CN108404221A - A kind of syringeability organosilicon/chitosan nano composite hydrogel and the preparation method and application thereof - Google Patents
A kind of syringeability organosilicon/chitosan nano composite hydrogel and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of syringeability organosilicon/chitosan nano composite hydrogels and its preparation method and application, select water-soluble amination polyhedral oligomeric silsesquioxane (POSS), after mixing with chitosan solution by it, it is mixed with second of water-soluble polymers with aldehyde radical, the schiff base reaction carried out with aldehyde radical macromolecule using amino contained on POSS, chitosan, generates a kind of organosilicon/chitosan nano composite hydrogel.POSS is uniformly dispersed in chitosan system.Organosilicon/chitosan nano composite hydrogel prepared by the present invention there is reversible response, the more traditional aquagel of mechanical property to be largely increased pH, and have syringeability and self-healing performance.The hydrogel preparation method and simple for process does not use toxic organic molecule crosslinking agent, environmentally protective, be suitble to it is extensive prepare, can be used for biomedical materials field.
Description
Technical field
The invention belongs to new material technology fields, and in particular to a kind of organosilicon/chitosan nano composite hydrogel and its
Preparation method and application.
Background technology
Syringeability hydrogel is formed in situ in vivo, is equivalent to extracellular matrix in nature, can reach very
Deep tissue defects have the invasive of very little and provide good Defect Edge adaptability, can be to avoid in surgical operation
It is highly traumatic, the effects that playing and reduce infection risk, accelerating wound healing, reduce Principle of Pain and reduction surgery cost.Mesh
Preceding syringeability hydrogel is mainly prepared by the method for being chemically crosslinked and being physical crosslinking, compared to chemical crosslinking, physical crosslinking
Gel is formed by intermolecular interaction force, is not related to chemically reacting, thus it is easier and safe.But physics
The shortcomings that being crosslinked injection aquagel is that mechanical strength is poor.Therefore, document report improves its power by introducing nanometer strengthener
Learn performance, including nanoclay, carbon nanotube and graphene etc..
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxanes, POSS) has
There is organic/inorganic cage structure, the skeleton of cage is made of silica element, and the outside of cage is then covered by organic substituents
The diameter of the entire molecules of POSS is generally in 1 ~ 3 nm.Since the caged surface of POSS is made of organic substituents, this makes
Obtaining it has good polymer compatibility, biocompatibility and some other surface compatability.Such as with other nanometer strengtheners
Unlike carbon nanotube, nanoclay and graphene, POSS molecules have determining size and molecular weight, surface functional group
Quantity and position controllable precise, there is more powerful MOLECULE DESIGN, be more easy to obtain the height of desired specific molecular structure
Performance or functional material.Different from toxic organic molecule and carbon nanotube, POSS is non-toxic and tasteless, has excellent biofacies
Capacitive, and tetravalence silicon atom is conducive to the proliferation of cell and the expression of gene, it is considered to be new-generation Biomedical Materials.
Invention content
For problems of the prior art, it is compound that the present invention provides a kind of syringeability organosilicon/chitosan nano
Hydrogel and its preparation method and application, the hydrogel preparation method and simple for process are handed over without using toxic organic molecule
Join agent, it is environmentally protective, it is suitble to extensive preparation, can be used for biomedical materials field.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of syringeability organosilicon/chitosan nano composite hydrogel, it is by POSS, chitosan, aldehyde radical macromolecule and goes
Ion water making is 100 at the weight ratio of, the POSS, chitosan, aldehyde radical macromolecule and deionized water:80:120:4000~
100:400:600:4000。
The POSS is eight poly ammonium chloride propyl polysilsesquioxanes（OCAPS）, the eight poly- silsesquioxanes of poly ammonium chloride phenyl
Alkane（OCABS）Or eight poly ammonium chloride benzyl polysilsesquioxane（OCAMBS）In one kind.
The aldehyde radical macromolecule is aldehyde radical sodium alginate, aldehyde radical hydroxypropyl cellulose, aldehyde radical ethoxy fibre
One kind in dimension element, aldehyde radical glucan or aldehyde radical starch.
