CN109627462A - A kind of preparation method of high intensity methacrylation aquagel - Google Patents
A kind of preparation method of high intensity methacrylation aquagel Download PDFInfo
- Publication number
- CN109627462A CN109627462A CN201811419778.0A CN201811419778A CN109627462A CN 109627462 A CN109627462 A CN 109627462A CN 201811419778 A CN201811419778 A CN 201811419778A CN 109627462 A CN109627462 A CN 109627462A
- Authority
- CN
- China
- Prior art keywords
- mixed liquor
- methacrylation
- chitosan
- methylene chloride
- later
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a kind of preparation methods of high-intensitive methacrylation aquagel; it is specifically implemented according to the following steps: first; it dissolves the chitosan in solvent; methacrylic anhydride is added; obtain the chitosan solution of methacrylation; it is reloaded into bag filter and dialyses; freeze-drying; refrigeration, it is later that methacrylation chitosan is soluble in water, acrylated F127 is added; photoinitiator is added into mixed liquor; it stirs evenly, prepares hydrogel using the UV photo-crosslinking of 5~10W, high-strength chitosan hydrogel can be obtained.This method can be obtained the high resiliency hydrogel of 2~4MPa compressive strength, while also improving the stability of hydrogel structure by photo-crosslinking water soluble chitosan and F127 derivative.
Description
Technical field
The invention belongs to hydrogel material preparation technical fields, and in particular to a kind of high intensity methacrylation chitosan
The preparation method of hydrogel.
Background technique
Macromolecule hydrogel is the Space network of polymer formed by hydrophilic macromolecule chain chemically or physically, because
Its similar cell epimatrix structure has potential using value in terms of tissue engineering bracket.Hydrogel can by synthesize macromolecule,
Natural polymer and biomolecule etc. are prepared, such as polyethylene glycol, poly hydroxy ethyl acrylate, chitosan, seaweed
Sour sodium, spider's thread protein etc..Chitosan has the excellent properties such as tasteless, odorless, nontoxic and antibacterial, uses extensively as natural polysaccharide
In preparation cell culture hydrogel scaffold, for example, Chinese patent " porous chitosan scaffold, neural stem cell porous chitosan branch
Frame and application thereof " (application number: CN201010532905.5) provide it is a kind of using glutaraldehyde cross-linking to can be used for nerve cord thin
The porous chitosan scaffold of born of the same parents' culture；Chinese patent " a kind of chitosan stent and preparation method thereof for orienting pore-forming " (application number:
201510334698.5) a kind of orientation that can be used for organizational project Bone Defect Repari is obtained using sodium hydroxide and fast freezing processing
Hole chitosan stent.Since chitosan is confined to be dissolved in acetic acid, in the acid mediums solution such as hydrochloric acid, the preparation of these brackets is again
Using glutaraldehyde, sodium hydroxide and other matter makees crosslinking agent, and phase separation agent, therefore, it is difficult to contain and three-dimensional training for cells in situ
It supports.In order to solve this problem, Chinese patent " the preparation side of a kind of UV curable and water-soluble chitosan magnetic hydrogel
Method " (application number: CN201310275379.2) provides a kind of UV curable and water-soluble N- methacrylation is magnetic
Aquagel technology of preparing.The above technology is by molecular modification, and the water soluble chitosan of preparation is, it can be achieved that cell three-dimensional packet
It carries and cultivates.However, the universal mechanical strength of hydrogel of chitosan and its derivative composition is low at present, fragile structure is frangible, sternly
Its reparation and regeneration field for being applied to the histoorgans such as cartilage, skin, blood vessel to the marrow as structural material is limited again.For
Overcome the defect of hydrogel mechanical performance, researcher has designed and synthesized the diversified water-setting with new network structure
Glue.It is representative to establish dual network structure, with " movable crosslinking points " replace covalent cross-linking point, with nano particle be huge more function
The effects of energy crosslinking points or introducing " sacrificing key ", noncovalent interaction and Supramolecular self assembly, absorbs energy, reduces because of covalent bond
Stress collection neutralizes network structure and destroys caused by uneven distribution, to improve the intensity and toughness of gel.For example, China is specially
Sharp " a kind of preparation method of high intensity hydrogel " (application number: is disclosed in 201510080672.2) through dispersion montmorillonite extremely
Chitosan/methyl acrylic acid mixed aqueous solution, then cause and prepare the high intensity hydrogel that elongation at break surpasses 3000%.With top
High intensity hydrogel obtained in method also added acrylamide, N, N'- dimethyl allene in addition to using natural polymer
The compositions such as amide, acrylic acid and its salt, methacrylic acid and its salt, octadecyl methacrylate, lauryl methacrylate,
These chemical analysis can generate toxicity to cell culture before and after initiation, polymerization and cross-linking process.Therefore, it avoids using above-mentioned
Chemical analysis develops cell and good biocompatibility, and the hydrogel for meeting mechanical strength requirement is organizational project and regenerative medicine
The focal issue of research.
In order to solve the water solubility of chitosan, by carrying out methacrylation to it, obtain can UV photo-crosslinking water
Dissolubility methacrylation chitosan；In order to improve its crosslink density, using the F127 of functionalization as crosslinking agent, drawn with UV
Hair, is prepared for the aquagel of the hydrogel of high compression-strength, cell and good biocompatibility.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of high-intensitive methacrylation aquagel, solve
Existing hydrogel mechanical strength is weak, structural stability is poor problem.
The technical scheme adopted by the invention is that a kind of preparation side of high intensity methacrylation aquagel
Method is specifically implemented according to the following steps:
Step 1, the chitosan solution modified containing double bond is prepared；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, F127 derivative is added later, is mixed
Liquid is closed, finally mixed liquor is post-processed, methacrylation aquagel can be obtained；
F127 derivative is aldehyde radical F127 or acrylated F127；
When F127 derivative is aldehyde radical F127, by mixed liquor in 30~37 DEG C of 0.5~1h of placement, methyl can be obtained
Acrylated aquagel；Methacrylation chitosan solution, aldehyde radical F127, water mass ratio be 1~2:10~
15:100；
When F127 derivative is acrylated F127, photoinitiator is added into mixed liquor, stirs evenly, using 5~
The UV photo-crosslinking of 10W prepares hydrogel, and high-strength chitosan hydrogel can be obtained；Methacrylation chitosan solution, third
The mass ratio that alkene is acylated F127, water and photoinitiator is 1~2:10~15:100:1.
