CN109382048A - A kind of hydrogel and preparation method thereof being made of regular bricked aggregation - Google Patents
A kind of hydrogel and preparation method thereof being made of regular bricked aggregation Download PDFInfo
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Abstract
A kind of hydrogel and preparation method thereof being made of regular bricked aggregation of the present invention.The preparation method includes the following steps: that (1) cyclic compound and perfluorinated surfactant are added into carbonate aqueous solution, is reacted after heating；(2) low-carbon alcohols are added in the system into step (1) after reaction, removing bubble is placed in isoperibol to fully reacting to obtain the final product.By the type and concentration of control cyclic compound and perfluorinated surfactant, bricked aggregation can be realized from nano flake to oblique parallelepiped, the transformation of lineal hexahedral the present invention, to realize the purpose regulated and controled to the viscoplasticity and microstructure of hydrogel.Since the microstructure of hydrogel has decisive impact its performance and application, the present invention enriches the preparation field of the hydrogel material with diverse microcosmic structure, be conducive to extend its in medicament transport and control delivery systme, prepare the template of nano material, construct the application in the fields such as supermolecule soft material, inductor.
Description
Technical field
The present invention relates to a kind of hydrogels and preparation method thereof being made of regular bricked aggregation, belong to hydrogel material
Field.
Background technique
Hydrogel refers to using water as solvent but cannot dissolve, and keeps a large amount of hydrone to maintain in the form of it after expansion
Three-dimensional aggregates network structure.Hydrogel material is that one kind is different from solid material and fluent material and has both the excellent spy of the two
Property a kind of novel special material, in addition its good biocompatibility and intelligent swelling character, have extremely in different field
Broad application prospect.
Mid-twentieth century, Wichterle and Lim (Nature 185 (1960) 117-118) are for the first time by poly- 2- ethoxy
Methacrylate hydrogels are applied to biological field, since then, the application of hydrogel gradually expand to the load of anticancer drug with
The fields such as sustained release, intellectual material, environmental pollution improvement, oilfield chemistry, and shown good characteristic and application value.Study table
Bright, the nano-hydrogel for loading anticancer drug utilizes thermoinduction (Mater.Sci.Eng.C 78,773 (2017)) and photo-thermal effect
The control release of anticancer drug can be achieved in (Chem.Commun., 52,978 (2016)), shows good anti-cancer properties.In intelligence
Can Material Field can use hydrogel light sensitive characteristic realize supramolecular hydrogel light-operated selfreparing, using its, pressure-sensitive spy
Property regulation gel film material liquid seepage (Adv.Mater., 25,4636 (2013)).In water environment protection, utilize
The three-dimensional porous network structure of sub-micron to the micron level of hydrogel connection can effectively remove the organic pollutant in sewage,
Such as humic acid, have a good application prospect (Eur.Polym.J., 92,126 (2017)).In oilfield chemistry, vermiform
Micella hydrogel has good shear stability, thermal stability as oil field clean fracturing fluid, takes sand, and leak-off it is few,
Compatibility is good, noresidue (353 (2011) 231-236 of Journal of Colloid&Interface Science).
It is reported that hydrogel has microstructure more abundant, such as spherical vesicles, polyhedral vesicle, vermiculate glues
With plane layer shape structure etc., these aggregate structures are assembled into increasingly complex supramolecular structure by further arranging,
There is high viscoelastic supramolecular hydrogel to be formed.Just because of this polymorphic, various dimensions, the multi-functional knot of hydrogel
Structure, so always by the concern of many scholars, and the hydrogel for constructing diverse microcosmic structure is hydrogel material preparation field
Critical issue.Imitated vesicle structure hydrogel is used for drug pack and cell membrane mould because of its similitude with natural biological film
Quasi-, 3D reticular structure hydrogel is used for organizational engineering field because of its quick selfreparing and good bio-compatibility, sea
Continuous shape hydrogel is used for environmental improvement because of its porous structure and good swelling behavior, and vermiculate glues hydrogel is because of it
Good outstanding Sha Xinger is used as clean fracturing fluid.It can be seen that the microstructure of hydrogel determines it in different field
Using and function.But up to the present, it is rarely reported by the hydrogel that regular brick aggregation is constituted.
Summary of the invention
The object of the present invention is to provide a kind of hydrogel and preparation method thereof, the micromorphology of the hydrogel is in regular brick
Type aggregation, and bricked structure shows the regularity of height, structure novel.
The preparation method of hydrogel provided by the present invention, includes the following steps:
(1) cyclic compound and perfluorinated surfactant are added into carbonate aqueous solution, is reacted after heating；
(2) low-carbon alcohols are added in the system into step (1) after reaction, removing bubble is placed in isoperibol to reaction
Completely to get the hydrogel.