The preparation method of the syringeability organosilicon/chitosan nano composite hydrogel, steps are as follows：By chitosan
It is dissolved in acetum, is configured to the chitosan-acetic acid solution that mass fraction is 5%, POSS is added into chitosan-acetic acid solution
Obtain chitosan/POSS solution；Aldehyde radical macromolecule is dissolved in deionized water, until it is completely dissolved to obtain aldehyde radical macromolecule
Then aldehyde radical Polymer Solution is uniformly mixed by solution with chitosan/POSS solution, 37 DEG C of water bath with thermostatic control reactions for 24 hours, are made
Syringeability organosilicon/chitosan nano composite hydrogel.
The POSS, chitosan, aldehyde radical macromolecule and deionized water weight ratio be 100:80:120:4000~100:
400:600:4000。
Syringeability organosilicon/chitosan nano the composite hydrogel is applied to biomedical materials field.
Beneficial effects of the present invention：In the Nanometer composite hydrogel, contained amino and aldehyde radical on POSS and chitosan
The macromolecule of change carries out schiff base reaction, increases the crosslink density of system, generates the figurate solid gel of tool, and
It is added without the chitosan and aldehyde radical high molecular weight reactive of POSS, as a result cannot form the gel of fixed shape.With POSS contents
Increase, storage modulus increases to 1661Pa from 620 Pa, and loss modulus increases to 156Pa from 13Pa, improves chitosan nano
The mechanical strength of rice composite hydrogel.The Nanometer composite hydrogel has reversible response to pH, can realize at various ph values
The multiple reversible transition of sol-gel.The Nanometer composite hydrogel has certain syringeability energy, can be adjusted according to the needs
Gelation time is 1-15 min.The Nanometer composite hydrogel has certain self-healing performance.
Description of the drawings
Fig. 1 is the infrared spectrogram of organosilicon/chitosan nano composite hydrogel.
Fig. 2 is the XRD spectra of organosilicon/chitosan nano composite hydrogel.
Fig. 3 is the scanning electron microscope (SEM) photograph of organosilicon/chitosan nano composite hydrogel.
Fig. 4 is the rheological property curve of organosilicon/chitosan nano composite hydrogel.
Specific implementation mode
With reference to specific embodiment, the present invention is further illustrated.The embodiment be only used for the description of the invention without
It is to limit the scope of the invention.In addition, after reading the content taught by the present invention, those skilled in the art can be to this hair
Bright various modifications may be made or change, and these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1
Eight poly ammonium chloride propyl polysilsesquioxanes（OCAPS）：By the 3- aminopropyl triethoxysilanes (KH550) of 30 mL and
The concentrated hydrochloric acid of 27 mL is added sequentially in the single port bottle for filling 200 mL absolute methanols, at room temperature magnetic agitation, in reaction process
There is white precipitate generation, after a week, suction filtration products therefrom, 40oC is dried in vacuo 24 hours, and i.e. eight polychlorostyrene of water solubility POSS are made
Change ammonium propyl polysilsesquioxane（OCAPS）.
Embodiment 2
CS/HPC/OCAPS2.50The preparation of Nanometer composite hydrogel：It is 1% to weigh 0.20g chitosans to be dissolved in 4ml mass fractions
In acetum, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, 0.10g is then added into chitosan-acetic acid solution
OCAPS；It weighs 0.30g aldehyde radical hydroxypropyl celluloses to be dissolved in 4ml deionized waters, until it is completely dissolved, then will dissolve
Full aldehyde radical hydroxypropyl cellulose solution is uniformly mixed with chitosan solution, and 37oC waters bath with thermostatic control are reacted 24 hours, are prepared for
A kind of tri compound hydrogel.
The CS/HPC/OCAPS of the present embodiment2.50Nanometer composite hydrogel, wherein 2.50 meaning refers to OCAPS poly- in shell
Mass fraction in sweet and sour acid solution, i.e. 2.5wt%, similarly hereinafter.
Embodiment 3
CS/HPC/OCAPS3.75The preparation of Nanometer composite hydrogel：It is 1wt%'s to weigh 0.2g chitosans to be dissolved in 4ml mass fractions
In acetum, it is configured to the chitosan-acetic acid solution that mass fraction is 5 wt %, is then added into chitosan-acetic acid solution
0.15g OCAPS.0.3g aldehyde radical hydroxypropyl celluloses are weighed to be dissolved in 4ml deionized waters, until it is completely dissolved, it then will be molten
It solves complete aldehyde radical hydroxypropyl cellulose solution to be uniformly mixed with chitosan solution, 37oC waters bath with thermostatic control are reacted 24 hours, system
For a kind of tri compound hydrogel.
