylamide and 0.321g nano-cellulose, stir evenly.Then 0.036g initiator potassium persulfate is added, 0.03g is handed over Join agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, is quickly uniformly mixing to obtain mixed solution.
Finally, mixed solution is quickly injected in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness, 12h is reacted under the conditions of 20 DEG C, obtains the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-.
Embodiment 3
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-comprising Following steps:
Discongested firstly, first paper pulp 20g is placed in suitable distilled water, sequentially add 0.32gTEMPO and 2.32gNaBr adds the NaClO solution of 100-284g (6.3%, effective chlorine) after mixing, is added after the reaction was completed suitable It measures dehydrated alcohol and terminates reaction, PH remains constant, completely reacted cellulose is placed in homogeneous in high pressure homogenizer and obtains nanometer Cellulose.
It is added in 30mL deionized water secondly, weighing 2.1g gelatin, uniform solution is heated at 60 DEG C, is then added 6.4g acrylamide and 0.192g nano-cellulose, stir evenly.Then 0.036g initiator potassium persulfate is added, 0.03g is handed over Join agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, is quickly uniformly mixing to obtain mixed solution.
Finally, mixed solution is quickly injected in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness, 12h is reacted under the conditions of 20 DEG C, obtains the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-.
Embodiment 4
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-comprising Following steps:
Discongested firstly, first paper pulp 20g is placed in suitable distilled water, sequentially add 0.32gTEMPO and 2.32gNaBr adds the NaClO solution of 100-284g (6.3%, effective chlorine) after mixing, is added after the reaction was completed suitable It measures dehydrated alcohol and terminates reaction, PH remains constant, completely reacted cellulose is placed in homogeneous in high pressure homogenizer and obtains nanometer Cellulose.
It is added in 30mL deionized water secondly, weighing 3g gelatin, uniform solution is heated at 60 DEG C, is then added 6.4g acrylamide and 0.192g nano-cellulose, stir evenly.Then 0.036g initiator potassium persulfate is added, 0.03g is handed over Join agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, is quickly uniformly mixing to obtain mixed solution.
Finally, mixed solution is quickly injected in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness, 12h is reacted under the conditions of 20 DEG C, obtains the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-.
Embodiment 5
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-comprising Following steps:
Discongested firstly, first paper pulp 20g is placed in suitable distilled water, sequentially add 0.32gTEMPO and 2.32gNaBr adds the NaClO solution of 100-284g (6.3%, effective chlorine) after mixing, is added after the reaction was completed suitable It measures dehydrated alcohol and terminates reaction, PH remains constant, completely reacted cellulose is placed in homogeneous in high pressure homogenizer and obtains nanometer Cellulose.
It is added in 30mL deionized water secondly, weighing 3g gelatin, uniform solution is heated at 60 DEG C, is then added 6.4g acrylamide and 0.064g nano-cellulose, stir evenly.Then 0.036g initiator potassium persulfate is added, 0.03g is handed over Join agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, is quickly uniformly mixing to obtain mixed solution.
Finally, mixed solution is quickly injected in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness, 12h is reacted under the conditions of 20 DEG C, obtains the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-.
Embodiment 6
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-comprising Following steps:
Discongested firstly, first paper pulp 20g is placed in suitable distilled water, sequentially add 0.32gTEMPO and 2.32gNaBr adds the NaClO solution of 100-284g (6.3%, effective chlorine) after mixing, is added after the reaction was completed suitable It measures dehydrated alcohol and terminates reaction, PH remains constant, completely reacted cellulose is placed in homogeneous in high pressure homogenizer and obtains nanometer Cellulose.
It is added in 30mL deionized water secondly, weighing 3g gelatin, uniform solution is heated at 60 DEG C, is then added 6.4g acrylamide and 0.321g nano-cellulose, stir evenly.Then 0.036g initiator potassium persulfate is added, 0.03g is handed over Join agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, is quickly uniformly mixing to obtain mixed solution.
Finally, mixed solution is quickly injected in the glass mold being made by the sheet rubber of two sheet glass and 2mm thickness, 12h is reacted under the conditions of 20 DEG C, obtains the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-.
Embodiment 7-10
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, with implementation The roughly the same dosage that the difference is that only nano-cellulose, polyacrylamide and gelatin of example 6, in embodiment 7-10, gelatin Dosage be 10mg/mL, the dosage of acrylamide is 6.4g.
