CN109503757A - The preparation of novel double-net network hydrogel and obtained double-network hydrogel and application - Google Patents
The preparation of novel double-net network hydrogel and obtained double-network hydrogel and application Download PDFInfo
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Abstract
The invention discloses a kind of preparation of novel double-net complex ion hydrogel and obtained double-network hydrogel and applications, the method is as follows: obtaining sodium alginate Supramolecular fiber network first, then it is carried out to cross-linked polymeric together with acrylamide monomers, obtain the novel double-net network hydrogel, i.e. sodium alginate-polyacrylamide double-network hydrogel.The preparation method is simple, it is easy to accomplish；Obtained ionic conduction double-network hydrogel has the excellent characteristics such as strong, tough, soft, bullet and endurance, solves the contradiction between " strong " and " tough ", " soft " and " bullet ", while having excellent injectable and self-healing capability；The novel double-net network hydrogel can generate effective current at ultra low voltage (0.04V), the induction to the strain of extra small and super large can be achieved, reach ultra-wide strain induction range (0.3%-1800%), can be used for ion skin, histoorgan, wearable device, resistance type sensor etc. that 3d is printed.
Description
Technical field
The present invention relates to natural macromolecular material fields, and in particular to a kind of novel double-net network hydrogel particularly relates to
And sodium alginate-polyacrylamide ionic conduction double-network hydrogel preparation method and applications.
Background technique
Hydrogel, which refers to, can absorb rapidly and keep large quantity of moisture and three-dimensional network macromolecular structure not soluble in water.
Hydrogel can keep higher water content by the swelling of polymer, form special flexible hygrometric state structure, have between solid
Property between body and liquid.This characteristic makes hydrogel have wide application, such as organizational project, medicine controlled releasing, biology
The fields such as nanotechnology.However, most of traditional synthetic hydrogel mechanical strength is weaker and toughness is insufficient, the harm of this defect
It has been hindered further to apply.
In order to improve the mechanical property of hydrogel, Recent study person proposes many thinkings, wherein more successful one
Kind is the concept of double-network hydrogel (Double network hydrogel, DN).In the prior art, double-network hydrogel
Mentality of designing be higher first layer network of synthesizing cross-linked degree, as template, introduce neutral low crosslinking degree the wherein
Double layer network, to form dual network structure.First layer network provides rigid backbone for DN hydrogel, keeps the outer of hydrogel
Shape, and the second layer network flexible fills up the effect for wherein functioning well as and absorbing stress.Studies have shown that DN hydrogel is being protected
While having held high-moisture, intensity and toughness are all greatly improved.But pair that currently available technology is related to
The hydrogel that network structure obtains still has the disadvantages of restorative poor, poor flexibility and poor, manufacturability is poor functionality.
Summary of the invention
In order to overcome the above problem, present inventor has performed sharp studies, first with sodium alginate and monovalent cation
Sodium alginate supermolecule hydrogen bond reciprocal networks are constructed, it is then compound with polyacrylamide cross-linked network, realize the increasing of hydrogel
By force, novel double-net network hydrogel, i.e. sodium alginate-polyacrylamide dual network ionic conduction hydrogel are obtained, thus complete
At the present invention.
One of the objects of the present invention is to provide a kind of preparation method of novel double-net network hydrogel, be embodied in
Under several aspects:
(1) a kind of preparation method of novel double-net network hydrogel, wherein the described method comprises the following steps:
Step 1 constructs sodium alginate Supramolecular fiber network using monovalent cation salt and sodium alginate；
Acrylamide monomers, crosslinking are added into the sodium alginate Supramolecular fiber network that step 1 obtains for step 2
Agent, initiator and catalyst, are stirred；
It is reacted under step 3, heating, illumination or radiation, obtains the novel double-net network hydrogel, i.e. sodium alginate-
Polyacrylamide dual network ionic conduction hydrogel.
(2) preparation method according to above-mentioned (1), wherein step 1 includes following sub-step:
Step 1-1, monovalent cation salt is added to the water, stirs, obtains monovalent cation salting liquid；
Step 1-2, in the monovalent cation salting liquid for obtaining sodium alginate addition step 1-1, stirring is mixed
Solution；
Step 1-3, the obtained mixed solution of step 1-2 is stood, forms sodium alginate Supramolecular fiber network.
(3) preparation method according to above-mentioned (1) or (2), wherein in step 1-1,
The monovalent cation salt is water-soluble monovalent cation salt, it is preferable that the monovalent cation salt is selected from water-soluble
Property one or more of sodium salt, water-soluble sylvite and water-soluble lithium salts, it is highly preferred that the monovalent cation salt is selected from chlorine
Change one or more of sodium, sodium carbonate, sodium iodide, potassium chloride, potassium carbonate, lithium chloride；And/or
The concentration of the monovalent cation salting liquid be 0.5~5wt%, preferably 1~4wt%, more preferably 1.5~
3.5wt%.
(4) preparation method according to one of above-mentioned (1) to (3), wherein
In step 1-1 and step 1-2, the weight ratio of the monovalent cation salt and sodium alginate is (0.5~2.5):
1, preferably (1~2): 1, more preferably (1.5~2): 1；And/or
In step 1-2, the weight average molecular weight of the sodium alginate is 10~600kDa, preferably 100~600kDa,
More preferably 200~600kDa.