The features of the present invention also characterized in that:
In step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, be added methacrylic anhydride, be placed on 60 DEG C~
3h~5h is reacted under conditions of 65 DEG C, obtains the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 1~2:100:1~2；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:50~100；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 3000~
Dialyse 7 days~10 days in 8000 bag filter, later under conditions of -55~-65 DEG C be freeze-dried 48h~72h, finally -
It is refrigerated under conditions of 18 DEG C~-25 DEG C, it is spare.
In step 2, the light intensity of UV light is 10~15mW/cm2, light application time is 1~2min；Photoinitiator is 2- hydroxyl-
2- methyl phenyl ketone.
In step 2, the preparation method of acrylated F127, specifically:
Pluronic F127 is dissolved in anhydrous methylene chloride, is placed in 0 DEG C~4 DEG C of ice-water bath, three second are added
Amine is passed through 15~20min of nitrogen protection, obtains mixed liquor a；
The molar ratio of Pluronic F127, anhydrous methylene chloride and triethylamine are 1:5:10~20；
By it is per second 1 drop~2 drop speed acryloyl chloride is added dropwise into mixed liquor a, the ice-water bath for being placed on 0 DEG C~4 DEG C
Middle reaction 48h~60h, obtains reaction mixture, then reaction mixture is filtered, and removes filter residue, obtains reaction solution；Propylene
The mass ratio of acyl chlorides and mixed liquor a are 1:10~20；
Petroleum ether is added into reaction solution, precipitates 15min~30min, obtained solid matter is placed in vacuum later and is done
It is dry in dry case, obtain acrylated F127；
The volume ratio of reaction solution and petroleum ether is 1:10~15；
Drying temperature is 25 DEG C~35 DEG C, and drying time is 12h~for 24 hours.
In step 2, the preparation method of aldehyde radical F127, specifically:
F127 is uniformly mixed with toluene, later under conditions of 45~50 DEG C revolving removal toluene, revolving the time be 1~
2h adds dry methylene chloride, stirring and dissolving F127,20~30min of mixing time, later under 1~5 DEG C of condition of ice bath
Triethylamine is added into F127, mesyl chloride is finally slowly dropped to F127 in 30~45min under conditions of 0~2 DEG C
In, continue to react 1~3h under this condition after being added dropwise, obtains mixed liquor b；F127, toluene, methylene chloride, triethylamine, first
The molar ratio of sulfonic acid chloride is 0.1~0.2:85~100:150:1.2；
The temperature of mixed liquor b is risen to 30~35 DEG C, is continued after being stirred to react 24 hours, into mixed liquor b be added go from
Sub- water stands split-phase, and liquid phase is extracted with dichloromethane five times, merges organic phase, later successively with dilute salt of 0.8~1.2mol/L
Acid solution wash, saturated salt solution respectively wash organic phase twice, then stand split-phase, and organic phase anhydrous sodium sulfate is at 30~35 DEG C
Under the conditions of dry 12~for 24 hours, obtain mixed liquor c；
Mixed liquor b, deionized water, methylene chloride, saturated salt solution, anhydrous sodium sulfate mass ratio 1:1~2:10:10~
20:10；
Mixed liquor c is rotated, in mixed liquor 60%~80% solvent is removed, obtains concentrate, it later will concentration
Liquid successively precipitates 1~2h in ice ether, dissolves 20~30min in methylene chloride, repeats precipitating-dissolution three times, filtering, will
To filter residue be placed in drying at room temperature 12 in 30~35 DEG C of vacuum drying ovens~for 24 hours, mesylated F127 can be obtained；
Concentrate, ice ether, methylene chloride mass ratio be 1:5~10:5；
Mesylated F127, n,N-Dimethylformamide, 4- hydroxy benzaldehyde and potassium carbonate are uniformly mixed, in 80 DEG C
Under the conditions of under be stirred to react three days, obtain mixed liquor d, mixed liquor d be cooled to room temperature later, deionized water is added and is sufficiently stirred
Afterwards, adopt and be extracted with dichloromethane six times, merge organic phase, organic phase anhydrous sodium sulfate dry 12 under the conditions of 30~35 DEG C~
For 24 hours, mixed liquor e is obtained；
Mesylated F127:DMF:4- hydroxy benzaldehyde: the molar concentration rate of potassium carbonate is 1:100~200:5:5；
Mixed liquor d, deionized water, methylene chloride, anhydrous sodium sulfate mass ratio 1:5~10:10~20:10；
Mixed liquor e is rotated, in mixed liquor 60%~80% solvent is removed, obtains concentrate a, it later will concentration
Liquid a successively precipitates 1~2h in ice ether, dissolves 20~30min in methylene chloride, repeats precipitating-dissolution three times, filters, will
Obtained filter residue is placed in drying at room temperature 12 in 30~35 DEG C of vacuum drying ovens~for 24 hours, and mesylated F127 can be obtained；
Concentrate a, ice ether, methylene chloride mass ratio be 1:10~15:5~10.
The beneficial effects of the present invention are:
This method can be obtained 2~4MPa compressive strength by photo-crosslinking water soluble chitosan and chitosan derivatives
High resiliency hydrogel, while also improving the stability of hydrogel structure.
