CN109971042A - A kind of high intensity dual network amphoteric ion hydrogel and preparation method thereof - Google Patents
A kind of high intensity dual network amphoteric ion hydrogel and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to macromolecule hydrogel technical fields, to solve the problems, such as that traditional amphoteric ion hydrogel mechanical strength is weaker, application range is limited, provide a kind of high-intensitive dual network amphoteric ion hydrogel and preparation method thereof, the high intensity dual network amphoteric ion hydrogel is made of flexible first network and the second network interpenetrating of brittleness, the flexibility first network is the covalent cross-linking network that sulphur sulfobetaines is formed by chemical crosslinking, and second network of brittleness is the physical cross-linked network that sodium alginate and polyvalent cation are formed by coordination.High-intensitive dual network amphoteric ion hydrogel mechanical performance of the invention is excellent, anti-pollution anti-microbial property and biocompatibility are good, has potential application prospect in bio-medical field；Preparation method operating procedure is simple, and mild condition is easily-controllable, to equipment without particular/special requirement, is conducive to large-scale industrial production.
Description
Technical field
The present invention relates to macromolecule hydrogel technical field more particularly to a kind of high-intensitive dual network amphoteric ion hydrogels
And preparation method thereof.
Background technique
Hydrogel (Hydrogel) is the gel using water as decentralized medium, is a kind of water solubility with cross-linked network
A part of hydrophobic grouping and hydrophilic residue, hydrophilic residue and water molecules are introduced in macromolecule, hydrone are connected to netted
Inside, and the cross-linked polymer of hydrophobic residue water-swellable.The use environment of hydrogel is mostly polar salt solution, particularly for doctor
When treating health field, therefore, salt tolerance is one of main performance index of hydrogel.
Compared with common anionic hydrogel, the salt tolerance of amphoteric ion hydrogel is relatively preferable.Amphoteric ion water
Contain anions and canons group on the strand of gel simultaneously, " structure-performance " relationship of such hydrogel depends on its strand
Electrostatic interaction between the composition of ionic group, distribution and ionic group.In each repetitive unit of amphoteric ion polymer simultaneously
With cation group and anionic group, it can be possessed by the aquation of electrostatic induction consumingly bound water molecule
Powerful hydratability, since surface charge is zero, water content is high, therefore this hydrogel has good antibiont adhesion work
Can, it may be used as the hydrogel contact glass of anti-albumen, lipidosis.
Traditional amphoteric ion hydrogel intensity is weaker, makes it in drug delivery vehicle, and wound dressing is used for organizational project
The application such as organization bracket in be limited.Disclosed in Chinese patent literature " a kind of amino acid amphoteric ion hydrogel material and its
Preparation method ", notification number are CN 103435746A, the invention by epoxy group cross-linked polymer with contain primary amine groups or secondary
Amino acid, amino-acid ester or the polypeptide of amido carry out amino acid amphoteric ion hydrogel material made from epoxy ring opening reaction,
PH is under 7 or so neutrallty conditions in amphoteric ion feature.But the amino acid amphoteric ion hydrogel material of the invention be easy by
The influence of use environment, while mechanical strength is also weaker, application range is small.Therefore, develop a kind of higher both sexes of intensity from
Sub- hydrogel has important research significance.
Summary of the invention
The present invention provides to overcome the problems, such as that traditional amphoteric ion hydrogel mechanical strength is weaker, application range is limited
A kind of mechanical performance is excellent, anti-pollution anti-microbial property and the good high-intensitive dual network amphoteric ion water-setting of biocompatibility
Glue.
The present invention also provides a kind of preparation method of high-intensitive dual network amphoteric ion hydrogel, this method operating procedures
Simply, mild condition is easily-controllable, to equipment without particular/special requirement, is conducive to large-scale industrial production.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of high intensity dual network amphoteric ion hydrogel, the high intensity dual network amphoteric ion hydrogel is by flexible first net
Network and the second network interpenetrating of brittleness are constituted, and the flexibility first network is formed for sulphur sulfobetaines by chemical crosslinking covalent
Cross-linked network, second network of brittleness are the physical crosslinking net that sodium alginate and polyvalent cation are formed by coordination
Network.