(5) preparation method according to one of above-mentioned (1) to (4), wherein in step 1-3,1~120h is stood,
It is preferred that 5~60h is stood, more preferably 10~20h of standing, such as 12h.
(6) preparation method according to one of above-mentioned (1) to (5), wherein
In step 2, the acrylamide monomers are selected from acrylamide and/or acrylamide derivative, the propylene
Amide derivatives include N, N- acrylamide, 2- acrylamido -2- methyl propane sulfonic acid, n-isopropyl acrylamide,
N- isobutyl group acrylamide, N tert butyl acrylamide and N- cyclohexyl acrylamide etc.；And/or
The weight ratio of acrylamide monomers and sodium alginate is (6~25): 1, preferably (10~20): 1, such as 15:
1。
(7) preparation method according to one of above-mentioned (1) to (6), wherein in step 2,
The crosslinking agent is selected from N, N '-methylene-bisacrylamide, N, N '-diallyl tartardiamide, divinyl
One or more of base benzene, multicondensed ethylene glycol diacrylate and Polyethylene glycol dimethacrylate, such as N, N '-
Methylene-bisacrylamide；And/or the weight ratio of the crosslinking agent and acrylamide monomers is (0.0003~0.001): 1,
Preferably (0.0004~0.0008): 1, such as 0.0006:1；And/or
The initiator is selected from thermal initiator or photoinitiator, it is preferable that the initiator is selected from ammonium persulfate, over cure
One or more of sour potassium, sodium peroxydisulfate, benzoyl peroxide and Irgacure 2959；And/or
The weight ratio of the initiator and acrylamide monomers is (0.0005~0.003): 1, such as 0.001:1；
And/or
The catalyst is selected from N, N, N ', N '-tetramethylethylenediamine, sodium sulfite, sodium hydrogensulfite and sodium thiosulfate
One or more of；And/or
The weight ratio of the catalyst and acrylamide monomers is (0.001~0.004): 1, such as 0.0025:1.
(8) preparation method according to one of above-mentioned (1) to (7), wherein in step 3,
When using heating, the reaction is following to be carried out: 0.5~6h is reacted at 40~60 DEG C, it is preferable that in 50 DEG C
2~4h of lower reaction, such as 3h；Or
It is described to react following progress when using illumination: to irradiate lower reaction (0.5~2) h in ultraviolet light, it is preferable that in
The ultraviolet light irradiation of (200~400) nm is lower to react (1~1.5) h.
The second purpose of the present invention is to provide a kind of novel double-net network hydrogels, preferably institute according to a first aspect of the present invention
Preparation method is stated to obtain, wherein
The elongation at break of the novel double-net network hydrogel is 1500~2500%；
The breaking strength of the novel double-net network hydrogel is 0.4~0.8MPa；
The fracture toughness of the novel double-net network hydrogel is 3~6MJ/m3.
The three of the object of the invention are to provide the novel double-net network water-setting that preparation method described in first aspect present invention obtains
The application of novel double-net network hydrogel described in glue or second aspect of the present invention is used for ion skin, wearable device, resistor-type
Sensor.
Detailed description of the invention
Fig. 1 a shows the formation schematic diagram of sodium alginate Supramolecular fiber network；
Fig. 1 b shows the schematic diagram of the formation self assembly of sodium alginate Supramolecular fiber network；
Fig. 2 shows the tensile mechanical properties curves for the product that embodiment 1 and comparative example 1~2 obtain；
Fig. 3 shows the tensile mechanical properties curve for the product that Examples 1 to 2 and comparative example 3 obtain；
Fig. 4 shows the tensile mechanical properties curve for the product that embodiment 1 and embodiment 3 obtain；
Fig. 5 shows intermediary-sodium alginate Supramolecular fiber network A FM figure that embodiment 1 obtains；
Fig. 6 shows intermediary-sodium alginate Supramolecular fiber network TEM figure that embodiment 1 obtains；
Fig. 7 shows tension-relaxation cycles curve that the product that embodiment 5 obtains carries out 20 circulations；
Fig. 8 show the product that embodiment 5 obtains carry out in continuous 20 stretching-relaxation cycles the dissipation energy of gel and
Recovery rate curve；
Fig. 9 a shows the resistance of hydrogel that embodiment 5 obtains when applying elongation strain with respect to change curve；
Fig. 9 b shows the resistance of hydrogel that embodiment 5 obtains when applying compression strain with respect to change curve；
Fig. 9 c shows the opposite variation of hydrogel that embodiment 5 the obtains resistance after 10 load cycles and keeps curve；
Comparative resistance variation-time graph when release finger, neck, knee and ancon is shown respectively in Figure 10 a~Figure 10 d；
Figure 10 e shows three different people and says when the same Chinese word " hello " has recorded three times comparative resistance at throat
Variation-time graph；
Figure 10 f shows the same person and says when the same Chinese word " hello, I am good, and hello " has recorded three times at throat
Comparative resistance variation-time graph；
Figure 10 g shows comparative resistance variation-time graph at the preceding wrist pulse with after activity of same people's activity；
Figure 10 h shows comparative resistance variation-time graph at the wrist pulse of different people.