Detailed description of the invention
Fig. 1 is the compression performance figure of the high-strength chitosan hydrogel of the method for the present invention preparation；
Fig. 2 is that the chitosan crosslinked F127DA hydrogel of methacrylation of the method for the present invention preparation is swollen in aqueous solution
Structural stability figure.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of preparation method of high-intensitive methacrylation aquagel of the present invention, it is specifically real according to the following steps
It applies:
Step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, be added methacrylic anhydride, be placed on 60 DEG C~
3h~5h is reacted under conditions of 65 DEG C, obtains the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 1~2:100:1~2；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:50~100；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 3000~
Dialyse 7 days~10 days in 8000 bag filter, later under conditions of -55~-65 DEG C be freeze-dried 48h~72h, finally -
It is refrigerated under conditions of 18 DEG C~-25 DEG C, it is spare；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, F127 derivative is added later, is mixed
Liquid is closed, finally mixed liquor is post-processed, methacrylation aquagel can be obtained；
F127 derivative is aldehyde radical F127 or acrylated F127；
When F127 derivative is aldehyde radical F127, by mixed liquor in 30~37 DEG C of 0.5~1h of placement, methyl can be obtained
Acrylated aquagel；Methacrylation chitosan solution, aldehyde radical F127, water mass ratio be 1~2:10~
15:100；
When F127 derivative is acrylated F127, photoinitiator is added into mixed liquor, stirs evenly, using 5~
The UV photo-crosslinking of 10W prepares hydrogel, and high-strength chitosan hydrogel can be obtained；Methacrylation chitosan solution, third
The mass ratio that alkene is acylated F127, water and photoinitiator is 1~2:10~15:100:1；
The light intensity of UV light is 10~15mW/cm2, light application time is 1~2min；Photoinitiator is 2- hydroxy-2-methyl benzene
Acetone；
The preparation method of acrylated F127, specifically:
Pluronic F127 is dissolved in anhydrous methylene chloride, is placed in 0 DEG C~4 DEG C of ice-water bath, three second are added
Amine is passed through 15~20min of nitrogen protection, obtains mixed liquor a；
The molar ratio of Pluronic F127, anhydrous methylene chloride and triethylamine are 1:5:10~20；
By it is per second 1 drop~2 drop speed acryloyl chloride is added dropwise into mixed liquor a, the ice-water bath for being placed on 0 DEG C~4 DEG C
Middle reaction 48h~60h, obtains reaction mixture, then reaction mixture is filtered, and removes filter residue, obtains reaction solution；Propylene
The mass ratio of acyl chlorides and mixed liquor a are 1:10~20；
Petroleum ether is added into reaction solution, precipitates 15min~30min, obtained solid matter is placed in vacuum later and is done
It is dry in dry case, obtain acrylated F127 (F127DA)；
The volume ratio of reaction solution and petroleum ether is 1:10~15；
Drying temperature is 25 DEG C~35 DEG C, and drying time is 12h~for 24 hours；
The preparation method of aldehyde radical F127, specifically:
F127 is uniformly mixed with toluene, revolving removal toluene under conditions of 45~50 DEG C, adds dry later
Triethylamine is added in methylene chloride, stirring and dissolving F127 under 1~5 DEG C of condition of ice bath into F127 later, finally at 0~2 DEG C
Under the conditions of mesyl chloride is slowly dropped in F127 in 30~45min, continue to react 1 after being added dropwise under this condition~
3h obtains mixed liquor b；
F127, toluene, methylene chloride, triethylamine, mesyl chloride molar ratio be 0.1~0.2:85~100:150:1.2；
The revolving time is 1~2h, 20~30min of mixing time；
The temperature of mixed liquor b is risen to 30~35 DEG C, is continued after being stirred to react 24 hours, into mixed liquor b be added go from
Sub- water stands split-phase, and liquid phase is extracted with dichloromethane five times, merges organic phase, later successively with dilute salt of 0.8~1.2mol/L
Acid solution wash, saturated salt solution respectively wash organic phase twice, then stand split-phase, and organic phase anhydrous sodium sulfate is at 30~35 DEG C
Under the conditions of dry 12~for 24 hours, obtain mixed liquor c；
Mixed liquor b, deionized water, methylene chloride, saturated salt solution, anhydrous sodium sulfate mass ratio 1:1~2:10:10~
20:10；
Mixed liquor c is rotated, in mixed liquor 60%~80% solvent is removed, obtains concentrate, it later will concentration
Liquid successively precipitates 1~2h in ice ether, dissolves 20~30min in methylene chloride, repeats precipitating-dissolution three times, filtering, will
To filter residue be placed in drying at room temperature 12 in 30~35 DEG C of vacuum drying ovens~for 24 hours, mesylated F127 can be obtained；
Concentrate, ice ether, methylene chloride mass ratio be 1:5~10:5；
Mesylated F127, n,N-Dimethylformamide, 4- hydroxy benzaldehyde and potassium carbonate are uniformly mixed, in 80 DEG C
Under the conditions of under be stirred to react three days, obtain mixed liquor d, mixed liquor d be cooled to room temperature later, deionized water is added and is sufficiently stirred
Afterwards, adopt and be extracted with dichloromethane six times, merge organic phase, organic phase anhydrous sodium sulfate dry 12 under the conditions of 30~35 DEG C~
For 24 hours, mixed liquor e is obtained；
Mesylated F127:DMF:4- hydroxy benzaldehyde: the molar concentration rate of potassium carbonate is 1:100~200:5:5；
Mixed liquor d, deionized water, methylene chloride, anhydrous sodium sulfate mass ratio 1:5~10:10~20:10；
Mixed liquor e is rotated, in mixed liquor 60%~80% solvent is removed, obtains concentrate a, it later will concentration
Liquid a successively precipitates 1~2h in ice ether, dissolves 20~30min in methylene chloride, repeats precipitating-dissolution three times, filters, will
Obtained filter residue is placed in drying at room temperature 12 in 30~35 DEG C of vacuum drying ovens~for 24 hours, and mesylated F127 can be obtained；
Concentrate a, ice ether, methylene chloride mass ratio be 1:10~15:5~10.