Embodiment 4
CS/HPC/OCAPS5.00The preparation of Nanometer composite hydrogel：It weighs 0.2g chitosans and is dissolved in the vinegar that 4ml mass fractions are 1%
In acid solution, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, 0.20g is then added into chitosan-acetic acid solution
OCAPS.It weighs 0.3g aldehyde radical hydroxypropyl celluloses to be dissolved in 4ml deionized waters, until it is completely dissolved, then will dissolve complete
Aldehyde radical hydroxypropyl cellulose solution be uniformly mixed with chitosan solution, 37oC waters bath with thermostatic control are reacted 24 hours, are prepared for one
Kind tri compound hydrogel.
Embodiment 5
CS/HPC/OCAPS6.25The preparation of Nanometer composite hydrogel：It weighs 0.2g chitosans and is dissolved in the vinegar that 4ml mass fractions are 1%
In acid solution, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, 0.25g is then added into chitosan-acetic acid solution
OCAPS.It weighs 0.3g aldehyde radical hydroxypropyl celluloses to be dissolved in 4ml deionized waters, until it is completely dissolved, then will dissolve complete
Aldehyde radical hydroxypropyl cellulose solution be uniformly mixed with chitosan solution, 37oC waters bath with thermostatic control are reacted 24 hours, are prepared for one
Kind tri compound hydrogel.
Embodiment 6
CS/SA/OCABS5.00The preparation of Nanometer composite hydrogel：It weighs 0.16g chitosans and is dissolved in the vinegar that 4ml mass fractions are 1%
In acid solution, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, 0.20g is then added into chitosan-acetic acid solution
OCABS.It weighs 0.3g aldehyde radical sodium alginates to be dissolved in 4ml deionized waters, until it is completely dissolved, then will dissolve complete aldehyde
Base sodium alginate soln is uniformly mixed with chitosan solution, and 37oC waters bath with thermostatic control are reacted 24 hours, and it is multiple to be prepared for a kind of ternary
Heshui gel.
Embodiment 7
CS/HEC/OCAMBS5.00The preparation of Nanometer composite hydrogel：It is 1% to weigh 0.2g chitosans to be dissolved in 4ml mass fractions
In acetum, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, 0.20g is then added into chitosan-acetic acid solution
OCAMBS.It weighs 0.3g aldehyde radical hydroxyethyl celluloses to be dissolved in 4ml deionized waters, until it is completely dissolved, then will dissolve
Full aldehyde radical hydroxyethyl cellulose solution is uniformly mixed with chitosan solution, and 37oC waters bath with thermostatic control are reacted 24 hours, are prepared for
A kind of tri compound hydrogel.
Embodiment 8
CS/DE/OCAMBS5.00The preparation of Nanometer composite hydrogel：It weighs 0.8g chitosans and is dissolved in the vinegar that 4ml mass fractions are 1%
In acid solution, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, 0.20g is then added into chitosan-acetic acid solution
OCAMBS.It weighs 0.3g aldehyde radical glucans to be dissolved in 4ml deionized waters, until it is completely dissolved, then will dissolve complete aldehyde
Base dextran solution is uniformly mixed with chitosan solution, and 37oC waters bath with thermostatic control are reacted 24 hours, and a kind of tri compound is prepared for
Hydrogel.
Embodiment 9
The preparation of the present embodiment syringeability organosilicon/chitosan nano composite hydrogel：It weighs 0.4g chitosans and is dissolved in 4ml matter
It measures in the acetum that score is 1%, is configured to the chitosan-acetic acid solution that mass fraction is 5%, it is then molten to chitosan acetic acid
0.1gPOSS is added in liquid；It weighs 0.6g oxidation hydroxypropyl celluloses to be dissolved in 4ml deionized waters, until it is completely dissolved, then
Complete aldehyde radical hydroxypropyl cellulose solution will be dissolved to be uniformly mixed with chitosan solution, 37oC waters bath with thermostatic control reaction 24 is small
When, syringeability organosilicon/chitosan nano composite hydrogel is made.