In above-mentioned preparation method, in step (1), the carbonate can be sodium carbonate or potassium carbonate；
The concentration of the carbonate aqueous solution can be 50~100mmolL-1, specifically can be used and dried at 270~300 DEG C
It does to the anhydrous carbonate standard reagent of constant and is prepared.
In above-mentioned preparation method, in step (1), the cyclic compound be Cucurbituril, alpha-cyclodextrin, beta-cyclodextrin,
Gamma-cyclodextrin, list (6- amino -6- deoxidation)-beta-cyclodextrin, carboxymethyl-beta-cyclodextrin, hydroxypropyl-β-cyclodextrin, sulphur butyl -
Beta-cyclodextrin, methyl-B-cyclodextrin or hydropropyl-y-cyclodextrin；
The perfluorinated surfactant is perfluoro hexyl potassium sulfonate, perfluoro octyl sulfonic acid potassium, full-fluorine octyl sulfuryl fluoride, propylene
Sour (N- methyl perfluoro hexyl sulfoamido) ethyl ester, polyacrylic acid 1,1- dihydro perfluoro capryl ester or N- methyl perfluoro hexyl sulphonyl
Aminoethanol.
In above-mentioned preparation method, in step (1), the cyclic compound, the perfluorinated surfactant and the carbon
In the system that acid sodium aqueous solution is formed, the total concentration of the cyclic compound and the perfluorinated surfactant is 50~
200mmol·L-1, such as 100mmolL-1；
The molar ratio of the cyclic compound and the perfluorinated surfactant is 1~9:1, such as 1~4:1,1~3:1,1:
1,3:1 or 4:1.
In above-mentioned preparation method, in step (1), the temperature of the heating is 40~80 DEG C, such as 60 DEG C；
The time of the reaction is 60~180min, such as 120min；
The reaction is carried out under agitation.
In above-mentioned preparation method, in step (2), the low-carbon alcohols can be ethyl alcohol, propyl alcohol, isopropanol, n-butanol or different
Butanol.
In above-mentioned preparation method, in step (2), the volume ratio of the low-carbon alcohols and the carbonate aqueous solution is 2~
5:1, such as 5:1；
The low-carbon alcohols are added under stirring conditions；
The low-carbon alcohols are added after system cooled to room temperature after reaction in step (1).
In above-mentioned preparation method, in step (2), bubble is removed in the way of centrifugal；
The revolving speed that the centrifuge is centrifuged is 500~1000r/min
In above-mentioned preparation method, in step (2), the isoperibol can be the constant temperature that setting temperature is 25~40 DEG C
Baking oven, water bath with thermostatic control or constant incubator.
In above-mentioned preparation method, in step (2), fully reacting needs to react 4~8 weeks and reaches balance to reaction, sentences
Disconnected standard be no longer changed using rheometry hydrogel viscoplasticity or scanning electron microscopic observation hydrogel microstructure not
It changes again.
In above-mentioned preparation method, in step (2), in reaction process, need periodically with hand gently shake promotion react into
Row, makes its quickening reach balance.
The hydrogel that the above method of the present invention is prepared also belongs to protection scope of the present invention.
The preparation method of hydrogel provided by the invention, easy to operate, reagent dosage is few, and gained hydrogel is with higher
Viscoplasticity, and elasticity modulus is much larger than viscous modulus, shows good mechanical performance.In addition, hydrogel prepared by the present invention
It is by closely packed bricked structure composition, structure novel, and bricked structure shows the regularity of height.
Existing surfactant hydrogel, structure are common spherical vesicles, tridimensional network, vermiform glue
Beam, micro-tubular structure, and preparation method is complicated.The preparation method of bricked aggregation hydrogel provided by the present invention, reaction condition
It is simple and easy to control with preparation process, avoid complicated synthesis process, gained hydrogel microstructure is that surface is smooth and high metric
Whole brick structure.And by the type and concentration of control cyclic compound and perfluorinated surfactant, bricked aggregation can
Realize from nano flake to oblique parallelepiped, the transformation of lineal hexahedral, thus realize to the viscoplasticity of hydrogel and microstructure into
The purpose of row regulation.Since the microstructure of hydrogel has decisive impact its performance and application, the present invention is enriched
The preparation field of hydrogel material with diverse microcosmic structure, be conducive to extend its medicament transport and control delivery systme,
It prepares the template of nano material, construct the application in the fields such as supermolecule soft material, inductor.
Detailed description of the invention
Fig. 1 is the SEM picture of hydrogel prepared by the embodiment of the present invention 1.
Fig. 2 is the visco elastic fluids varied curve of hydrogel prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM picture of hydrogel prepared by the embodiment of the present invention 2.