Embodiment 1
A kind of preparation method of high-intensitive methacrylation aquagel of the present invention, it is specifically real according to the following steps
It applies:
Step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, methacrylic anhydride is added, be placed on 60 DEG C
Under the conditions of react 3h, obtain the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 1:100:1；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:50；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 3000 it is saturating
It dialyses 7 days in analysis bag, is freeze-dried 48h under conditions of -55 DEG C later, is finally refrigerated under conditions of -18 DEG C, it is spare；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, aldehyde radical F127 is added later, is mixed
Liquid is closed, hydrogel finally is can be obtained into 30~37 DEG C of 0.5~1h of placement in mixed liquor；
The mass ratio of methacrylation chitosan solution, aldehyde radical F127 and water is 1~2:10~15:100；
The preparation method of aldehyde radical F127, specifically:
F127 is uniformly mixed with toluene, revolving removal toluene under conditions of 45 DEG C, adds dry dichloro later
Triethylamine is added in methane, stirring and dissolving F127 under 1 DEG C of condition of ice bath into F127 later, finally by first under conditions of 0 DEG C
Sulfonic acid chloride is slowly dropped in F127 in 30min, is continued to react 1h under this condition after being added dropwise, is obtained mixed liquor b；
F127, toluene, methylene chloride, triethylamine, mesyl chloride molar ratio be 0.1:85:150:1.2；
The revolving time is 1h, mixing time 20min；
The temperature of mixed liquor b is risen to 30 DEG C, continues after being stirred to react 24 hours, deionized water is added into mixed liquor b,
Split-phase is stood, liquid phase is extracted with dichloromethane five times, merges organic phase, is successively washed later with the dilute hydrochloric acid solution of 0.8mol/L
It washs, saturated salt solution respectively washs organic phase twice, then stands split-phase, drying under the conditions of 30 DEG C of organic phase anhydrous sodium sulfate
12h obtains mixed liquor c；
Mixed liquor b, deionized water, methylene chloride, saturated salt solution, anhydrous sodium sulfate mass ratio 1:1:10:10:10；
Mixed liquor c is rotated, in mixed liquor 60% solvent is removed, obtains concentrate, successively by concentrate later
1h is precipitated in ice ether, dissolves 20min in methylene chloride, repeats precipitating-dissolution three times, obtained filter residue is placed in by filtering
Drying at room temperature 12h in 30 DEG C of vacuum drying ovens, can be obtained mesylated F127；
Concentrate, ice ether, methylene chloride mass ratio be 1:5:5；
Mesylated F127, n,N-Dimethylformamide, 4- hydroxy benzaldehyde and potassium carbonate are uniformly mixed, in 80 DEG C
Under the conditions of under be stirred to react three days, obtain mixed liquor d, mixed liquor d be cooled to room temperature later, deionized water is added and is sufficiently stirred
Afterwards, it adopts and is extracted with dichloromethane six times, merge organic phase, organic phase anhydrous sodium sulfate dry 12h under the conditions of 30 DEG C is obtained
Mixed liquor e；
Mesylated F127:DMF:4- hydroxy benzaldehyde: the molar concentration rate of potassium carbonate is 1:100:5:5；
Mixed liquor d, deionized water, methylene chloride, anhydrous sodium sulfate mass ratio 1:5:10:10；
Mixed liquor e is rotated, remove mixed liquor in 60% solvent, obtain concentrate a, later by concentrate a according to
It is secondary to precipitate 1h in ice ether, dissolve 20min in methylene chloride, repeat precipitating-dissolution three times, obtained filter residue is set in filtering
The drying at room temperature 12h in 30 DEG C of vacuum drying ovens, can be obtained mesylated F127；
Concentrate a, ice ether, methylene chloride mass ratio be 1:10:5.
Embodiment 2
A kind of preparation method of high-intensitive methacrylation aquagel of the present invention, it is specifically real according to the following steps
It applies:
Step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, be added methacrylic anhydride, be placed on 60 DEG C DEG C
Under conditions of react 3.5h, obtain the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 2:100:2；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:70；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 4000 it is saturating
It dialyses 8 days in analysis bag, is freeze-dried 50h under conditions of -60 DEG C later, is finally refrigerated under conditions of -20 DEG C, it is spare；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, acrylated F127 is added later, obtains
Mixed liquor, backward mixed liquor in photoinitiator is added, stir evenly, prepare hydrogel using the UV photo-crosslinking of 5~10W, i.e.,
High-strength chitosan hydrogel can be obtained；
Methacrylation chitosan solution, acrylated F127, water and photoinitiator mass ratio be 1:10:100:1；
The light intensity of UV light is 10mW/cm2, light application time 2min；Photoinitiator is 2- hydroxy-2-methyl propiophenone；
The preparation method of acrylated F127, specifically:
Pluronic F127 is dissolved in anhydrous methylene chloride, is placed in 0 DEG C of ice-water bath, triethylamine is added, is led to
Enter nitrogen protection 15min, obtains mixed liquor a；
The molar ratio of Pluronic F127, anhydrous methylene chloride and triethylamine are 1:5:10；
By it is per second 1 drop~2 drop speed acryloyl chloride is added dropwise into mixed liquor a, the ice-water bath for being placed on 0 DEG C in react
48h obtains reaction mixture, then reaction mixture is filtered, and removes filter residue, obtains reaction solution；Acryloyl chloride with mix
The mass ratio of liquid a is 1:10；
Petroleum ether is added into reaction solution, precipitates 15min, is later placed in a vacuum drying oven obtained solid matter dry
It is dry, obtain acrylated F127 (F127DA)；
The volume ratio of reaction solution and petroleum ether is 1:10；
Drying temperature is 25 DEG C, drying time 12h.