Specific embodiment
Below by embodiment and experimental example, the present invention is described in more detail.Illustrated by these, spy of the invention
Point and advantage will become more apparent from clear.
The present invention provides a kind of preparation method of novel double-net network hydrogel, the described method comprises the following steps:
Step 1 constructs sodium alginate Supramolecular fiber network using monovalent cation salt and sodium alginate.
A kind of preferred embodiment according to the present invention, step 1 include following sub-step:
Step 1-1, monovalent cation salt is added to the water, stirs, obtains monovalent cation salting liquid；
Step 1-2, in the monovalent cation salting liquid for obtaining sodium alginate addition step 1-1, stirring is mixed
Solution；
Step 1-3, the obtained mixed solution of step 1-2 is stood, forms sodium alginate Supramolecular fiber network.
A kind of preferred embodiment according to the present invention, in step 1-1, the monovalent cation salt is water solubility one
Valence cationic salts.
In further preferred embodiment, in step 1-1, the monovalent cation salt be selected from water-soluble sodium salt,
One or more of water-soluble sylvite and water-soluble lithium salts.
In embodiment still more preferably, in step 1-1, the monovalent cation salt is selected from sodium chloride, carbon
One or more of sour sodium, sodium iodide, potassium chloride, potassium carbonate, lithium chloride.
Wherein, in the present invention, as illustrated in figs. 1A and ib, the monovalent cation salt plays the role of hydrophobic and to sea
The electrostatic screen of mosanom acts on, in this way, semirigid sodium alginate strand is caused to flock together, final self assembly is (logical
Cross H-bonding self-assembly) at the Supramolecular Network of nanofiber.
A kind of preferred embodiment according to the present invention, in step 1-1, the concentration of the monovalent cation salting liquid
For 0.5~5wt%.
In further preferred embodiment, in step 1-1, the concentration of the monovalent cation salting liquid is 1~
4wt%.
In embodiment still more preferably, in step 1-1, the concentration of the monovalent cation salting liquid is
1.5~3.5wt%.
Wherein, inventor has found by many experiments, in the building of sodium alginate supermolecule hydrogen bond reciprocal networks, one
The concentration of valence cationic salts solution is most important.It, cannot be to sodium alginate molecule if the concentration of monovalent cation salting liquid is too low
Chain carries out abundant self assembly, and then not sufficiently forms Supramolecular Network, in this way, will affect final dual network intensity and
Toughness；But inventor, it was also found that wherein the concentration of monovalent cation salting liquid also should not be too big, lot of experimental data is said
Bright, when concentration is too big, the intensity and toughness of obtained dual network can equally be reduced, also, when salinity is too high, can be sent out
It now saltouts and occurs mutually separating.
A kind of preferred embodiment according to the present invention, in step 1-1 and step 1-2, the monovalent cation salt and
The weight ratio of sodium alginate is (0.5~2.5): 1.
In further preferred embodiment, in step 1-1 and step 1-2, the monovalent cation salt and seaweed
The weight ratio of sour sodium is (1~2): 1.
In embodiment still more preferably, in step 1-1 and step 1-2, the monovalent cation salt and sea
The weight ratio of mosanom is (1.5~2): 1.
Wherein, inventor has found by many experiments, and the amount ratio of monovalent cation salt and sodium alginate determines to obtain
Sodium alginate Supramolecular fiber network and final double-network hydrogel performance.
A kind of preferred embodiment according to the present invention, in step 1-2, the weight average molecular weight of the sodium alginate is
10~600kDa.
In further preferred embodiment, in step 1-2, the weight average molecular weight of the sodium alginate is 100~
600kDa。
In embodiment still more preferably, in step 1-2, the weight average molecular weight of the sodium alginate is 200
~600kDa.
Wherein, if the molecular weight of sodium alginate is too small, it is unfavorable for forming Nanofiber Network；Molecular weight is too big, is added
Salt, sodium alginate are easy to that macroscopical precipitated phase separation occurs.
A kind of preferred embodiment according to the present invention stands 1~120h in step 1-3.
In further preferred embodiment, in step 1-3,5~60h is stood.
In embodiment still more preferably, in step 1-3,10~20h, such as 12h are stood.
Wherein, the purpose of standing is to make sodium alginate molecule interchain form hydrogen bond.
Acrylamide monomers, crosslinking are added into the sodium alginate Supramolecular fiber network that step 1 obtains for step 2
Agent, initiator and catalyst, are stirred.
A kind of preferred embodiment according to the present invention, in step 2, the acrylamide monomers are selected from acryloyl
Amine and/or acrylamide derivative.
Wherein, the acrylamide derivative includes N, N- acrylamide, 2- acrylamido -2- methyl-prop
Sulfonic acid, n-isopropyl acrylamide, N- isobutyl group acrylamide, N tert butyl acrylamide and N- cyclohexyl acrylamide etc..
In further preferred embodiment, the weight ratio of acrylamide monomers and sodium alginate is (6~25):
1。
In embodiment still more preferably, the weight ratio of acrylamide monomers and sodium alginate be (10~
20): 1, such as 16:1.