Embodiment 10
The preparation of the present embodiment syringeability organosilicon/chitosan nano composite hydrogel：It weighs 0.08g chitosans and is dissolved in 4ml
In the acetum that mass fraction is 1%, it is configured to the chitosan-acetic acid solution that mass fraction is 5%, then to chitosan acetic acid
0.1gPOSS is added in solution；It weighs 0.12g oxidation hydroxypropyl celluloses to be dissolved in 4ml deionized waters, until it is completely dissolved, so
After will dissolve complete aldehyde radical hydroxypropyl cellulose solution and be uniformly mixed with chitosan solution, 37oC waters bath with thermostatic control reaction 24 is small
When, syringeability organosilicon/chitosan nano composite hydrogel is made.
Comparative example 1
The preparation of CS/HPC systems：It weighs 0.2g chitosans to be dissolved in the acetum that 4ml mass fractions are 1%, is configured to quality
The chitosan-acetic acid solution that score is 5%.It weighs 0.3g oxidation hydroxypropyl celluloses to be dissolved in 4ml deionized waters, until it is completely molten
Solution, then will dissolve complete aldehyde radical hydroxypropyl cellulose solution and be uniformly mixed with chitosan solution, and 37oC waters bath with thermostatic control are anti-
It answers 24 hours, is prepared for a kind of chitosan colloidal sol.
With POSS contents（2.50%-6.25wt%）Increase, the crosslinking journey of organosilicon/chitosan nano composite hydrogel
Degree gradually increases, and the color of hydrogel gradually deepens（Gradually become light yellow by white）, and it is not added with the system of POSS（Comparison
Example 1）, cannot be molded, illustrate the introducing of POSS and the increase of content, promote the progress of schiff bases cross-linking reaction, improve water
The processability of gel.
Fig. 1 is the infrared spectrogram of organosilicon/chitosan nano composite hydrogel.It can be seen from the figure that in 1690cm-1-1660cm-1The absorption peak occurred in range is schiff bases key（-C=N-）Stretching vibration characteristic peak, in 3500cm-1-
3400cm-1With 1630 cm-1-1550 cm-1The absorption peak occurred in range be respectively amino N-H stretching vibration characteristic peak and
Bending vibration characteristic peak.In the reaction system, with the introducing of POSS and content（2.50%-6.25wt%）Increase, schiff bases
The stretching vibration characteristic peak of middle C=N becomes more sharp, illustrates that POSS can be same with chitosan as the crosslinking points of reaction system
When take part in schiff base reaction with aldehyde radical hydroxypropyl cellulose, form Nanometer composite hydrogel.
Fig. 2 is the XRD spectra of organosilicon/chitosan nano composite hydrogel.By map analysis it is found that in chitosan and aldehyde radical
Change after introducing POSS in hydroxypropyl cellulose system, disperse peak gradually weakens, and illustrates that the crystallinity of obtained product weakens, low
It, should be the result shows that the contracting of aldehyde amine occurs between POSS, chitosan and aldehyde radical hydroxypropyl cellulose in the crystallinity of original compound
Reaction is closed, the schiff bases key of formation destroys POSS, chitosan and the aldehyde radical hydroxypropyl cellulose ordered structure of itself, leads
The crystallinity of products therefrom is caused to decline.
Fig. 3 is the scanning electron microscope of organosilicon/chitosan nano composite hydrogel, it can be seen from the figure that organosilicon/shell is poly-
Sugared Nanometer composite hydrogel has the typical pore space structure of hydrogel, and hole diameter size belongs to micron order.For difference
The organosilicon of POSS contents/chitosan nano composite hydrogel system, CS/HPC/POSS2.50The hole diameter structure of hydrogel
It is larger, with POSS contents（2.50%-6.25wt%）Increase, the hole diameter of Nanometer composite hydrogel is gradually reduced, hole
Structure is more and more finer and close.This is because with the increase of POSS contents, the number as crosslinking points increases, can be with more aldehyde
Base chemical binding site reacts, and hole diameter is caused to be gradually reduced, and forms more fine and close three-dimensional netted cross-linked structure.