Polysulfonate acidic group glycine betaine is one of representative of amphoteric ion polymer, monomer-sulfonic group glycine betaine (SBMA)
Structure is similar to taurine, and taurine is a kind of nonprotein amino acid of sulfur-bearing, is widely present in many animal bodies.Both sexes
There is cation group and anionic group simultaneously in each repetitive unit of ionomer, it can pass through electrostatic induction
Aquation consumingly bound water molecule, possesses powerful hydratability.Alginate is as a kind of linear unramified natural
Hy-drophilic polysaccharide, good biocompatibility, be the most widely used natural material of synthesizing high-strength, injectable, self-healing hydrogel it
One.There are two types of repetitive unit, mannuronic acid (M unit) and guluronic acid (G unit) on the chain of alginates, it is rich on segment
The block of the block of G unit arrangement, the block of M unit arrangement and the arrangement of G and M units alternately.In aqueous solution, different alginates
G block in chain is by cation (for example, Ca2+、Fe3+Deng) ionomer is formed, so as to form network structure-in water
Alginate hydrogel.Polyvalent cation of the present invention be can with the carboxylate radical in sodium alginate formed ionic bond sun from
Son.
The present invention respectively using sulfonic group glycine betaine (SBMA) and sodium alginate (SA) as double-network hydrogel flexible the
The main component of the second network of one network and brittleness, sulfonic group glycine betaine form flexible first network by chemical crosslinking
(PSBMA) it is introduced into hydrogel, while making double net hydrogels that there is good anti-albumen non-specific adsorption performance, further
Improve mechanical strength；Sodium alginate and polyvalent cation form the second net of brittleness of physical crosslinking by Coordination interaction
Network makes double net hydrogels have good biocompatibility；In addition, PSBMA is that presentation is zwitterionic in 1 ~ 2 or more pH value
Feature, performance are not easy affected by environment, and application range is wider.
The dual network water-setting that amphoteric ion hydrogel of the invention is formed based on flexible first network and the second network of brittleness
The mechanism that glue (DN gel) can be improved mechanical strength is as follows: flexible first network is in the early stage compared with playing the part of " sacrifice key " under low stress
Role, when flexible first network is destroyed, will dissipate a large amount of stress, and soft and tough the second network of brittleness is in later period high stress
It is lower to play the effect for bearing big deformation, it keeps network complete, substantially increases the mechanical strength of amphoteric ion hydrogel, expand
Its application range.
Sodium alginate of the invention/polysulfonate acidic group glycine betaine anti-pollution double-network hydrogel mechanical performance is excellent, anti-pollution antibacterial
Performance and biocompatibility are good, and tensile strength is up to 0.93MPa, elasticity modulus 0.42MPa, and compressive strength is reachable
16MPa has potential application prospect in bio-medical field.
A kind of preparation method of high intensity dual network amphoteric ion hydrogel, comprising the following steps:
(1) sulfonic group glycine betaine and sodium alginate are dissolved in deionized water, crosslinking agent and photoinitiator is added, stirred to get
Even mixed solution；
(2) it is passed through nitrogen in the mixed solution obtained to step (1), is eliminated completely through ultrasound, centrifugation bubble into mixed solution；
Being passed through nitrogen is to prepare to drive out of the air in mixed solution for the Photoinitiated reactions of oxygen free condition；
(3) will treated, and mixed solution is injected into the glass mold of sealing by step (2), use ultraviolet lighting at room temperature
Reaction is penetrated, after reaction, obtains flexible first network；Sulphur sulfobetaines described in the reaction process passes through chemical crosslinking shape
At covalent cross-linking network, i.e., flexible first network；The sodium alginate molecule of free state is uniformly embedded in the flexibility first network；
(4) the flexible first network that step (3) obtains is impregnated in multivalent cation solutions, forms the second network of brittleness, i.e.,
Obtain high-intensitive dual network amphoteric ion hydrogel；During being somebody's turn to do, the alginic acid of the free state embedded in the flexibility first network
Sodium molecule and polyvalent cation pass through coordination formation physical cross-linked network, i.e. the second network of brittleness, flexible first net
Network and the second network interpenetrating of brittleness constitute high-intensitive dual network amphoteric ion hydrogel.