Wherein, inventor has found by many experiments, if very few pair that will lead to of the dosage of acrylamide monomers
The intensity of network aqueous gel is too low, and if the dosage of acrylamide monomers is excessive, toughness reduction.
A kind of preferred embodiment according to the present invention, in step 2, the crosslinking agent are selected from N, N '-di-2-ethylhexylphosphine oxide third
Acrylamide, N, N '-diallyl tartardiamide, divinylbenzene, multicondensed ethylene glycol diacrylate and multicondensed ethylene glycol
One or more of dimethylacrylate, such as N, N '-methylene-bisacrylamide.
In further preferred embodiment, the weight ratio of the crosslinking agent and acrylamide monomers is (0.0003
~0.001): 1.
In embodiment still more preferably, the weight ratio of the crosslinking agent and acrylamide monomers is
(0.0004~0.0008): 1, such as 0.0006:1.
Wherein, if the dosage of crosslinking agent is very few, it will affect the intensity of double cross-linked networks, still, dosage can not
Excessively high, inventor has found by many experiments, will affect the elongation at break of double cross-linked networks if dosage of crosslinking agent is excessively high.
A kind of preferred embodiment according to the present invention, in step 2, the initiator is selected from thermal initiator or light draws
Send out agent.
In further preferred embodiment, in step 2, the initiator be selected from ammonium persulfate, potassium peroxydisulfate,
One or more of sodium peroxydisulfate and benzoyl peroxide.
In embodiment still more preferably, the weight ratio of the initiator and acrylamide monomers is
(0.0005~0.003): 1, such as 0.001:1.
A kind of preferred embodiment according to the present invention, in step 2, the catalyst are selected from N, N, N ', N '-tetramethyl
One or more of base ethylenediamine, sodium sulfite, sodium hydrogensulfite and sodium thiosulfate.
In further preferred embodiment, the weight ratio of the catalyst and acrylamide monomers is (0.001
~0.004): 1, such as 0.0025:1.
It is reacted under step 3, heating, illumination or radiation, obtains the sodium alginate-polyacrylamide dual network
Ionic conduction hydrogel.
Wherein, it after step 2 mixes each reactant, then needs to carry out cross-linking reaction, in the present invention, cross-linking reaction
Progress can be heated, can also be carried out so that illumination or radiation are lower, as long as cross-linking reaction can be generated.Preferably, step 3 uses
Heating is reacted.
A kind of preferred embodiment according to the present invention, in step 3, when using heating when, it is described reaction as follows into
Row: 0.5~6h is reacted at 40~60 DEG C.
In further preferred embodiment, in step 3, when using heating, the reaction is following to be carried out: in
2~4h, such as 3h are reacted at 50 DEG C.
A kind of preferred embodiment according to the present invention, in step 3, when using illumination, the reaction as follows into
Row: lower reaction (0.5~2) h is irradiated in ultraviolet light.
In further preferred embodiment, in step 3, when using illumination, the reaction is following to be carried out: in
The ultraviolet light irradiation of 200~400nm is lower to react 1~1.5h, such as reacts 1h under the ultraviolet light irradiation of 365nm.
A kind of preferred embodiment according to the present invention, in step 3, when using radiation when, it is described reaction as follows into
Row: radioreaction (0.5~1.5) h under (such as Co- gamma-rays etc.).
In the present invention, by verification experimental verification, the double-network hydrogel shows the characteristics such as tough, soft and elastic,
This is generated by the covalent networks cooperative interaction of sodium alginate Supramolecular fiber network and polyacrylamide.
Wherein, inventor surprisingly has found, the double-network hydrogel with very excellent restorability, have it is viscous
Conjunction ability.It puts together after being sheared with blade to double-network hydrogel, then by be sheared two pieces, then in natural ring
Under border condition, no any outside stimulus, the two can be bonded spontaneously.
Flexible wearable increasingly causes the concern of people in recent years, and it is future that aqueous ionomer gel, which has stretchable, transparent,
The research hotspot of flexible wearable, however, there are poor mechanical properties, susceptibility for the ionic conduction hydrogel that technology obtains at present
Low, the disadvantages of machinability is poor.
And double-network hydrogel of the present invention can generate the effective current of very low-voltage (0.04V), can be used for from
Sub- skin, wearable device, resistance type sensor etc., while having many advantages, such as that excellent in mechanical performance and machinability are strong.
Beneficial effect possessed by the present invention includes:
(1) preparation method of the present invention is simple, it is easy to accomplish；
(2) double-network hydrogel that the preparation method obtains through the invention has the characteristics such as strong, tough, soft bullet；
(3) double-network hydrogel that the preparation method obtains through the invention have quick self-recovery ability and
Excellent fatigue durability；
The double-network hydrogel that the preparation method obtains through the invention has injectability and adhesion property；
(4) double-network hydrogel that the preparation method obtains through the invention has higher sensitivity, can be ultralow
Generate effective current under voltage (0.04V), realize ultra-wide strain induction range (0.3%-1800%), can be used for ion skin,
Wearable device, resistance type sensor etc..
Embodiment
The present invention is further described below by way of specific embodiment.But these embodiments are only exemplary, not
Any restrictions are constituted to protection scope of the present invention.