Fig. 4 is the rheological property curve of organosilicon/chitosan nano composite hydrogel.It can be seen from the figure that with
POSS contents（2.5%-6.25wt%）Increase, the storage modulus and loss modulus of hydrogel first increase to be slightly reduced afterwards, but
Higher than the system for being not added with POSS.This illustrates that the increase of POSS contents makes crosslink density in gel network structure increase, and improves
Mechanical strength, but if POSS contents reach 6.25%, it is possible that the aggregation of part, can reduce the modulus of gel instead.
Organosilicon/chitosan nano composite hydrogel of the present invention has syringeability：At room temperature, different POSS are contained
In the CS/HPC/POSS colloidal sols sucking 5ml syringes of amount, it is then injected into 37oIt is molded in C water, it is as seen from the figure, different
The organosilicon of POSS contents/chitosan nano composite hydrogel all has syringeability.
Organosilicon/chitosan nano composite hydrogel of the present invention has the reversible responses of pH：Micro HCl solution is added
Enter into gel, gel becomes the liquid that can be flowed, and a certain amount of NaOH solution is then added, and the liquid of flowing becomes again
Gel.By the cycle three times that pH is adjusted, hydrogel still maintains good mechanical strength, illustrates the Nanometer composite hydrogel
With the reversible responses of good pH.
Organosilicon/chitosan nano composite hydrogel of the present invention has self-healing performance：It is small that hydrogel is cut into gel
Its part is dyed, then gel bits is stitched together by block, after self-healing 24 hours, hydrogel is hung up, is gone forward side by side
Row simple extension.Suspension and drafting results show that the hydrogel based on schiff base reaction has certain self-healing performance.
The basic principles and main features and advantages of the present invention of the present invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (6)
1. a kind of syringeability organosilicon/chitosan nano composite hydrogel, it is characterised in that：It is by POSS, chitosan, aldehyde radical
Change macromolecule and deionized water to be made, the POSS, chitosan, aldehyde radical macromolecule and deionized water weight ratio be 100:
80:120:4000~100:400:600:4000。
2. syringeability organosilicon/chitosan nano composite hydrogel according to claim, it is characterised in that：It is described
POSS is that eight poly ammonium chloride propyl polysilsesquioxanes, eight poly ammonium chloride phenyl sesquisiloxanes or eight poly ammonium chloride benzyls are poly-
One kind in silsesquioxane.
3. syringeability organosilicon/chitosan nano composite hydrogel according to claim, it is characterised in that：Described
Aldehyde radical macromolecule is that aldehyde radical sodium alginate, aldehyde radical hydroxypropyl cellulose, aldehyde radical hydroxyethyl cellulose, aldehyde radical Portugal are poly-
One kind in sugar or aldehyde radical starch.
4. according to the preparation method of any syringeability organosilicon/chitosan nano composite hydrogels of claim 1-3,
It is characterized in that steps are as follows：Chitosan is dissolved in acetum, the chitosan-acetic acid solution that mass fraction is 5% is configured to,
POSS is added into chitosan-acetic acid solution and obtains chitosan/POSS solution；Aldehyde radical macromolecule is dissolved in deionized water, until
It is completely dissolved to obtain aldehyde radical Polymer Solution, then mixes aldehyde radical Polymer Solution with chitosan/POSS solution
Even, for 24 hours, syringeability organosilicon/chitosan nano composite hydrogel is made in 37 DEG C of water bath with thermostatic control reactions.
5. the preparation method of syringeability organosilicon/chitosan nano composite hydrogel according to claim 4, feature
It is：The POSS, chitosan, aldehyde radical macromolecule and deionized water weight ratio be 100:80:120:4000~100:400:
600:4000。
6. syringeability organosilicon/chitosan nano composite hydrogel described in claim 1 is applied to bio-medical material
Field.