Preferably, the concentration of sulfonic group glycine betaine is 0.5 ~ 2.0M in the mixed solution in step (1)；It is described mixed
The concentration for closing sodium alginate in solution is 0.04 ~ 0.06g/mL.It must be strictly controlled the concentration of above-mentioned monomer, excessive concentration, meeting
Cause mixed solution viscosity excessive, so that sodium alginate and the mixing of sulfonic group glycine betaine are uneven；Concentration is too low, will lead to seaweed
Sour sodium/polysulfonate acidic group glycine betaine composite hydrogel mechanical strength is very weak, is not easy to keep the shape of colloid, in addition also will affect double
The mechanical performance and antifouling property of net hydrogel.
Preferably, in step (1), the molecule viscosity control of the sodium alginate is in 180 ~ 220mPa.s(1%, 2oC).
It is the low sodium alginate of viscosity used in preparation process of the present invention, it is controllable in certain concentration range internal mobility.
Preferably, the crosslinking agent is N, N- methylene-bisacrylamide in step (1)；The addition of the crosslinking agent
Amount is the 0.03~0.3% of sulfonic group glycine betaine mole.
Preferably, the photoinitiator is α-ketoglutaric acid in step (1)；The additional amount of the photoinitiator is sulphur
The 1~4% of acidic group glycine betaine mole.
Must be strictly controlled the additional amount of above-mentioned crosslinking agent and photoinitiator, additional amount is excessively high, and it is excessive to will lead to the degree of cross linking,
The toughness of hydrogel dies down；Additional amount is too low, and the crosslinking points that will lead to hydrogel are inadequate, and mechanical performance is weaker.
Preferably, the time that is passed through of the nitrogen is 5 ~ 15min in step (2)；Ultrasonic power is controlled in 80 ~ 400W,
Ultrasonic time is controlled in 50 ~ 70min；Centrifugal rotational speed control is controlled in 6000 ~ 7500rpm, centrifugation time in 3 ~ 6min.
Preferably, the wavelength of ultraviolet light is 365nm in step (3)；Irradiation time is controlled in 6 ~ 8h.
Preferably, the polyvalent cation is selected from calcium ion, zinc ion and iron ion (Fe in step (4)3+) in one
Kind is several.
Preferably, the concentration of the multivalent cation solutions is 0.1 ~ 3.0M in step (4)；Soaking time control exists
10~240min.It must be strictly controlled soaking time, soaking time is too short, the tensile strength performance of double-network hydrogel obtained
It is poor with elongation at break, and when soaking time is 120min, effect is best.
Therefore, the invention has the following beneficial effects:
(1) dual network amphoteric ion hydrogel mechanical performance of the invention is excellent, anti-pollution anti-microbial property and biocompatibility are good
It is good, there is potential application prospect in bio-medical field；
(2) preparation method operating procedure is simple, and mild condition is easily-controllable, to equipment without particular/special requirement, is conducive to heavy industrialization
Production.
Detailed description of the invention
Fig. 1 is embodiment 1(A), embodiment 2(B) and embodiment 3(C) made from high intensity dual network amphoteric ion water-setting
The load-deformation curve of glue.
Fig. 2 is embodiment 4(A), embodiment 5(B) and embodiment 6(C) made from high intensity dual network amphoteric ion water-setting
The load-deformation curve of glue.
Fig. 3 is the load-deformation curve of the compression of high intensity dual network amphoteric ion hydrogel made from embodiment 6.
Fig. 4 is 50 second compressions of the resulting high-intensitive dual network amphoteric ion hydrogel of embodiment 6 under 50% compression strain
The load-time curve of circulation.
Fig. 5 is 50 second compressions of the high intensity dual network amphoteric ion hydrogel under 50% compression strain made from embodiment 6
The compressive stress strain curve of circulation.
Fig. 6 is the anti-albumen non-specific adsorption effect of high intensity dual network amphoteric ion hydrogel made from embodiment 6
Figure.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, the technical solutions of the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material is commercially available or the industry is common are following
Method in embodiment is unless otherwise instructed conventional method in that art.