In embodiment 7 dosage of nano-cellulose be 0g, 0% relative to acrylamide quality;
In embodiment 8 dosage of nano-cellulose be 0.064g, 1% relative to acrylamide quality;
In embodiment 9 dosage of nano-cellulose be 0.192g, 3% relative to acrylamide quality;
In embodiment 10 dosage of nano-cellulose be 0.32g, 5% relative to acrylamide quality.
Embodiment 11-15
The present embodiment provides a kind of preparation methods of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, with implementation The roughly the same dosage that the difference is that only nano-cellulose, polyacrylamide and gelatin of example 6, in embodiment 11-15, nanometer The dosage of cellulose is 0.32g, and the dosage of acrylamide is 6.4g.
The dosage of gelatin is 0mg/mL in embodiment 11;
The dosage of gelatin is 3mg/mL in embodiment 12;
The dosage of gelatin is 5mg/mL in embodiment 13;
The dosage of gelatin is 7mg/mL in embodiment 14;
The dosage of gelatin is 10mg/mL in embodiment 15.
Comparative example 1
This comparative example provides a kind of preparation method of PAM hydrogel, comprising the following steps:
(1) it weighs 6.4g acrylamide (PAM) to be dissolved in 30mL deionized water, 0.036g initiator persulfuric acid is added Potassium, 0.03g crosslinking agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, stir evenly.
(2) mixed solution of step (1) is quickly injected to the glass molds being made by the sheet rubber of two sheet glass and 2mm thickness In tool, 12h is reacted at 20 °C, obtains PAM hydrogel.
Comparative example 2
This comparative example provides a kind of preparation method of PAM-Gelatin hydrogel, comprising the following steps:
(1) it weighs 3g gelatin (Gelatin) to be added in 30mL deionized water, uniform solution is heated at 60 DEG C, so 6.4g acrylamide (PAM) is added afterwards, stirs evenly.Afterwards plus 0.036g initiator potassium persulfate, 0.03g crosslinking agent N, N'- are sub- The double propylene phthalein amine of methyl and 30 μ L catalyst tetramethylethylenediamines, quickly stir evenly.
(2) mixed solution of step (1) is quickly injected to the glass molds being made by the sheet rubber of two sheet glass and 2mm thickness In tool, 12h is reacted at 20 °C, obtains PAM-Gelatin hydrogel.
Comparative example 3
This comparative example provides a kind of preparation method of TOCN-PAM hydrogel, comprising the following steps:
(1) 6.4g acrylamide (PAM) and 0.321g nano-cellulose (TOCN) are weighed, is stirred evenly.Afterwards plus 0.036g Initiator potassium persulfate, 0.03g crosslinking agent N, N'- methylene-bisacrylamide and 30 μ L catalyst tetramethylethylenediamines, quickly It stirs evenly.
(2) mixed solution of step (1) is quickly injected to the glass molds being made by the sheet rubber of two sheet glass and 2mm thickness In tool, 12h is reacted at 20 °C, obtains TOCN-PAM hydrogel.
Test example 1
The performance for the hydrogel being prepared in embodiment 1-6 and comparative example 1-3 is surveyed using conventional method Examination, the test including shape memory rate, tensile deformation and tensile stress the results are shown in Table 1.
1 hydrogel the performance test results of table
Test example 2
The deformation for measuring TOCN-PAM-Gelatin composite hydrogel shape recovery process generates, fixed and restore and multiple The shape-memory properties comparison diagram of Heshui gel, the test result of embodiment 7-15 is as shown in Figure 1-Figure 3, and Fig. 1 a is wherein to implement The test mode figure of example 7.
TOCNx-PAM-Gelatiny, x is percentage (%) of the TOCN relative to AM monomer mass, and y is the use of Gelatin It measures (mg/mL).Wherein hydrogel TOCN0-PAM-Gelatin10, TOCN1-PAM-Gelatin10, TOCN3-PAM- of Fig. 1 Gelatin10, TOCN5-PAM-Gelatin10 are respectively labeled as TOCN0, TOCN1, TOCN3, TOCN5.Hydrogel TOCN5- PAM-Gelatin0, TOCN5-PAM-Gelatin3, TOCN5-PAM-Gelatin5, TOCN5-PAM-Gelatin7 and TOCN5-PAM-Gelatin10 is respectively labeled as Gelatin0, Gelatin3, Gelatin5, Gelatin7, Gelatin10.