Embodiment 3
A kind of preparation method of high-intensitive methacrylation aquagel of the present invention, it is specifically real according to the following steps
It applies:
Step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, methacrylic anhydride is added, be placed on 65 DEG C
Under the conditions of react 5h, obtain the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 2:100:1；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:50；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 7000 it is saturating
It dialyses 8 days in analysis bag, is freeze-dried 60h under conditions of -65 DEG C later, is finally refrigerated under conditions of -25 DEG C, it is spare；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, aldehyde radical F127 is added later, is mixed
Liquid is closed, methacrylation aquagel finally is can be obtained into 35 DEG C of placement 1h in mixed liquor；Methacrylation shell
Glycan solution, aldehyde radical F127, water mass ratio be 1:15:100；
The preparation method of aldehyde radical F127, specifically:
F127 is uniformly mixed with toluene, revolving removal toluene under conditions of 50 DEG C, adds dry dichloro later
Triethylamine is added in methane, stirring and dissolving F127 under 5 DEG C of condition of ice bath into F127 later, finally by first under conditions of 2 DEG C
Sulfonic acid chloride is slowly dropped in F127 in 45min, is continued to react 3h under this condition after being added dropwise, is obtained mixed liquor b；
F127, toluene, methylene chloride, triethylamine, mesyl chloride molar ratio be 0.2:100:150:1.2；
The revolving time is 2h, mixing time 25min；
The temperature of mixed liquor b is risen to 30~35 DEG C, is continued after being stirred to react 24 hours, into mixed liquor b be added go from
Sub- water stands split-phase, and liquid phase is extracted with dichloromethane five times, merges organic phase, successively uses the dilute hydrochloric acid solution of 1mol/L later
Washing, saturated salt solution respectively wash organic phase twice, then stand split-phase, and organic phase anhydrous sodium sulfate is dry under the conditions of 35 DEG C
12h obtains mixed liquor c；
Mixed liquor b, deionized water, methylene chloride, saturated salt solution, anhydrous sodium sulfate mass ratio 1:2:10:15:10；
Mixed liquor c is rotated, in mixed liquor 80% solvent is removed, obtains concentrate, successively by concentrate later
2h is precipitated in ice ether, dissolves 25min in methylene chloride, repeats precipitating-dissolution three times, obtained filter residue is placed in by filtering
Drying at room temperature 20h in 35 DEG C of vacuum drying ovens, can be obtained mesylated F127；
Concentrate, ice ether, methylene chloride mass ratio be 1:8:5；
Mesylated F127, n,N-Dimethylformamide, 4- hydroxy benzaldehyde and potassium carbonate are uniformly mixed, in 80 DEG C
Under the conditions of under be stirred to react three days, obtain mixed liquor d, mixed liquor d be cooled to room temperature later, deionized water is added and is sufficiently stirred
Afterwards, adopt and be extracted with dichloromethane six times, merge organic phase, organic phase anhydrous sodium sulfate dry 12 under the conditions of 35 DEG C~for 24 hours,
Obtain mixed liquor e；
Mesylated F127:DMF:4- hydroxy benzaldehyde: the molar concentration rate of potassium carbonate is 1:150:5:5；
Mixed liquor d, deionized water, methylene chloride, anhydrous sodium sulfate mass ratio 1:10:20:10；
Mixed liquor e is rotated, remove mixed liquor in 80% solvent, obtain concentrate a, later by concentrate a according to
It is secondary to precipitate 2h in ice ether, dissolve 30min in methylene chloride, repeat precipitating-dissolution three times, obtained filter residue is set in filtering
For 24 hours, mesylated F127 can be obtained in drying at room temperature in 35 DEG C of vacuum drying ovens；
Concentrate a, ice ether, methylene chloride mass ratio be 1:10:5.
Embodiment 4
A kind of preparation method of high-intensitive methacrylation aquagel of the present invention, it is specifically real according to the following steps
It applies:
Step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, methacrylic anhydride is added, be placed on 65 DEG C
Under the conditions of react 5h, obtain the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 2:100:2；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:80；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 8000 it is saturating
It dialyses 10 days in analysis bag, is freeze-dried 48h under conditions of -65 DEG C later, is finally refrigerated under conditions of -25 DEG C, it is spare；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, acrylated F127 is added later, obtains
Photoinitiator is added into mixed liquor for mixed liquor, stirs evenly, and prepares hydrogel using the UV photo-crosslinking of 5~10W, can obtain
To high-strength chitosan hydrogel；Methacrylation chitosan solution, acrylated F127, water and photoinitiator mass ratio
For 1:15:100:1；
The light intensity of UV light is 15mW/cm2, light application time 2min；Photoinitiator is 2- hydroxy-2-methyl propiophenone；
The preparation method of acrylated F127, specifically:
Pluronic F127 is dissolved in anhydrous methylene chloride, is placed in 4 DEG C of ice-water bath, triethylamine is added, is led to
Enter nitrogen protection 20min, obtains mixed liquor a；
The molar ratio of Pluronic F127, anhydrous methylene chloride and triethylamine are 1:5:20；
By it is per second 2 drop speed acryloyl chloride is added dropwise into mixed liquor a, the ice-water bath for being placed on 4 DEG C in react 60h,
Reaction mixture is obtained, then reaction mixture is filtered, filter residue is removed, obtains reaction solution；Acryloyl chloride is with mixed liquor a's
Mass ratio is 1:20；
Petroleum ether is added into reaction solution, precipitates 30min, is later placed in a vacuum drying oven obtained solid matter dry
It is dry, obtain acrylated F127 (F127DA)；
The volume ratio of reaction solution and petroleum ether is 1:15；
Drying temperature is 35 DEG C, and drying time is for 24 hours.
Embodiment 5
A kind of preparation method of high-intensitive methacrylation aquagel of the present invention, it is specifically real according to the following steps
It applies:
Step 1, the chitosan solution modified containing double bond is prepared, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, methacrylic anhydride is added, be placed on 65 DEG C
Under the conditions of react 5h, obtain the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 2:100:1；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:100；
Step 1.2, by the methacrylation chitosan solution obtained after step 1.1 be packed into molecular weight be 8000 it is saturating
It dialyses 10 days in analysis bag, is freeze-dried 72h under conditions of -65 DEG C later, is finally refrigerated under conditions of -25 DEG C, it is spare；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, aldehyde radical F127 is added later, is mixed
It closes liquid and methacrylation aquagel can be obtained by mixed liquor in 30 DEG C of placement 1h；Methacrylation chitosan
Solution, aldehyde radical F127, water mass ratio be 1~2:15:100；
The preparation method of aldehyde radical F127, specifically:
F127 is uniformly mixed with toluene, revolving removal toluene under conditions of 50 DEG C, adds dry dichloro later
Triethylamine is added in methane, stirring and dissolving F127 under 5 DEG C of condition of ice bath into F127 later, finally by first under conditions of 2 DEG C
Sulfonic acid chloride is slowly dropped in F127 in 45min, is continued to react 3h under this condition after being added dropwise, is obtained mixed liquor b；
F127, toluene, methylene chloride, triethylamine, mesyl chloride molar ratio be 0.1:100:150:1.2；
The revolving time is 2h, mixing time 30min；
The temperature of mixed liquor b is risen to 35 DEG C, continues after being stirred to react 24 hours, deionized water is added into mixed liquor b,
Split-phase is stood, liquid phase is extracted with dichloromethane five times, merges organic phase, is successively washed later with the dilute hydrochloric acid solution of 1.2mol/L
It washs, saturated salt solution respectively washs organic phase twice, then stands split-phase, drying under the conditions of 35 DEG C of organic phase anhydrous sodium sulfate
For 24 hours, mixed liquor c is obtained；
Mixed liquor b, deionized water, methylene chloride, saturated salt solution, anhydrous sodium sulfate mass ratio 1:2:10:20:10；
Mixed liquor c is rotated, in mixed liquor 80% solvent is removed, obtains concentrate, successively by concentrate later
2h is precipitated in ice ether, dissolves 30min in methylene chloride, repeats precipitating-dissolution three times, obtained filter residue is placed in by filtering
For 24 hours, mesylated F127 can be obtained in drying at room temperature in 35 DEG C of vacuum drying ovens；
Concentrate, ice ether, methylene chloride mass ratio be 1:10:5；
Mesylated F127, n,N-Dimethylformamide, 4- hydroxy benzaldehyde and potassium carbonate are uniformly mixed, in 80 DEG C
Under the conditions of under be stirred to react three days, obtain mixed liquor d, mixed liquor d be cooled to room temperature later, deionized water is added and is sufficiently stirred
Afterwards, it adopts and is extracted with dichloromethane six times, merge organic phase, drying under the conditions of 30 DEG C of organic phase anhydrous sodium sulfate for 24 hours, obtains
Mixed liquor e；
Mesylated F127:DMF:4- hydroxy benzaldehyde: the molar concentration rate of potassium carbonate is 1:200:5:5；
Mixed liquor d, deionized water, methylene chloride, anhydrous sodium sulfate mass ratio 1:10:20:10；
Mixed liquor e is rotated, remove mixed liquor in 80% solvent, obtain concentrate a, later by concentrate a according to
It is secondary to precipitate 2h in ice ether, dissolve 30min in methylene chloride, repeat precipitating-dissolution three times, obtained filter residue is set in filtering
For 24 hours, mesylated F127 can be obtained in drying at room temperature in 35 DEG C of vacuum drying ovens；
Concentrate a, ice ether, methylene chloride mass ratio be 1:15:10.