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| CN110857359A (en) * | 2018-08-23 | 2020-03-03 | 天津大学 | Preparation method of polysiloxane nanocomposite |
| CN111205485A (en) * | 2020-03-11 | 2020-05-29 | 江南大学 | Preparation method of reinforced modified carboxymethyl chitosan hydrogel |
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| CN113440650A (en) * | 2021-05-21 | 2021-09-28 | 上海大学 | Method for preparing injectable hydrogel through gel crumbling recombination |
| CN114316273A (en) * | 2021-11-18 | 2022-04-12 | 国科广化精细化工孵化器(南雄)有限公司 | Schiff base containing cage type silsesquioxane as well as preparation method and application thereof |
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| CN114539574A (en) * | 2022-02-28 | 2022-05-27 | 浙江农林大学 | Preparation method and application of piezoelectric-triboelectric coupling induction material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539888A (en) * | 2013-09-11 | 2014-01-29 | 郑州轻工业学院 | Organic and inorganic hybrid hydrogel as well as preparation method and application thereof |
| CN103601917A (en) * | 2013-09-11 | 2014-02-26 | 郑州轻工业学院 | Water-soluble organosilicon/cellulose ether nanometer hybrid material, preparation method thereof and applications thereof |
| CN103739862A (en) * | 2013-07-25 | 2014-04-23 | 天津大学 | Gelatin/carboxymethyl chitosan/POSS (polyhedral oligomeric silsesquioxane) photo-crosslinking hydrogel and preparation method |
| CN104479150A (en) * | 2014-10-29 | 2015-04-01 | 上海大学 | Preparation method of multiple cross-linked polysaccharide injectable hydrogel |
| CN106693931A (en) * | 2017-02-27 | 2017-05-24 | 福州大学 | Glucosamine oligosaccharide-functionalized hybrid silica monolithic column and preparation method |
-
2018
- 2018-04-09 CN CN201810310168.0A patent/CN108404221A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739862A (en) * | 2013-07-25 | 2014-04-23 | 天津大学 | Gelatin/carboxymethyl chitosan/POSS (polyhedral oligomeric silsesquioxane) photo-crosslinking hydrogel and preparation method |
| CN103539888A (en) * | 2013-09-11 | 2014-01-29 | 郑州轻工业学院 | Organic and inorganic hybrid hydrogel as well as preparation method and application thereof |
| CN103601917A (en) * | 2013-09-11 | 2014-02-26 | 郑州轻工业学院 | Water-soluble organosilicon/cellulose ether nanometer hybrid material, preparation method thereof and applications thereof |
| CN104479150A (en) * | 2014-10-29 | 2015-04-01 | 上海大学 | Preparation method of multiple cross-linked polysaccharide injectable hydrogel |
| CN106693931A (en) * | 2017-02-27 | 2017-05-24 | 福州大学 | Glucosamine oligosaccharide-functionalized hybrid silica monolithic column and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| YU-TIE BI ET AL.: "Preparation and characterization of Octa(aminophenyl)silsesquioxane–alde-", 《 EUROPEAN POLYMER JOURNAL》 * |
| 窦竞成等: "POSS/壳聚糖/羟丙基纤维素可注射纳米复合水凝胶的制备与性能", 《2017全国高分子学术论文报告会》 * |
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| CN110857359A (en) * | 2018-08-23 | 2020-03-03 | 天津大学 | Preparation method of polysiloxane nanocomposite |
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| CN114316273A (en) * | 2021-11-18 | 2022-04-12 | 国科广化精细化工孵化器(南雄)有限公司 | Schiff base containing cage type silsesquioxane as well as preparation method and application thereof |
| CN114479118A (en) * | 2021-12-24 | 2022-05-13 | 华南理工大学 | Conductive hydrogel based on nanocellulose-polyacrylamide-metal ions and preparation method and application thereof |
| CN114539574A (en) * | 2022-02-28 | 2022-05-27 | 浙江农林大学 | Preparation method and application of piezoelectric-triboelectric coupling induction material |
| CN114539574B (en) * | 2022-02-28 | 2023-06-06 | 浙江农林大学 | Preparation method and application of piezoelectric-triboelectric coupling induction material |
| CN114773595A (en) * | 2022-03-10 | 2022-07-22 | 曾国鸿 | Preparation method of octamercapto POSS (polyhedral oligomeric silsesquioxane) functionalized modified triphenylamine-based hybrid porous material |
| CN114773595B (en) * | 2022-03-10 | 2024-04-05 | 刘春晓 | Preparation method of octamercapto POSS functionalized modified triphenylamine hybrid porous material |
| CN118516100A (en) * | 2024-07-23 | 2024-08-20 | 盘锦辽河油田华联实业集团有限公司 | Thickening agent for improving recovery ratio and preparation method thereof |
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