Fig. 4 is the visco elastic fluids varied curve of hydrogel prepared by the embodiment of the present invention 2.
Fig. 5 is the SEM picture of hydrogel prepared by the embodiment of the present invention 3.
Fig. 6 is the visco elastic fluids varied curve of hydrogel prepared by the embodiment of the present invention 3.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1,
The natrium carbonicum calcinatum standard reagent that 10.6000g has been dried to constant at 270~300 DEG C is accurately weighed, is placed in 300
In the beaker of milliliter, appropriate distilled water is added to dissolve, moves in 1000 milliliters of volumetric flasks, be diluted to scale and shake up, obtaining concentration is
100mmol·L-1Carbonic acid sodium standard solution.Weigh 1.8837g hydroxypropyl-β-cyclodextrin and 0.1076g perfluoro octyl sulfonic acid potassium
Powder, 10.00ml is added, and prepared sodium carbonate liquor is configured to two kinds of surfactant total concentrations as 100mmolL in advance-1
And concentration, with the rate heating stirring 120min of 400r/min at 60 DEG C, reacts it sufficiently than the solution for 4:1.To institute
After obtaining solution cooled to room temperature, the ethyl alcohol of 2.00ml is added dropwise while stirring, is after mixing placed in a centrifuge solution
Entrained air bubbles are centrifuged off with the revolving speed of 1000r/min.It is placed in again and reaches balance to reaction within 4 weeks in 25 DEG C of constant temperature ovens and (need
Promotion reaction is periodically gently shaken with hand to carry out, its quickening is made to reach balance；Judgment criteria is to utilize rheometry hydrogel
Viscoplasticity is no longer changed), obtain milky hydrogel.
The SEM picture of hydrogel manufactured in the present embodiment is as shown in Figure 1, it can be seen that and its microstructure is nano flake,
Surface is smooth and height is regular.
The visco elastic fluids varied curve of hydrogel manufactured in the present embodiment as shown in fig. 2, it can be seen that hydrogel have it is higher
Viscoplasticity, and elasticity modulus be much larger than viscous modulus, illustrate the hydrogel have good mechanical performance.
Embodiment 2,
The Anhydrous potassium carbonate standard reagent that 10.6000g has been dried to constant at 270~300 DEG C is accurately weighed, is placed in 300
In the beaker of milliliter, appropriate distilled water is added to dissolve, moves in 1000 milliliters of volumetric flasks, be diluted to scale and shake up, obtaining concentration is
100mmol·L-1Carbonic acid sodium standard solution.Weigh 0.4864g alpha-cyclodextrin and 0.2285g N- methyl perfluoro hexyl sulfonamide
Base ethyl alcohol powder, 10.00ml is added, and prepared sodium carbonate liquor is configured to two kinds of surfactant total concentrations and is in advance
100mmol·L-1And concentration, with the rate heating stirring 120min of 400r/min at 60 DEG C, fills it than the solution for 1:1
Divide reaction.After acquired solution cooled to room temperature, the propyl alcohol of 2.00ml is added dropwise while stirring, after mixing sets solution
Entrained air bubbles are centrifuged off with the revolving speed of 1000r/min in centrifuge.It is placed in 25 DEG C of constant temperature ovens 4 weeks and reaches to reaction again
Balance (needs periodically gently to be shaken promotion reaction with hand to carry out, its quickening is made to reach balance；Judgment criteria is to utilize scanning electron microscope
Observation hydrogel microstructure is no longer changed), obtain milky hydrogel.
The SEM picture of hydrogel manufactured in the present embodiment is fig. 3, it is shown that its microstructure is oblique parallel six
The bricked structure of face body, surface is smooth and height is regular.
The visco elastic fluids varied curve of hydrogel manufactured in the present embodiment is as shown in Figure 4, it can be seen that hydrogel has higher
Viscoplasticity, and elasticity modulus be much larger than viscous modulus, illustrate the hydrogel have good mechanical performance.
Embodiment 3,
The natrium carbonicum calcinatum standard reagent that 10.6000g has been dried to constant at 270~300 DEG C is accurately weighed, is placed in 300
In the beaker of milliliter, appropriate distilled water is added to dissolve, moves in 1000 milliliters of volumetric flasks, be diluted to scale and shake up, obtaining concentration is
100mmol·L-1Carbonic acid sodium standard solution.0.7198g Cucurbituril and 0.1255g full-fluorine octyl sulfuryl fluoride powder are weighed, is added
Prepared sodium carbonate liquor is configured to two kinds of surfactant total concentrations as 100mmolL to 10.00ml in advance-1And concentration ratio
It is reacted sufficiently with the rate heating stirring 120min of 400r/min at 60 DEG C for the solution of 3:1.Certainly to acquired solution
After being so cooled to room temperature, the propyl alcohol of 2.00ml is added dropwise while stirring, solution is placed in a centrifuge with 1000r/ after mixing
The revolving speed of min is centrifuged off entrained air bubbles.It is placed in again and reaches balance to reaction within 4 weeks in 25 DEG C of constant temperature ovens and (need periodically to use hand
Gently concussion promotes reaction to carry out, its quickening is made to reach balance；Judgment criteria is to utilize rheometry hydrogel viscoplasticity not
Change again), obtain milky hydrogel.