The method of the present invention is prepared for by the hydrogel of methacrylation chitosan and F127 derivative cross-linking reaction, tool
There is excellent compressibility, as shown in Figure 1, its compressive strength is up to 2~4MPa.The mechanism of high resiliency natural chitosan hydrogel
It is: the micella using hydrophobic segment as core, hydrophilic segment for shell is formed in aqueous solution using F127 derivative, since micella is in power
Under the action of, it is easily-deformable, after external force revocation, it can restore or spontaneously form again micella in time, this provides good for hydrogel
Good energy dissipation；By the double bond of hydrophilic segment end with methacrylation is chitosan crosslinked reacts, improve gel net
The crosslink density of network, so that gel mechanical strength increases.
The hydrogel prepared using chitosan and acrylated F127, wherein chitosan molecule can be by F127DA micella
And its gel network is fixed, it is made to be difficult to be swollen, and keeps the globality of hydrogel, in addition, the knot of the hydrogel of this method preparation
Structure is relatively stable, as shown in Fig. 2, structure does not change after the hydrogel is placed 15 days, it was demonstrated that its structure has higher
Stability.This method solves the structural instability critical issue of Pluronic F127 hydrogel external application simultaneously.
Present invention obtains the high resiliency hydrogels that compressive strength reaches 2~4MPa, and the gel is in organizational project such as joint
The fields such as cartilage, skin have potential using value.
Claims (6)
1. a kind of preparation method of high intensity methacrylation aquagel, which is characterized in that specifically according to following step
It is rapid to implement:
Step 1, the chitosan solution modified containing double bond is prepared；
Step 2, high-intensitive methacrylation aquagel is prepared, specifically:
The methacrylation chitosan obtained after step 1 is soluble in water, F127 derivative is added later, is mixed
Liquid finally post-processes mixed liquor, and methacrylation aquagel can be obtained；
F127 derivative is aldehyde radical F127 or acrylated F127；
When F127 derivative is aldehyde radical F127, by mixed liquor in 30~37 DEG C of 0.5~1h of placement, metering system can be obtained
Acylation chitosan hydrogel；Methacrylation chitosan solution, aldehyde radical F127, water mass ratio be 1~2:10~15:
100；
When F127 derivative is acrylated F127, photoinitiator is added into mixed liquor, stirs evenly, uses 5~10W's
UV photo-crosslinking prepares hydrogel, and high-strength chitosan hydrogel can be obtained；It is methacrylation chitosan solution, acrylated
The mass ratio of F127, water and photoinitiator are 1~2:10~15:100:1.
2. a kind of preparation method of high-intensitive methacrylation aquagel according to claim 1, feature
It is, in the step 1, prepares the chitosan solution modified containing double bond, specifically:
Step 1.1, dissolve the chitosan in solvent, stir evenly, be added methacrylic anhydride, be placed on 60 DEG C~65 DEG C
Under conditions of react 3h~5h, obtain the chitosan solution of methacrylation；
The mass ratio of chitosan, solvent and methacrylic anhydride is 1~2:100:1~2；
Solvent is acetic acid aqueous solution, and the volume ratio of acetic acid and water is 1:50~100；
Step 1.2, the methacrylation chitosan solution obtained after step 1.1 is packed into molecular weight is 3000~8000
Dialyse 7 days~10 days in bag filter, later under conditions of -55~-65 DEG C be freeze-dried 48h~72h, finally -18 DEG C~-
It is refrigerated under conditions of 25 DEG C, it is spare.
3. a kind of preparation method of high-intensitive methacrylation aquagel according to claim 1, feature
It is, in the step 2, the light intensity of UV light is 10~15mW/cm2, light application time is 1~2min；Photoinitiator is 2- hydroxyl-
2- methyl phenyl ketone.
4. a kind of preparation method of high-intensitive methacrylation aquagel according to claim 1, feature
It is, in the step 2, the preparation method of acrylated F127, specifically:
Pluronic F127 is dissolved in anhydrous methylene chloride, is placed in 0 DEG C~4 DEG C of ice-water bath, triethylamine is added,
It is passed through 15~20min of nitrogen protection, obtains mixed liquor a；
The molar ratio of Pluronic F127, anhydrous methylene chloride and triethylamine are 1:5:10~20；
Acryloyl chloride is added dropwise into mixed liquor a by the speed of~2 drop of 1 drop per second, the ice-water bath for being placed on 0 DEG C~4 DEG C in it is anti-
48h~60h is answered, obtains reaction mixture, then reaction mixture is filtered, filter residue is removed, obtains reaction solution；Acryloyl chloride
Mass ratio with mixed liquor a is 1:10~20；
Petroleum ether is added into reaction solution, precipitates 15min~30min, obtained solid matter is placed in vacuum oven later
Middle drying obtains acrylated F127.