Embodiment 1
By quality 1.75:1,1.75g sodium chloride, 1g sodium alginate are weighed respectively, it is spare；
Taken sodium chloride is added into deionized water dissolving, is configured to the sodium chloride solution that mass percent concentration is 3.6%,
Taken sodium alginate powder is dissolved in above-mentioned sodium chloride solution, is stirred evenly, obtaining sodium alginate concentration is 2wt%'s
Mixed solution；
Mixed solution is stood into 12h, forms it into Supramolecular fiber network.
16g acrylamide, 0.0096g N, N '-di-2-ethylhexylphosphine oxide third are added in the Supramolecular fiber network formed after to standing
Acrylamide, 0.016g ammonium persulfate, 0.04g N, N, N ', N '-tetramethylethylenediamine stirs evenly, stands 0.5h at room temperature,
And 3h is reacted at 50 DEG C, obtain sodium alginate-acrylamide double-network hydrogel.
As shown in figures 2-3, obtained sodium alginate Supramolecular fiber network-polyacrylamide double-network hydrogel is disconnected
Splitting elongation is 1995%, breaking strength 0.65MPa, fracture toughness 4.77MJ/m3。
Embodiment 2
The process of embodiment 1 is repeated, difference is: the weight ratio of sodium alginate and monomer being changed to 1:20 by 1:16, i.e.,
Using 20g acrylamide monomer.
As shown in figure 3, obtained sodium alginate-polyacrylamide double-network hydrogel elongation at break is 1515%,
Breaking strength is 0.75MPa, fracture toughness 4.13MJ/m3.
Embodiment 3
The process of embodiment 1 is repeated, difference is: by N, N '-methylene-bisacrylamide crosslinking agent and acrylamide list
The mass ratio of body is changed to 0.0003 by 0.0006, that is, uses 0.0048g N, N '-methylene-bisacrylamide.
As shown in figure 4, obtained sodium alginate-polyacrylamide double-network hydrogel elongation at break is 2135%,
Breaking strength is 0.38MPa, fracture toughness 3.6MJ/m3。
Embodiment 4
The process of embodiment 1 is repeated, difference is: acrylamide monomer is replaced with N, N- acrylamide list
Body, other conditions are constant.
Obtained sodium alginate-poly- N, N- acrylamide double-network hydrogel elongation at break is 1345%,
Breaking strength is 0.21MPa, fracture toughness 0.89MJ/m3。
Embodiment 5
Repeating the process of embodiment 1, wherein the concentration of NaCl is 1.77wt%, and the concentration of sodium alginate is 1.5wt%,
The concentration of acrylamide is 24wt%, remaining condition is constant.
The elongation at break of obtained product, breaking strength and fracture toughness are similar to Example 1.
Comparative example
Comparative example 1
The process in embodiment 1 is repeated, difference is: when preparing sodium alginate Supramolecular fiber network, being added without chlorine
Change sodium.
As shown in Fig. 2, the elongation at break of obtained product is 1687%, breaking strength 0.16MPa, it is broken tough
Property is 1.09MJ/m3。
Comparative example 2
Repeat the process in embodiment 1, difference is: the mass ratio of sodium chloride and sodium alginate is 2.92:1, i.e., finally
Sodium chloride solution concentration be 6wt%.
As shown in Fig. 2, obtained sodium alginate Supramolecular fiber network-polyacrylamide double-network hydrogel fracture
Elongation is 895%, breaking strength 0.28MPa, fracture toughness 1.25MJ/m3。
Comparative example 3
The process of embodiment 1 is repeated, difference is: the weight ratio of sodium alginate and monomer being changed to 1:6 by 1:16, i.e.,
Using 6g acrylamide monomer.
As shown in figure 3, obtained sodium alginate-polyacrylamide double-network hydrogel elongation at break is 1555%,
Breaking strength is 0.13MPa, fracture toughness 0.51MJ/m3。
Comparative example 4
The process in embodiment 1 is repeated, difference is: N, N '-methylene-bisacrylamide crosslinking agent and acrylamide list
The mass ratio of body is 0.0012.
Obtained sodium alginate-polyacrylamide double-network hydrogel elongation at break is 1687%, and breaking strength is
0.16MPa, fracture toughness 1.09MJ/m3。
Comparative example 5
The process of embodiment 1 is repeated, difference is: only carrying out the preparation of cross-linked polyacrylamide, that is, be added without sodium chloride
And sodium alginate.
The elongation at break of obtained polyacrylamide list network aqueous gel is 1720%, and breaking strength is
0.11MPa, fracture toughness 0.83MJ/m3。
Comparative example 6
The process of embodiment 1 is repeated, difference is, replaces sodium chloride using divalent calcium salt.
The elongation at break of product is 1500%, breaking strength 0.25MPa, and does not have injectable and adhesive capacity.
Experimental example
1 stretching mechanical property testing of experimental example
(1) in order to analyze the influences of different monovalent cation salt dosages, embodiment 1 and comparative example 1~2 are obtained
Product carries out stretching mechanical property testing, as a result as shown in Fig. 2 and table 1.