It will be seen from figure 1 that (1) plural gel has preferable shape memory function.Hydrogel is curled into such as figure first Shape is placed in cold water and shapes, and can obtain a temporary shapes.When there is the hydrogel batten of temporary shapes to be placed on 90 DEG C In hot water, hydrogel batten can be restored to original state within a short period of time.(2) the shape memory rate of hydrogel batten by The influence of TOCN content is little, is mainly determined by Gelatin content.The shape of TOCN5/PAM/Gelatin10 plural gel is remembered Recalling rate is about 65%, and the Gelatin for comparing other low contents is much higher, and the plural gel without gelatin does not have shape memory Function.All these gels for being fixed temporary shapes can all restore its original-shape in 90 DEG C of hot water.
As seen from Figure 2, TOCN-PAM-Gelatin plural gel shows preferable tensile property, and plural gel can It is stretched with being relatively easy to.Furthermore TOCN-PAM-Gelatin plural gel can be modelled out the shape of various complexity.
From Fig. 3 a can be seen that with TOCN content increase plural gel maximum tensile stress and elasticity modulus also with Increase.The addition of Gelatin has active influence for the promotion of elasticity modulus and tensile strength.For TOCN5-PAM- Its tensile deformation of Gelatin10 plural gel can achieve 683%, tensile stress 237kPa.It is this that there is shape memory function Can high-intensitive hydrogel be expected to be applied to field of biomedicine, as organizational project, medicament slow release, cell culturing bracket and Cartilaginous tissue etc..
In conclusion a kind of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-provided by the invention, passes through It is formed in the nano-cellulose that acrylamide crosspolymer network and gelatin cross-linked network are formed in double-network hydrogel after load oxidation Composite hydrogel has good mechanical strength, while improving the biocompatibility and biological degradability of hydrogel.
A kind of preparation method of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-provided by the invention, passes through Nano-cellulose is obtained after cellulose to be carried out to oxidation and homogeneous in oxidation system, with what is obtained after nanofiber and water mixing Nano-cellulose solution materials, after it is mixed with gelatin aqueous dispersions, acrylamide, initiator, crosslinking agent and catalyst To mixed solution, composite hydrogel is prepared after mixed solution is reacted in molding die.Simple process is easy, and condition is held Easy to control, the composite hydrogel being prepared has good mechanical performance, can be in organizational project, medicament slow release, cell training The fields such as bracket and the driving of soft substance are supported to be used widely.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts Every other embodiment, shall fall within the protection scope of the present invention.

Claims (10)

1. a kind of gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-, which is characterized in that by acrylamide crosspolymer network Double-network hydrogel is formed with gelatin cross-linked network, and load has the nano-cellulose after oxidation in the double-network hydrogel.
2. the preparation method of the gelatin-compounded hydrogel of nano-cellulose-polyacrylamide-according to claim 1, special Sign is, comprising the following steps:
After cellulose is aoxidized in oxidation system, then carry out homogeneous and obtain nano-cellulose, and by the nano-cellulose with Water is mixed to get nano-cellulose solution;
After the nano-cellulose solution is mixed with gelatin aqueous dispersions, acrylamide, initiator, crosslinking agent and catalyst To mixed solution;
The mixed solution is injected in mold and reacts 10-15h.
3. preparation method according to claim 2, which is characterized in that the nano-cellulose, the gelatin aqueous dispersions The mass ratio of middle gelatin dosage and the acrylamide is 0.01-0.05:0.1-0.5:1.
4. preparation method according to claim 2, which is characterized in that the initiator be potassium peroxydisulfate or ammonium persulfate, The crosslinking agent is N, and N'- methylene-bisacrylamide, the catalyst is tetramethylethylenediamine.
5. preparation method according to claim 2, which is characterized in that the oxysome during the cellulose oxidation System is TEMPO/NaBr/NaClO oxidation system.
6. preparation method according to claim 5, which is characterized in that the preparation step of the nano-cellulose include: by Paper pulp is discongested in water, then with TEMPO, NaBr and NaClO hybrid reaction, then using dehydrated alcohol terminate reaction.
7. preparation method according to claim 5, which is characterized in that the solid content of the nano-cellulose solution is 1%- 2%.