5. a kind of preparation method of high-intensitive methacrylation aquagel according to claim 4, feature
It is, the volume ratio of reaction solution and petroleum ether is 1:10~15；Drying temperature be 25 DEG C~35 DEG C, drying time be 12h~
24h。
6. a kind of preparation method of high-intensitive methacrylation aquagel according to claim 1, feature
It is, in the step 2, the preparation method of aldehyde radical F127, specifically:
F127 is uniformly mixed with toluene, revolving removal toluene under conditions of 45~50 DEG C, revolving time are 1~2h later,
Add dry methylene chloride, stirring and dissolving F127,20~30min of mixing time, later under 1~5 DEG C of condition of ice bath to
Triethylamine is added in F127, is finally slowly dropped to mesyl chloride in F127 in 30~45min under conditions of 0~2 DEG C,
Continue to react 1~3h under this condition after being added dropwise, obtains mixed liquor b；F127, toluene, methylene chloride, triethylamine, methylsulphur
The molar ratio of acyl chlorides is 0.1~0.2:85~100:150:1.2；
The temperature of mixed liquor b is risen to 30~35 DEG C, continues after being stirred to react 24 hours, deionized water is added into mixed liquor b,
Split-phase is stood, liquid phase is extracted with dichloromethane five times, merges organic phase, successively molten with the dilute hydrochloric acid of 0.8~1.2mol/L later
Liquid washing, saturated salt solution respectively wash organic phase twice, then stand split-phase, and organic phase anhydrous sodium sulfate is in 30~35 DEG C of conditions
Lower drying 12~for 24 hours, obtain mixed liquor c；
Mixed liquor b, deionized water, methylene chloride, saturated salt solution, anhydrous sodium sulfate mass ratio 1:1~2:10:10~20:
10；
Mixed liquor c is rotated, remove mixed liquor in 60%~80% solvent, obtain concentrate, later by concentrate according to
It is secondary to precipitate 1~2h in ice ether, dissolve 20~30min in methylene chloride, repeat precipitating-dissolution three times, filtering, by what is obtained
Filter residue is placed in drying at room temperature 12 in 30~35 DEG C of vacuum drying ovens~for 24 hours, and mesylated F127 can be obtained；
Concentrate, ice ether, methylene chloride mass ratio be 1:5~10:5；
Mesylated F127, n,N-Dimethylformamide, 4- hydroxy benzaldehyde and potassium carbonate are uniformly mixed, in 80 DEG C of conditions
It is lower to be stirred to react three days, mixed liquor d is obtained, mixed liquor d is cooled to room temperature after addition deionized water is sufficiently stirred later and is adopted
Be extracted with dichloromethane six times, merge organic phase, organic phase anhydrous sodium sulfate dry 12 under the conditions of 30~35 DEG C~for 24 hours,
Obtain mixed liquor e；
Mesylated F127:DMF:4- hydroxy benzaldehyde: the molar concentration rate of potassium carbonate is 1:100~200:5:5；
Mixed liquor d, deionized water, methylene chloride, anhydrous sodium sulfate mass ratio 1:5~10:10~20:10；
Mixed liquor e is rotated, in mixed liquor 60%~80% solvent is removed, concentrate a is obtained, later by concentrate a
1~2h is successively precipitated in ice ether, dissolves 20~30min in methylene chloride, repeats precipitating-dissolution three times, filtering will obtain
Filter residue be placed in drying at room temperature 12 in 30~35 DEG C of vacuum drying ovens~for 24 hours, mesylated F127 can be obtained；
Concentrate a, ice ether, methylene chloride mass ratio be 1:10~15:5~10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811419778.0A CN109627462A (en) | 2018-11-26 | 2018-11-26 | A kind of preparation method of high intensity methacrylation aquagel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811419778.0A CN109627462A (en) | 2018-11-26 | 2018-11-26 | A kind of preparation method of high intensity methacrylation aquagel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109627462A true CN109627462A (en) | 2019-04-16 |
Family
ID=66069610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811419778.0A Pending CN109627462A (en) | 2018-11-26 | 2018-11-26 | A kind of preparation method of high intensity methacrylation aquagel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627462A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110156915A (en) * | 2019-05-27 | 2019-08-23 | 北京科技大学 | A kind of catechol/N- methacrylation chitosan derivatives and preparation method thereof |
| CN110699322A (en) * | 2019-10-07 | 2020-01-17 | 潍坊医学院 | Three-dimensional tumor cell culture medium and preparation method thereof |
| CN111234267A (en) * | 2020-03-25 | 2020-06-05 | 西安交通大学第二附属医院 | Conductive photo-thermal self-healing composite hydrogel dressing and preparation method and application thereof |
| CN111494702A (en) * | 2020-05-08 | 2020-08-07 | 杭州口腔医院集团有限公司 | Antibacterial hydrogel and preparation method and application thereof |
| CN111533940A (en) * | 2020-04-11 | 2020-08-14 | 东华大学 | Tannic acid functionalized photo-crosslinked hydrogel stent and preparation method thereof |
| CN111574816A (en) * | 2020-04-27 | 2020-08-25 | 华东理工大学 | High-strength biomedical hydrogel material and bath-supported hydrogel 3D printing method |
| CN113024847A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Application of natural polysaccharide hydrogel in hemostasis field |
| CN113230464A (en) * | 2021-04-01 | 2021-08-10 | 暨南大学 | Anti-restenosis 3D printing self-expanding degradable intravascular stent and preparation method thereof |
| CN114392270A (en) * | 2021-12-22 | 2022-04-26 | 苏州浩微生物医疗科技有限公司 | Chitosan microsphere, preparation method and application thereof |
| CN114404665A (en) * | 2022-01-12 | 2022-04-29 | 广东省科学院生物与医学工程研究所 | Magnetic hydrogel and preparation method and application thereof |
| CN114805713A (en) * | 2022-05-17 | 2022-07-29 | 广州贝奥吉因生物科技股份有限公司 | Hydrogel, microneedle, preparation method and application thereof |
| CN117379587A (en) * | 2023-09-15 | 2024-01-12 | 中山大学中山眼科中心 | Tissue adhesive material, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170116811A (en) * | 2016-04-12 | 2017-10-20 | 아주대학교산학협력단 | Injectable double network hydrogels and biomedical use thereof |
-
2018