Table 1:
It can be seen from Fig. 2 and table 1 when not adding monovalent cation salt (comparative example 1), the fracture of obtained product
Intensity is very low, only 0.16MPa, illustrates, the presence of monovalent cation salt, so that passing through hydrogen between sodium alginate strand
Key self assembly, and hydrogen bond therein can assign final products excellent mechanical property really；Equally, if monovalent cation salt
Dosage it is excessive (comparative example 2), also will affect the mechanical property of final products, including elongation at break, breaking strength and fracture
Toughness declines.Illustrate, the dosage of monovalent cation salt is most important.
(2) in order to analyze the influence of different sodium alginates/monomer amount ratio, Examples 1 to 2 and comparative example 3 are obtained
Product carry out stretching mechanical property testing, as a result as shown in Fig. 3 and table 2.
Table 2:
It can be seen from Fig. 3 and table 2 when the dosage of monomer is very few (comparative example 3), the breaking strength of obtained product
Clearly with fracture toughness decline, illustrate, in the preparation of double-network hydrogel of the present invention, it is necessary to strict control sea
The dosage of mosanom and monomer.
(3) in order to analyze influence of the different amounts to product of crosslinking agent, to embodiment 1, embodiment 3 and comparative example 4
The product that (not providing in Fig. 4) obtains carries out stretching mechanical property testing, as a result as shown in Fig. 4 and table 3.
Table 3:
It can be seen from Fig. 4 and table 3 when crosslinking agent and monomer dosage it is smaller be 0.0003 when (embodiment 3), compare
In embodiment 1 (amount ratio 0.0006), breaking strength has more reductions, but elongation at break has more raisings；But such as
Fruit dosage of crosslinking agent is excessive, when with monomer amount ratio being 0.0012 (comparative example 4), elongation at break degradation, and breaking
Resistance to spalling and fracture toughness are also declined.Illustrate, in the preparation of double-network hydrogel of the present invention, power in order to obtain
The product haveing excellent performance is learned, the amount ratio of strict control crosslinking agent and monomer is needed.
Experimental example 2AFM test
The intermediary obtained to embodiment 1-sodium alginate Supramolecular fiber network carries out AFM test, as a result such as Fig. 5 institute
Show, in Fig. 5 it can be seen from monovalent cation is mixed with sodium alginate after, available supramolecular network structure.
Experimental example 3TEM test
The intermediary obtained to embodiment 1-sodium alginate Supramolecular fiber network carries out TEM test, as a result such as Fig. 6 institute
Show, by Fig. 6 it can be observed that diameter be 10~50nm and several microns of long super-molecular nano fibers, illustrate, by monovalence sun from
After son is mixed with sodium alginate, sodium alginate strand has carried out being self-assembly of super-molecular nano fiber.
4 mechanical strength test of experimental example
(1) according to embodiment 1 the step of, is reacted in certain moduli tool, 1.5g hydrogel thin slice is obtained, to it
Mechanical strength carries out on-the-spot test, it is found that its weight that can lift 2kg has been more than 1300 times of own wt；
Also, the hydrogel has very high transparency, and can knot, and stretches, braiding, compression and throwing
Light etc. is able to bear high-caliber deformation.
(2) according to embodiment 1 the step of, is reacted in certain moduli tool, obtains flat cylindrical body hydrogel, right
It applies mechanical load and is pressed, and makes its compression, still, after removing mechanical load, hydrogel is re-formed rapidly initially
Shape shows that gel has excellent intensity, elasticity and shape recovery energy without any damage.
5 elasticity of experimental example and restorative test
(1) tension-relaxation cycles of 20 circulations are carried out to the product that embodiment 5 obtains under 1000% strain, as a result
As shown in Figure 7, it can be seen that may be the residual stress due to remaining in original hydrogel, in first time loading-unloading
After occurring small hysteresis cycle in circulation, the load-deformation curve of cycles left is not in hysteresis, and is complete
Overlapping.
(2) dissipation energy of gel and recovery rate are as shown in Figure 8 in continuous 20 stretching-relaxation cycles, it can be seen that
In preceding 5 circulations of the Large strain of load 1000%, dissipation energy and recovery rate have dropped 97.5%, 98.3% respectively.This
Afterwards, the energy consumption of cycles left and response rate remain unchanged, and gel can restore its mechanical property, table completely at room temperature
Hydrous gel has extremely strong elasticity and restorability, this is the typical behaviour of elastomer.
Further confirm quick recovery rate of the double-network hydrogel of the present invention under high stress working environment, reliable
Mechanical property and longer service life.
The test of 6 compression performance of experimental example
The production that embodiment 5, comparative example 1 (sodium chloride is not added) and comparative example 5 (sodium chloride and sodium alginate is not added) are obtained
Product carry out compression test, it is found that when being compressed to 98% original height:
The product that embodiment 5 obtains has elasticity, can compress, and can return to the original form upon compression；
The product that comparative example 1 obtains can also be compressed, but cannot be restored upon compression；
The product that comparative example 5 obtains not can be carried out compression, and product is integrally gone to sticks and staves after compression.
Show that double-network hydrogel of the present invention has very strong and excellent elastic compression performance.
Test of 7 strains of the experimental example-resistance with respect to qualitative change
The hydrogel that embodiment 5 obtains is become relatively in the resistance for applying stretching (Fig. 9 a) and compressing when (Fig. 9 b) is strained
Change is detected, and obtains strain-resistance with respect to change curve, it is shown that resistance dependence of the ion conductor to the stress of application.