Embodiment 1
It (1) is 180mPa.s(1% by 0.838 g (0.5 M) sulfonic group glycine betaine (SBMA) and 0.24 g molecule viscosity, 2oC)
Sodium alginate (SA) be added in 6 mL deionized waters, be added 0.1 mol%(relative to SBMA) N, N- methylene bisacrylamide
Amide (MBAA) and 4 mol%(are relative to SBMA) α-ketoglutaric acid, stirs 10 min, obtains uniform mixed solution；
(2) be passed through nitrogen 10min in Xiang Shangshu mixed solution, under 80W ultrasonic power conditions ultrasound 60min, 7500 rpm from
5 min of the heart；
(3) it will be injected into the glass mold of sealing by step (2) processed mixed solution, it is ultraviolet with 365 nm at room temperature
8 h of illumination, after reaction, sulphur sulfobetaines form covalent cross-linking network by chemical crosslinking, i.e., flexible first network；The
The sodium alginate molecule of free state is uniformly embedded in one network；
(4) first network for obtaining step (3) is in the CaCl of 3 M210min, the trip embedded in first network are impregnated in solution
The sodium alginate molecule and polyvalent cation of amorph form physical cross-linked network, i.e. the second network of brittleness by coordination, soft
Property first network and the second network interpenetrating of brittleness constitute PSBMA/SA-Ca2+High-intensitive dual network amphoteric ion hydrogel.
PSBMA/SA-Ca made from the present embodiment2+The tensile stress of high-intensitive dual network amphoteric ion hydrogel-strain is bent
Line such as Figure 1A, tensile strength are 0.41 MPa, and elongation at break is 326 %.
Embodiment 2
It (1) is 210mPa.s(1% by 0.838 g(0.5 M) sulfonic group glycine betaine (SBMA) and 0.30 g molecule viscosity, 2oC)
Sodium alginate (SA) is added in 6 mL deionized waters, and 0.1 mol%(is added relative to SBMA) N, N- methylene bisacrylamide acyl
Amine (MBAA) and 4 mol%(are relative to SBMA) α-ketoglutaric acid, stirs 10 min, obtains uniform mixed solution；
(2) 15 min of nitrogen is passed through in Xiang Shangshu mixed solution, ultrasound 50 min, 6000 rpm under 400W ultrasonic power conditions
It is centrifuged 6 min；
(3) it will be injected into the glass mold of sealing by step (2) processed mixed solution, it is ultraviolet with 365 nm at room temperature
6 h of illumination, after reaction, sulphur sulfobetaines form covalent cross-linking network by chemical crosslinking, i.e., flexible first network；The
The sodium alginate molecule of free state is uniformly embedded in one network；
(4) first network for obtaining step (3) is in the CaCl of 2 M2120min, the trip embedded in first network are impregnated in solution
The sodium alginate molecule and polyvalent cation of amorph form physical cross-linked network, i.e. the second network of brittleness by coordination, soft
Property first network and the second network interpenetrating of brittleness constitute PSBMA/SA-Ca2+High-intensitive dual network amphoteric ion hydrogel.
PSBMA/SA-Ca made from the present embodiment2+The tensile stress-strain curve of high-intensitive dual network amphoteric ion water-setting
Such as Figure 1B, tensile strength is 0.49 MPa, and elongation at break is 282 %.
Embodiment 3
It (1) is 185mPa.s(1% by 0.838 g(0.5 M) sulfonic group glycine betaine (SBMA) and 0.36 g molecule viscosity, 2oC)
Sodium alginate (SA) is added in 6 mL deionized waters, and 0.1 mol%(is added relative to SBMA) N, N- methylene bisacrylamide acyl
Amine (MBAA) and 4 mol%(are relative to SBMA) α-ketoglutaric acid, stirs 10 min, obtains uniform mixed solution；
(2) 10 min of nitrogen is passed through in Xiang Shangshu mixed solution, ultrasound 55 min, 6000 rpm under 300W ultrasonic power conditions
It is centrifuged 5 min；
(3) it will be injected into the glass mold of sealing by step (2) processed mixed solution, it is ultraviolet with 365 nm at room temperature
8 h of illumination, after reaction, sulphur sulfobetaines form covalent cross-linking network by chemical crosslinking, i.e., flexible first network；The
The sodium alginate molecule of free state is uniformly embedded in one network；
(4) first network for obtaining step (3) is in the CaCl of 1.5M2100min is impregnated in solution, is embedded in first network
The sodium alginate molecule and polyvalent cation of free state form physical cross-linked network, i.e. the second network of brittleness by coordination,
Flexible first network and the second network interpenetrating of brittleness constitute PSBMA/SA-Ca2+High-intensitive dual network amphoteric ion hydrogel.