- 2018-11-26 CN CN201811419778.0A patent/CN109627462A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170116811A (en) * | 2016-04-12 | 2017-10-20 | 아주대학교산학협력단 | Injectable double network hydrogels and biomedical use thereof |
Non-Patent Citations (2)
| Title |
|---|
| QU, JIN ET AL.: "Antibacterial adhesive injectable hydrogels with rapid self-healing, extensibility and compressibility as wound dressing for joints skin wound healing", 《BIOMATERIALS》 * |
| SOHN, SANG SOO ET AL.: "Biomimetic and photo crosslinked hyaluronic acid/pluronic F127 hydrogels with enhanced mechanical and elastic properties to be applied in tissue engineering", 《MACROMOLECULAR RESEARCH》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110156915A (en) * | 2019-05-27 | 2019-08-23 | 北京科技大学 | A kind of catechol/N- methacrylation chitosan derivatives and preparation method thereof |
| CN110699322A (en) * | 2019-10-07 | 2020-01-17 | 潍坊医学院 | Three-dimensional tumor cell culture medium and preparation method thereof |
| CN110699322B (en) * | 2019-10-07 | 2021-07-20 | 潍坊医学院 | Three-dimensional tumor cell culture medium and preparation method thereof |
| CN111234267A (en) * | 2020-03-25 | 2020-06-05 | 西安交通大学第二附属医院 | Conductive photo-thermal self-healing composite hydrogel dressing and preparation method and application thereof |
| CN111533940A (en) * | 2020-04-11 | 2020-08-14 | 东华大学 | Tannic acid functionalized photo-crosslinked hydrogel stent and preparation method thereof |
| CN111574816A (en) * | 2020-04-27 | 2020-08-25 | 华东理工大学 | High-strength biomedical hydrogel material and bath-supported hydrogel 3D printing method |
| CN111494702B (en) * | 2020-05-08 | 2021-09-17 | 杭州口腔医院集团有限公司 | Antibacterial hydrogel and preparation method and application thereof |
| CN111494702A (en) * | 2020-05-08 | 2020-08-07 | 杭州口腔医院集团有限公司 | Antibacterial hydrogel and preparation method and application thereof |
| CN113024847A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Application of natural polysaccharide hydrogel in hemostasis field |
| CN113230464A (en) * | 2021-04-01 | 2021-08-10 | 暨南大学 | Anti-restenosis 3D printing self-expanding degradable intravascular stent and preparation method thereof |
| CN113230464B (en) * | 2021-04-01 | 2022-04-12 | 暨南大学 | Anti-restenosis 3D printing self-expanding degradable intravascular stent and preparation method thereof |
| CN114392270A (en) * | 2021-12-22 | 2022-04-26 | 苏州浩微生物医疗科技有限公司 | Chitosan microsphere, preparation method and application thereof |
| CN114404665A (en) * | 2022-01-12 | 2022-04-29 | 广东省科学院生物与医学工程研究所 | Magnetic hydrogel and preparation method and application thereof |
| CN114805713A (en) * | 2022-05-17 | 2022-07-29 | 广州贝奥吉因生物科技股份有限公司 | Hydrogel, microneedle, preparation method and application thereof |
| CN114805713B (en) * | 2022-05-17 | 2023-08-04 | 广州贝奥吉因生物科技股份有限公司 | Hydrogel, microneedle, preparation method and application thereof |
| CN117379587A (en) * | 2023-09-15 | 2024-01-12 | 中山大学中山眼科中心 | Tissue adhesive material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627462A (en) | A kind of preparation method of high intensity methacrylation aquagel | |
| Zhang et al. | Fabrication of gelatin–hyaluronic acid hybrid scaffolds with tunable porous structures for soft tissue engineering | |
| CN105175755B (en) | High stretching dual network physical cross-linking hydrogel of a kind of high intensity and preparation method thereof | |
| CN105504166A (en) | Sodium alginate-acrylamide composite aquagel, and preparation method and application thereof | |
| CN105131185B (en) | Pineapple bran hemicellulose group pH responsive types porous aquagel and its preparation method and application | |
| CN108047465A (en) | A kind of methacrylate gelatin/chitosan interpenetration network hydrogel, preparation method and application | |
| JP2006524742A (en) | Technology for forming durable superporous hydrogels | |
| WO2020156291A1 (en) | Physical and chemical double cross-linked network high-strength gelatin hydrogel and preparation method therefor | |
| CN105566674B (en) | A kind of chitin nano fiber aeroge of high-specific surface area and preparation method thereof | |
| CN110003506A (en) | A kind of preparation method of high intensity Injectable micelle cross-linked polysaccharides hydrogel | |
| CN103980440A (en) | Semi-interpenetrating intelligent hydrogel and preparation method and application thereof | |
| CN110157012A (en) | A kind of preparation method of high-intensity and high-tenacity gelatin based aquagel | |
| CN113214809A (en) | Environment-friendly profile control and water shutoff system, preparation method thereof and application thereof in medium-low temperature high water-cut oil reservoir | |
| CN103965403A (en) | Novel method for grafting chitosan onto 2-acrylamido-2-methylpropanesulfonic acid (AMPS) | |
| CN109593213A (en) | A kind of preparation method of high intensity hydrogel | |
| Hu et al. | Photo-degradable salecan/xanthan gum ionic gel induced by iron (III) coordination for organic dye decontamination | |
| CN107459590A (en) | A kind of preparation method of hyaluronic acid quaternary ammonium salt | |
| CN110128594A (en) | A kind of temperature/pH Lazer type high-strength nano composite hydrogel and preparation method thereof | |
| CN114316375A (en) | Hierarchical pore structure composite aerogel and preparation method thereof | |
| CN112940295A (en) | Recyclable and reusable green hydrogel at room temperature and preparation method and application thereof | |
| CN104910393A (en) | Cellulose sulfate hydrogel and preparation method thereof | |
| CN110343264A (en) | Aquagel and the preparation method and application thereof | |
| CN110578181B (en) | Preparation method of radiation-proof porous fiber with oriented pore structure, product and application | |
| CN109628031B (en) | Intelligent biological adhesive and preparation method thereof | |
| WO2019192628A2 (en) | Thiolated chitosan derivative, chitosan hydrogel, and preparation methods therefor and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190416 |
|
| RJ01 | Rejection of invention patent application after publication |