The SEM picture of hydrogel manufactured in the present embodiment is as shown in Figure 5, it can be seen that its microstructure is straight parallel six
The bricked structure of face body, surface is smooth and height is regular.
The visco elastic fluids varied curve of hydrogel manufactured in the present embodiment is as shown in Figure 6, it can be seen that hydrogel has higher
Viscoplasticity, and elasticity modulus be much larger than viscous modulus, illustrate the hydrogel have good mechanical performance.
Claims (11)
1. a kind of preparation method of hydrogel, includes the following steps:
(1) cyclic compound and perfluorinated surfactant are added into carbonate aqueous solution, is reacted after heating；
(2) low-carbon alcohols are added into the system after reaction in step (1), removing bubble is placed in isoperibol to having reacted
Entirely to get the hydrogel.
2. preparation method according to claim 1, it is characterised in that: in step (1), the carbonate is sodium carbonate or carbon
Sour potassium.
3. preparation method according to claim 1 or 2, it is characterised in that: in step (1), the carbonate aqueous solution
Concentration is 50~100mmolL-1。
4. preparation method according to any one of claim 1-3, it is characterised in that: in step (1), the ring-type chemical combination
Object is Cucurbituril, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, list (6- amino -6- deoxidation)-beta-cyclodextrin, carboxymethyl-β-ring
Dextrin, hydroxypropyl-β-cyclodextrin, Sulfobutyl ether β _ cyclodextrin, methyl-B-cyclodextrin or hydropropyl-y-cyclodextrin；
The perfluorinated surfactant is perfluoro hexyl potassium sulfonate, perfluoro octyl sulfonic acid potassium, full-fluorine octyl sulfuryl fluoride, acrylic acid
(N- methyl perfluoro hexyl sulfoamido) ethyl ester, polyacrylic acid 1,1- dihydro perfluoro capryl ester or N- methyl perfluoro hexyl sulfonamide
Base ethyl alcohol.
5. preparation method described in any one of -4 according to claim 1, it is characterised in that: in step (1), the ring-type chemical combination
In the system that object, the perfluorinated surfactant and the aqueous sodium carbonate are formed, the cyclic compound and the perfluor
The total concentration of surfactant is 50~200mmolL-1；
The molar ratio of the cyclic compound and the perfluorinated surfactant is 1~9:1.
6. preparation method according to any one of claims 1-5, it is characterised in that: in step (1), the temperature of the heating
Degree is 40~80 DEG C；
The time of the reaction is 60~180min；
The reaction is carried out under agitation.
7. preparation method according to claim 1 to 6, it is characterised in that: in step (2), the low-carbon alcohols are
Ethyl alcohol, propyl alcohol, isopropanol, n-butanol or isobutanol.
8. preparation method described in any one of -7 according to claim 1, it is characterised in that: in step (2), the low-carbon alcohols with
The volume ratio of the aqueous sodium carbonate is 2~5:1；
The low-carbon alcohols are added under stirring conditions.
9. preparation method according to claim 1 to 8, it is characterised in that: in step (2), using centrifuge from
The mode of the heart removes bubble；
The revolving speed that the centrifuge is centrifuged is 500~1000r/min.
10. preparation method according to claim 1 to 9, it is characterised in that: in step (2), be placed in 25~40
DEG C isoperibol in react 4~8 weeks.
11. the hydrogel of any one of claim 1-10 the method preparation.
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2018
- 2018-11-19 CN CN201811375095.XA patent/CN109382048B/en active Active
Patent Citations (4)
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| US5582813A (en) * | 1993-01-28 | 1996-12-10 | Alliance Pharmaceutical Corp. | Iodine-containing fluorocarbon contrast agents |
| US9150788B2 (en) * | 2007-09-18 | 2015-10-06 | Syracuse University | Non-amphiphile-based water-in-water emulsion and uses thereof |
| CN104549077A (en) * | 2014-12-25 | 2015-04-29 | 中国石油大学(北京) | Cationic-anionic surfactant mixed system gel and preparation method thereof |
| CN107930542A (en) * | 2017-11-13 | 2018-04-20 | 王华楠 | One-step method continuously prepares the microflow control technique of calcium alginate microgel |
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