PSBMA/SA-Ca made from the present embodiment2+The tensile stress of high-intensitive dual network amphoteric ion hydrogel-strain is bent
Line such as Fig. 1 C, tensile strength are 0.54 MPa, and elongation at break is 282 %.
Embodiment 4
It (1) is 200mPa.s(1% by 0.838 g (0.5 M) sulfonic group glycine betaine (SBMA) and 0.36 g molecule viscosity, 2oC)
Sodium alginate (SA) be added in 6 mL deionized waters, be added 0.2 mol%(relative to SBMA) N, N- methylene bisacrylamide
Amide (MBAA) and 4 mol%(are relative to SBMA) α-ketoglutaric acid, stirs 10 min, obtains uniform mixed solution；
(2) 10 min of nitrogen is passed through in Xiang Shangshu mixed solution, ultrasound 55 min, 7500 rpm under 200W ultrasonic power conditions
It is centrifuged 5 min；
(3) it will be injected into the glass mold of sealing by step (2) processed mixed solution, it is ultraviolet with 365 nm at room temperature
8 h of illumination, after reaction, sulphur sulfobetaines form covalent cross-linking network by chemical crosslinking, i.e., flexible first network；The
The sodium alginate molecule of free state is uniformly embedded in one network；
(4) first network for obtaining step (3) is in the CaCl of 0.15M2200min is impregnated in solution, is embedded in first network
The sodium alginate molecule and polyvalent cation of free state form physical cross-linked network, i.e. the second network of brittleness by coordination,
Flexible first network and the second network interpenetrating of brittleness constitute PSBMA/SA-Ca2+High-intensitive dual network amphoteric ion hydrogel.
PSBMA/SA-Ca made from the present embodiment2+The tensile stress of high-intensitive dual network amphoteric ion hydrogel-strain is bent
Line such as Fig. 2A, tensile strength are 0.79 MPa, and elongation at break is 222 %.
Embodiment 5
It (1) is 220mPa.s(1% by 2.514 g (1.5 M) sulfonic group glycine betaine (SBMA) and 0.36 g molecule viscosity, 2oC)
Sodium alginate (SA) be added in 6 mL deionized waters, be added 0.2 mol%(relative to SBMA) N, N- methylene bisacrylamide
Amide (MBAA) and 4 mol%(are relative to SBMA) α-ketoglutaric acid, stirs 10 min, obtains uniform mixed solution；
(2) 15 min of nitrogen is passed through in Xiang Shangshu mixed solution, ultrasound 70 min, 7000 rpm under 300W ultrasonic power conditions
It is centrifuged 4 min；
(3) it will be injected into the glass mold of sealing by step (2) processed mixed solution, it is ultraviolet with 365 nm at room temperature
8 h of illumination, after reaction, sulphur sulfobetaines form covalent cross-linking network by chemical crosslinking, i.e., flexible first network；The
The sodium alginate molecule of free state is uniformly embedded in one network；
(4) first network for obtaining step (3) is in the CaCl of 0.1M2240min is impregnated in solution, is embedded in first network
The sodium alginate molecule and polyvalent cation of free state form physical cross-linked network, i.e. the second network of brittleness by coordination,
Flexible first network and the second network interpenetrating of brittleness constitute PSBMA/SA-Ca2+High-intensitive dual network amphoteric ion hydrogel.
PSBMA/SA-Ca made from the present embodiment2 +Tensile stress-strain of high-intensitive dual network amphoteric ion hydrogel
Curve such as Fig. 2 B, tensile strength are 0.50 MPa, elongation at break 283%.
Embodiment 6
It (1) is 180mPa.s(1% by 3.352 g(2.0 M) sulfonic group glycine betaine (SBMA) and 0.36 g molecule viscosity, 2oC)
Sodium alginate (SA) is added in 6 mL deionized waters, and 0.2 mol%(is added relative to SBMA) N, N- methylene bisacrylamide acyl
Amine (MBAA) and 4 mol%(are relative to SBMA) α-ketoglutaric acid, stirs 10 min, obtains uniform mixed solution；
(2) 10 min of nitrogen is passed through in Xiang Shangshu mixed solution, ultrasound 65 min, 7500 rpm under 350W ultrasonic power conditions
It is centrifuged 5 min；
(3) it will be injected into the glass mold of sealing by step (2) processed mixed solution, it is ultraviolet with 365 nm at room temperature
6 h of illumination, after reaction, sulphur sulfobetaines form covalent cross-linking network by chemical crosslinking, i.e., flexible first network；The
The sodium alginate molecule of free state is uniformly embedded in one network；
(4) first network for obtaining step (3) is in the CaCl of 2.5M2120min is impregnated in solution, is embedded in first network
The sodium alginate molecule and polyvalent cation of free state form physical cross-linked network, i.e. the second network of brittleness by coordination,
Flexible first network and the second network interpenetrating of brittleness constitute PSBMA/SA-Ca2+High-intensitive dual network amphoteric ion hydrogel.