8. preparation method according to claim 2, which is characterized in that the preparation of the gelatin aqueous dispersions be by gelatin with Water mixes under the conditions of 40-60 DEG C of temperature, it is preferable that the incorporation time of the gelatin and water is 2-3h.
9. preparation method according to claim 2, which is characterized in that be first will in the preparation process of the mixed solution The nano-cellulose solution, the gelatin aqueous dispersions and the acrylamide after mixing, then with the initiator, institute State crosslinking agent and catalyst mixing.
10. nano-cellulose-polyacrylamide-gelatin that preparation method described in any one of claim 2-9 is prepared Application of the composite hydrogel in the driving of organizational project, medicament slow release, cell culturing bracket and soft substance.
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CN112121225A (en) * 2020-10-16 2020-12-25 广西大学 Nanocomposite hydrogel for bleeding control and preparation method thereof
CN112608495A (en) * 2020-11-10 2021-04-06 深圳大学 Hydrogel composite material, preparation method and application
CN113318267A (en) * 2021-05-27 2021-08-31 东华大学 Mussel bionic infrared-responsive antibacterial hydrogel dressing and preparation method thereof
CN113921793A (en) * 2021-10-10 2022-01-11 郑州大学 Inorganic composite hydrogel electrolyte membrane, preparation thereof and application thereof in water-based zinc ion battery
WO2022025488A1 (en) * 2020-07-28 2022-02-03 광주과학기술원 Hydrogel complex comprising gelatin and synthetic polymer and production method thereof
CN114456527A (en) * 2022-02-08 2022-05-10 西北工业大学深圳研究院 nanocellulose/g-C3N4/polyacrylamide composite hydrogel and preparation method and application thereof
CN115353672A (en) * 2021-12-10 2022-11-18 云南师范大学 Luminous hydrogel material with shape memory function and preparation and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016105582A1 (en) * 2014-12-24 2016-06-30 Nunn Philip A Compositions for ileo-jejunal drug delivery
CN108525018A (en) * 2018-05-14 2018-09-14 四川大学 A kind of high intensity hydrogel and preparation method thereof based on three-dimensional network holder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016105582A1 (en) * 2014-12-24 2016-06-30 Nunn Philip A Compositions for ileo-jejunal drug delivery
CN108525018A (en) * 2018-05-14 2018-09-14 四川大学 A kind of high intensity hydrogel and preparation method thereof based on three-dimensional network holder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI NAN,等: "Rapid shape memory TEMPO-oxidized cellulose nanofibers/polyacrylamide/gelatin hydrogels with enhanced mechanical strength", 《CARBOHYDRATE POLYMERS》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110767470A (en) * 2019-10-25 2020-02-07 华南理工大学 Super capacitor based on anti-freezing hydrogel electrolyte and preparation method thereof
WO2022025488A1 (en) * 2020-07-28 2022-02-03 광주과학기술원 Hydrogel complex comprising gelatin and synthetic polymer and production method thereof
KR20220014164A (en) * 2020-07-28 2022-02-04 광주과학기술원 Hydrogel composite comprising gelatin and synthetic polymer, and process for preparing the same
KR102440646B1 (en) * 2020-07-28 2022-09-06 광주과학기술원 Hydrogel composite comprising gelatin and synthetic polymer, and process for preparing the same
CN112121225A (en) * 2020-10-16 2020-12-25 广西大学 Nanocomposite hydrogel for bleeding control and preparation method thereof
CN112608495A (en) * 2020-11-10 2021-04-06 深圳大学 Hydrogel composite material, preparation method and application
CN113318267A (en) * 2021-05-27 2021-08-31 东华大学 Mussel bionic infrared-responsive antibacterial hydrogel dressing and preparation method thereof
CN113921793A (en) * 2021-10-10 2022-01-11 郑州大学 Inorganic composite hydrogel electrolyte membrane, preparation thereof and application thereof in water-based zinc ion battery
CN113921793B (en) * 2021-10-10 2022-10-28 郑州大学 Inorganic composite hydrogel electrolyte membrane, preparation thereof and application thereof in water-based zinc ion battery
CN115353672A (en) * 2021-12-10 2022-11-18 云南师范大学 Luminous hydrogel material with shape memory function and preparation and application thereof
CN114456527A (en) * 2022-02-08 2022-05-10 西北工业大学深圳研究院 nanocellulose/g-C3N4/polyacrylamide composite hydrogel and preparation method and application thereof

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