The dual network obtained by the embodiment 5 that two copper sheets (electrode) in circuit clip is used it can be seen from Fig. 9 a
The light emitting diode (LED) of water-setting glue connection observes the tension stress variation of double-network hydrogel.It is obvious that with
The increase of elongation strain, light emitting diode is dimmed, loses up to 1800% Large strain light, it is excellent to further display out its
Electrical draftability.
With the increase of compressive deformation it can be seen from Fig. 9 b, light emitting diode becomes brighter.
It is worth noting that, after 10 load cycles, the opposite variation of the high resistance of double-network hydrogel and primitiveness
It is able to maintain unanimously, shows at room temperature with the excellent electrical stability (as is shown in fig. 9 c) of height.
8 ion skin performance evaluation of experimental example
It, will in order to evaluate double-network hydrogel of the present invention performance of skin as an example in actual working environment
The double-network hydrogel that embodiment 5 obtains is fitted in the different parts of human body, monitors the comparative resistance of various human motions in real time
The relationship of variation and time.
(1) finger, neck, knee and ancon are bent and discharged respectively, is tested, as a result such as Figure 10 a~Figure 10 d；
The increase of the stretcher strain due to caused by the bending degree of finger, neck, knee and ancon, the electricity of ion skin
Resistance increases to different levels.Especially as can be seen that the variation of resistance and the movement of finger, neck, knee and ancon are complete
It is synchronous, repeatedly without any hysteresis phenomenon, show quick response, the reliability properties of instant recovery and high conductivity, institute
Double-network hydrogel is stated with excellent elasticity；The result shows that the double-network hydrogel can be used as ion transducer, prison
The big strain and big movement for surveying human body, have very big application potential in artificial muscle and electronic skin.
(2) to testing at throat: three different people say that the same Chinese word " hello " has recorded three times, as a result
As illustrated in figure 10e；The same person says that the same Chinese word " hello, I am good, and hello " has recorded three times, as a result such as Figure 10 f institute
Show.
Since the double-network hydrogel can be used as ionic skin sensor, sensitivity with higher not only may be used
To detect the large deformation of human body limb movement, but also it is complicated and micro- when speaking and in wrist pulse to measure people
Wonderful muscular movement.The resistance change curves of obtained time correlation are in the same person while when saying identical word three times
Similar feature peak and valley is shown, and shows different feature peak and valleys when different people says identical word；
In order to further study its sensibility and repeatability, same people record simultaneously three times " hello, I am good, everybody
It is good " this Chinese phrase.This curve shows identical characteristic peak and low repeatability.Pass through the quick pressure of sensitivity
Induction, the double-network hydrogel provide an interesting and effective method as ion skin for speech recognition, this is main
It is as caused by the deformation of throat's Surrounding muscles during speech.
(3) to being tested at wrist pulse: the wrist before same people's activity and after activity
In medical treatment, health and Sports Practice, wrist pulse is the important indicator of arterial pressure and heart rate, is non-intruding
Sex medicine diagnosis provides a large amount of useful information；
Due to Large strain sensibility, the double-network hydrogel can monitoring personnel activity before and after it is delicate
Pressure difference (Figure 10 g).Figure 10 g is shown after relaxation (before activity) and rope skipping (after activity), and the eparterial ion of wrist passes
The relationship of the real time resistance of sensor opposite variation and time graph.Obviously, it is 65 beats/min that a people, which is laid flat pulse frequency, arteries and veins
It fights regular shape, repeats, the pulse frequency of rope skipping descendant is 90 beats/min, amplitude and enhanced strength and irregular；
The human wrist pulse amplifying figure (Figure 10 h) that can reflect the delicate variation health of wrist arteries and veins is clearly illustrated and is received
Strike wave (P wave) related with diastolic pressure, tidal wave (T wave), valley and diastolic wave (D wave), ventricular pressure and heart rate are pressed in contracting.It obtains
The train of thought curve obtained includes important clinical information, can be derived from certain characteristic points by mathematical analysis, and people one are given
The guidance of a little medical treatment and sentific training.
Preferred embodiment and exemplary example is combined to describe the invention in detail above.It but needs to state
, these specific embodiments are not constituted to protection scope of the present invention any to illustrative explanations of the invention
Limitation.Without departing from spirit of that invention and protection scope, can to the technology of the present invention content and embodiments thereof into
The various improvement of row, equivalencing or modification, these fall within the protection scope of the present invention.Protection scope of the present invention is with institute
Subject to attached claim.
Claims (10)
1. a kind of preparation method of novel double-net network hydrogel, which is characterized in that the described method comprises the following steps:
Step 1 constructs sodium alginate supermolecule hydrogen bond reciprocal networks using monovalent cation salt and sodium alginate；
Acrylamide monomers, crosslinking agent, initiation are added into the sodium alginate Supramolecular fiber network that step 1 obtains for step 2
Agent and catalyst, are stirred；
It is reacted under step 3, heating, illumination or radiation, obtains the novel double-net network hydrogel, i.e. sodium alginate-poly- third
Acrylamide dual network ionic conduction hydrogel.