PSBMA/SA-Ca made from the present embodiment2+The tensile stress of high-intensitive dual network amphoteric ion hydrogel-strain is bent
Line such as Fig. 2 C, tensile strength are 0.61 MPa, elongation at break 372%.Its compressive stress strain curve such as Fig. 3, compression are strong
Degree is 16 MPa.
PSBMA/SA-Ca made from the present embodiment2+High-intensitive continuous 50 second compression 50% of dual network amphoteric ion hydrogel
Compression-relaxation cycles load-time graph such as Fig. 4 and compressive stress strain curve such as Fig. 5.Its anti-albumen non-specificity is inhaled
Attached effect such as Fig. 6, it is known that PSBMA/SA-Ca2+High-intensitive double-network hydrogel has excellent anti-albumen non-specificity effect.
Embodiment 7
Embodiment 7 the difference from embodiment 1 is that, in step (4), polyvalent cation is zinc ion, remaining technique and embodiment 1
It is identical, PSBMA/SA-Zn obtained2+The performance and embodiment 1 of high-intensitive double-network hydrogel are suitable.
Embodiment 8
Embodiment 8 the difference from embodiment 1 is that, in step (4), polyvalent cation be iron ion (Fe3+), remaining technique with
Embodiment 1 is identical, PSBMA/SA-Fe obtained3+The performance and embodiment 1 of high-intensitive double-network hydrogel are suitable.
Performance test
(1) drawing mechanical performance is tested: with the glass mold of 1 mm thickness, preparing a length of 40 mm, width is the hydrogel of 10 mm
Batten, it is 16 mm, wide 4 mm, the hydrogel batten of 1 mm of thickness that gauge length, which is made, with " dumbbell " shape cut-off knife.3 battens are taken to exist
Mechanical stretch experiment is carried out on 5966 universal testing machine of Instron, 100 mm/min of tensile speed measures its mechanical property
Energy.
(2) the cylindrical hydrogel of a height of 8 mm compressor mechanical performance test: is prepared with the glass mold that diameter is 8 mm
Sample takes 3 samples to carry out mechanics compression experiment, 2 mm/ of compression speed on 5966 universal testing machine of Instron
Min measures its mechanical property.When recycling compression verification, resistance to compression disk height is 50%, 2 mm/min of compression speed, and it is anti-to measure it
Fatigue behaviour.
(3) anti-albumen non-specific adsorption experiment: the cuboid hydrogel sample of 5 × 5 × 1 mm of preparation, first with 75 % second
Alcohol impregnates 30 min sterilizing, then impregnates 30 min of PBS buffer solution, and hydrogel is put into 24 orifice plates, and 1 mL, 1 μ g/mL is added
Hydrogel is transferred in the PBS buffer solution of 1 mL after impregnating 1.5 h, is impregnating PBS respectively by HRP-IgG protein enzyme solution
After the h of solution 0.5 and 3, it is transferred to 1 mL citrate-phosphate salt buffer solution and (contains 0.03 % H2O2, 20 μ g/mL neighbour benzene two
Amine) in, with 2 M H after 15 min of reaction2SO4Enzyme reaction is terminated, is tested at 492 nm with microplate reader.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, and is not surpassing
There are also other variations and modifications under the premise of technical solution documented by claim out.
Claims (10)
1. a kind of high intensity dual network amphoteric ion hydrogel, which is characterized in that the high intensity dual network amphoteric ion water-setting
Glue is made of flexible first network and the second network interpenetrating of brittleness, and the flexibility first network is that sulphur sulfobetaines passes through chemistry
The covalent cross-linking network being cross-linked to form, second network of brittleness are that sodium alginate and polyvalent cation are formed by coordination
Physical cross-linked network.
2. a kind of preparation method of high-intensitive dual network amphoteric ion hydrogel as described in claim 1, which is characterized in that packet
Include following steps:
(1) sulfonic group glycine betaine and sodium alginate are dissolved in deionized water, crosslinking agent and photoinitiator is added, stirred to get
Even mixed solution；
(2) it is passed through nitrogen in the mixed solution obtained to step (1), is eliminated completely through ultrasound, centrifugation bubble into mixed solution；
(3) will treated, and mixed solution is injected into the glass mold of sealing by step (2), use ultraviolet lighting at room temperature
Reaction is penetrated, after reaction, obtains flexible first network；
(4) the flexible first network that step (3) obtains is impregnated in multivalent cation solutions, forms the second network of brittleness, i.e.,
Obtain high-intensitive dual network amphoteric ion hydrogel.
3. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(1) in, the concentration of sulfonic group glycine betaine is 0.5 ~ 2.0M in the mixed solution；The concentration of sodium alginate in the mixed solution
For 0.04 ~ 0.06g/mL.
4. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(1) in, the molecule viscosity of the sodium alginate is controlled in 180 ~ 220mPa.s.
5. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(1) in, the crosslinking agent is N, N- methylene-bisacrylamide；The additional amount of the crosslinking agent is sulfonic group glycine betaine mole
0.03~0.3%.
6. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(1) in, the photoinitiator is α-ketoglutaric acid；The additional amount of the photoinitiator be sulfonic group glycine betaine mole 1~
4%。
7. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(2) in, the time that is passed through of the nitrogen is 5 ~ 15min；Ultrasonic power control is controlled in 80 ~ 400W, ultrasonic time 50 ~ 70
min；Centrifugal rotational speed control is controlled in 6000 ~ 7500rpm, centrifugation time in 3 ~ 6 min.
8. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(3) in, the wavelength of ultraviolet light is 365nm；Irradiation time is controlled in 6 ~ 8h.
9. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
(4) in, the polyvalent cation is selected from one or more of calcium ion, zinc ion and iron ion.
10. the preparation method of high intensity dual network amphoteric ion hydrogel according to claim 2, which is characterized in that step
Suddenly in (4), the concentration of the multivalent cation solutions is 0.1 ~ 3.0M；Soaking time is controlled in 10 ~ 240min.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437472A (en) * | 2019-08-12 | 2019-11-12 | 浙江工业大学 | A kind of high-intensitive, salt response double-network hydrogel and its application |
| CN110742087A (en) * | 2019-11-28 | 2020-02-04 | 山东省农作物种质资源中心 | Pea germination accelerating seed soaking liquid and preparation method thereof |
| CN112641994A (en) * | 2020-12-16 | 2021-04-13 | 北京化工大学常州先进材料研究院 | Sports colloid dressing based on betaine derivative and alginate |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396562A (en) * | 2013-07-09 | 2013-11-20 | 西安交通大学 | Preparation method for sodium alginate-acrylamide-based hydrogel |
| CN104311841A (en) * | 2014-09-30 | 2015-01-28 | 江南大学 | Method for preparing high-intensity covalence/ion interpenetrating polymer network easily molded gel |
| CN106749888A (en) * | 2016-11-15 | 2017-05-31 | 中国科学院兰州化学物理研究所 | A kind of preparation method of labyrinth double-network hydrogel pipe |
| CN107011609A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-strength chemical-physical double-network hydrogel with automatic recovery ability and preparation method and application |
| CN107216467A (en) * | 2017-04-25 | 2017-09-29 | 同济大学 | A kind of preparation method of high-strength poly- zwitterion intelligent function gel |
| CN107722301A (en) * | 2017-10-23 | 2018-02-23 | 青岛科技大学 | A kind of preparation method of chemistry/ion double cross connection interpenetration network hydrogel |
| CN107814881A (en) * | 2017-11-14 | 2018-03-20 | 西南石油大学 | A kind of quick copolymer gel of temperature sensitive salt and preparation method thereof |