2. preparation method according to claim 1, which is characterized in that step 1 includes following sub-step:
Step 1-1, monovalent cation salt is added to the water, stirs, obtains monovalent cation salting liquid；
Step 1-2, in the monovalent cation salting liquid for obtaining sodium alginate addition step 1-1, stirring obtains mixed solution；
Step 1-3, the obtained mixed solution of step 1-2 is stood, forms sodium alginate Supramolecular fiber network.
3. preparation method according to claim 1 or 2, which is characterized in that in step 1-1,
The monovalent cation salt is water-soluble monovalent cation salt, it is preferable that the monovalent cation salt is selected from water-soluble sodium
One or more of salt, water-soluble sylvite and water-soluble lithium salts, it is highly preferred that the monovalent cation salt be selected from sodium chloride,
One or more of sodium carbonate, sodium iodide, potassium chloride, potassium carbonate, lithium chloride；And/or
The concentration of the monovalent cation salting liquid be 0.5~5wt%, preferably 1~4wt%, more preferably 1.5~
3.5wt%.
4. according to claim 1 to preparation method described in one of 3, which is characterized in that
In step 1-1 and step 1-2, the weight ratio of the monovalent cation salt and sodium alginate is (0.5~2.5): 1, it is excellent
It is selected as (1~2): 1, more preferably (1.5~2): 1；And/or
In step 1-2, the weight average molecular weight of the sodium alginate is 10~600kDa, preferably 100~600kDa, more preferably
For 200~600kDa.
5. according to claim 1 to preparation method described in one of 4, which is characterized in that in step 1-3,1~120h is stood,
It is preferred that 5~60h is stood, more preferably 10~20h of standing, such as 12h.
6. preparation method according to one of claims 1 to 5, which is characterized in that
In step 2, the acrylamide monomers are selected from acrylamide and/or acrylamide derivative, the acrylamide
Derivative includes N, and N- acrylamide, 2- acrylamido -2- methyl propane sulfonic acid, n-isopropyl acrylamide, N- are different
Butylacrylamide, N tert butyl acrylamide and N- cyclohexyl acrylamide etc.；And/or
The weight ratio of acrylamide monomers and sodium alginate is (6~25): 1, preferably (10~20): 1, such as 15:1.
7. preparation method according to one of claims 1 to 6, which is characterized in that in step 2,
The crosslinking agent be selected from N, N '-methylene-bisacrylamide, N, N '-diallyl tartardiamide, divinylbenzene,
One or more of multicondensed ethylene glycol diacrylate and/or Polyethylene glycol dimethacrylate, such as N, N '-methylene
Base bisacrylamide；And/or
The weight ratio of the crosslinking agent and acrylamide monomers is (0.0003~0.001): 1, preferably (0.0004~
0.0008): 1, such as 0.0006:1；And/or
The initiator be selected from thermal initiator or photoinitiator, it is preferable that the initiator be selected from ammonium persulfate, potassium peroxydisulfate,
One or more of sodium peroxydisulfate, benzoyl peroxide and Irgacure2959；And/or
The weight ratio of the initiator and acrylamide monomers is (0.0005~0.003): 1, such as 0.001:1；And/or
The catalyst is selected from N, N, N ', in N '-tetramethylethylenediamine, sodium sulfite, sodium hydrogensulfite and sodium thiosulfate
It is one or more of；And/or
The weight ratio of the catalyst and acrylamide monomers is (0.001~0.004): 1, such as 0.0025:1.
8. according to claim 1 to preparation method described in one of 7, which is characterized in that in step 3,
When using heating, the reaction is following to be carried out: 0.5~6h is reacted at 40~60 DEG C, it is preferable that react at 50 DEG C
2~4h, such as 3h；Or
When using illumination, the reaction is following to be carried out: being irradiated in ultraviolet light and lower is reacted 0.5~2h, it is preferable that in 200~
The ultraviolet light irradiation of 400nm is lower to react 1~1.5h.
9. a kind of novel double-net network hydrogel, preferably obtains to preparation method described in one of 8 according to claim 1, wherein
The elongation at break of the novel double-net network hydrogel is 1500~2500%；
The breaking strength of the novel double-net network hydrogel is 0.4~0.8MPa；
The fracture toughness of the novel double-net network hydrogel is 3~6MJ/m3。
10. the novel double-net network hydrogel that obtains according to claim 1 to preparation method described in one of 8 or according to claim 9
The application of the novel double-net network hydrogel is used for ion skin, wearable device, resistance type sensor.
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| CN115028861A (en) * | 2022-07-26 | 2022-09-09 | 深圳微检无忧科技有限公司 | High-conductivity double-network hydrogel and preparation method and flexible sensing application thereof |
| CN115490807A (en) * | 2022-08-30 | 2022-12-20 | 广东省科学院化工研究所 | Double-network conductive hydrogel and preparation method and application thereof |
| CN115490807B (en) * | 2022-08-30 | 2023-10-13 | 广东省科学院化工研究所 | Double-network conductive hydrogel and preparation method and application thereof |
| CN115518005A (en) * | 2022-10-24 | 2022-12-27 | 海南省人民医院 | Oral care gel and preparation method thereof |
| CN115518005B (en) * | 2022-10-24 | 2023-06-20 | 海南省人民医院 | Oral care gel and preparation method thereof |
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