| CN108276522A (en) * | 2018-02-06 | 2018-07-13 | 湖北工业大学 | Can 3D printing the double cross-linked alginate-polyacrylamide acrylic acid high-performance water gels of iron ion preparation method |
| CN108864494A (en) * | 2017-05-09 | 2018-11-23 | 中国科学院大学 | A kind of dynamic crosslinking double-network hydrogel and the preparation method and application thereof |
| CN109232921A (en) * | 2018-09-06 | 2019-01-18 | 宁波大学 | A kind of preparation method of triplicated network hydrogel |
-
2019
- 2019-03-15 CN CN201910198634.5A patent/CN109971042A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396562A (en) * | 2013-07-09 | 2013-11-20 | 西安交通大学 | Preparation method for sodium alginate-acrylamide-based hydrogel |
| CN104311841A (en) * | 2014-09-30 | 2015-01-28 | 江南大学 | Method for preparing high-intensity covalence/ion interpenetrating polymer network easily molded gel |
| CN107011609A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-strength chemical-physical double-network hydrogel with automatic recovery ability and preparation method and application |
| CN106749888A (en) * | 2016-11-15 | 2017-05-31 | 中国科学院兰州化学物理研究所 | A kind of preparation method of labyrinth double-network hydrogel pipe |
| CN107216467A (en) * | 2017-04-25 | 2017-09-29 | 同济大学 | A kind of preparation method of high-strength poly- zwitterion intelligent function gel |
| CN108864494A (en) * | 2017-05-09 | 2018-11-23 | 中国科学院大学 | A kind of dynamic crosslinking double-network hydrogel and the preparation method and application thereof |
| CN107722301A (en) * | 2017-10-23 | 2018-02-23 | 青岛科技大学 | A kind of preparation method of chemistry/ion double cross connection interpenetration network hydrogel |
| CN107814881A (en) * | 2017-11-14 | 2018-03-20 | 西南石油大学 | A kind of quick copolymer gel of temperature sensitive salt and preparation method thereof |
| CN108276522A (en) * | 2018-02-06 | 2018-07-13 | 湖北工业大学 | Can 3D printing the double cross-linked alginate-polyacrylamide acrylic acid high-performance water gels of iron ion preparation method |
| CN109232921A (en) * | 2018-09-06 | 2019-01-18 | 宁波大学 | A kind of preparation method of triplicated network hydrogel |
Non-Patent Citations (5)
| Title |
|---|
| CHAO ZHAO等: ""Dual Functionality of Antimicrobial and Antifouling of Poly(N-hydroxyethylacrylamide)/Salicylate Hydrogels"", 《LANGMUIR》 * |
| LUO MI等: ""Integrated Antimicrobial and Nonfouling Zwitterionic Polymers"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| YAN SHI等: ""Mechanical and tribological behaviors of PVA/PAAm double network hydrogels under varied strains as cartilage replacement"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 常春雨等: "《新型纤维素、甲壳素水凝胶的构建、结构和性能》", 31 October 2015, 知识产权出版社 * |
| 强圣璐: ""磺酸盐甜菜碱型两性聚合物水凝胶的制备及应用"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437472B (en) * | 2019-08-12 | 2022-03-08 | 浙江工业大学 | High-strength salt-responsive double-network hydrogel and application thereof |
| CN110437472A (en) * | 2019-08-12 | 2019-11-12 | 浙江工业大学 | A kind of high-intensitive, salt response double-network hydrogel and its application |
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| CN112908726A (en) * | 2021-02-03 | 2021-06-04 | 沈阳大学 | Preparation method of double-network full-hydrogel stretchable solid supercapacitor |
| CN112908726B (en) * | 2021-02-03 | 2022-11-15 | 沈阳大学 | Preparation method of double-network full-hydrogel stretchable solid supercapacitor |
| CN113336974A (en) * | 2021-07-21 | 2021-09-03 | 浙江大学 | Easily degradable histidine-based coordination hydrogel with fluidity and preparation method and application thereof |
| CN113336974B (en) * | 2021-07-21 | 2022-06-10 | 浙江大学 | Easily degradable histidine-based coordination hydrogel with fluidity and preparation method and application thereof |
| CN114344571A (en) * | 2021-12-13 | 2022-04-15 | 中国科学院宁波材料技术与工程研究所 | Antibacterial material and preparation method and application thereof |
| CN114196058A (en) * | 2021-12-17 | 2022-03-18 | 浙江工业大学 | Amphoteric ion gel sponge and preparation method thereof |
| CN114196058B (en) * | 2021-12-17 | 2023-04-18 | 浙江工业大学 | Amphoteric ion gel sponge and preparation method thereof |
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