CN112812326B - Self-powered hydrogel containing zinc chloride electrolyte and preparation method thereof - Google Patents
Self-powered hydrogel containing zinc chloride electrolyte and preparation method thereof Download PDFInfo
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 239000000017 hydrogel Substances 0.000 title claims abstract description 85
- 239000011592 zinc chloride Substances 0.000 title claims abstract description 44
- 235000005074 zinc chloride Nutrition 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003792 electrolyte Substances 0.000 title claims abstract description 27
- 239000000499 gel Substances 0.000 claims abstract description 154
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002994 raw material Substances 0.000 claims abstract description 48
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 28
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 28
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000002347 injection Methods 0.000 claims abstract description 17
- 239000007924 injection Substances 0.000 claims abstract description 17
- 230000008054 signal transmission Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims description 30
- 150000001450 anions Chemical class 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005341 cation exchange Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000005349 anion exchange Methods 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims description 6
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 5
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VSFOXJWBPGONDR-UHFFFAOYSA-M potassium;3-prop-2-enoyloxypropane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)CCCOC(=O)C=C VSFOXJWBPGONDR-UHFFFAOYSA-M 0.000 claims description 5
- 229940047670 sodium acrylate Drugs 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229940045998 sodium isethionate Drugs 0.000 claims description 5
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 claims description 5
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 5
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 5
- 239000011664 nicotinic acid Substances 0.000 abstract description 13
- 230000006870 function Effects 0.000 abstract description 12
- 238000004891 communication Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000005483 Hooke's law Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QEOWFDYSNYCPRK-UHFFFAOYSA-N OCC[Na] Chemical compound OCC[Na] QEOWFDYSNYCPRK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Colloid Chemistry (AREA)
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Abstract
The invention relates to the technical field of chemical industry, and discloses a self-powered hydrogel containing zinc chloride electrolyte and a preparation method thereof, wherein the method adopts a free radical copolymerization method, acrylamide, N, N ' -methylene bisacrylamide with the mass ratio of 0.01-2%, ammonium persulfate with the mass ratio of 0.01-5%, potassium persulfate with the mass ratio of 0.01-5% and N, N, N ', N ' -tetramethyl ethylenediamine with the mass ratio of 0.001-10% are taken as raw materials of a gel unit, and a vortex oscillator is used for fully dispersing the raw materials in a proper amount of deionized water; after bubbles are removed by ultrasonic waves, the mixed solution is injected into a mould by a precise injection pump; standing at room temperature to obtain gel unit; different hydrogels can be prepared by adjusting the number of gel units and the injection sequence of the gel units. The bionic skin material solves the problem that the existing bionic skin material cannot have the functions of sensing, communication and signal transmission at the same time, has excellent mechanical durability of the skin and the function of communication or signal transmission of skin electronic products, and has wide prospects in the field of bionic skin, bionic sensors and skin-like electronic products.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to self-powered hydrogel containing zinc chloride electrolyte and a preparation method thereof.
Background
The bionic skin has unique advantages in mechanical durability and the capability of measuring large-area complex sensation and has great potential in the field of manufacturing mechanically compatible multifunctional skin electronic products; new materials and manufacturing methods are being developed and brain/machine interfaces are being improved to allow signals of the skin, e.g. electrical signals, to be transmitted to the body.
The inventor finds that at least the following problems exist in the prior art: these skin-like electronics are based on an array of sensors and control circuits on the surface of a flexible material to sense the external environment, whereas these materials have the disadvantage of poor mechanical durability and do not have the function of sensing communication or signal transmission. There is an urgent need in the market for new materials that have both excellent mechanical properties of the skin and the functions of electronic products sensing, communication and signal transmission of the skin.
Reference 1: application publication No. CN 108864494A is a dynamic cross-linked double-network hydrogel and a preparation method and application thereof.
Reference 2: application publication number CN 109320673A is a self-repairing flexible hydrogel electro-sensitive material, and a preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a self-powered hydrogel containing a zinc chloride electrolyte and a preparation method thereof, so that a novel material with excellent mechanical and repairability of skin and communication or signal transmission function of skin electronic products is provided.
To solve the above technical problems, embodiments of the present invention provide a method for preparing a self-powered hydrogel containing a zinc chloride electrolyte, formed of at least two gel units among a low salt concentration gel unit, a high salt concentration gel unit, a cation selective gel unit, and an anion selective gel unit in different combination sequences, comprising the steps of:
(1) Preparing a raw material A: the raw material A comprises acrylamide, N, N ' -methylene bisacrylamide with the mass ratio of 0.01-2%, ammonium persulfate with the mass ratio of 0.01-5%, potassium persulfate with the mass ratio of 0.01-5% and N, N, N ', N ' -tetramethyl ethylene diamine with the mass ratio of 0.001-10%;
(2) Preparing a raw material B: the raw material B is at least two of 0.01-10% of zinc chloride, 10-50% of zinc chloride, 1-50% of cation exchange group compound and 1-50% of anion exchange group compound by mass ratio;
(3) Using a vortex oscillator to fully disperse each raw material in the raw materials A and B in a proper amount of deionized water respectively to obtain at least two mixed raw material liquids;
(4) Removing bubbles in each mixed raw material liquid by ultrasonic waves, and injecting each mixed solution by using a precise injection pump;
(5) Standing at room temperature to obtain at least two gel units selected from a low-salt-concentration gel unit, a high-salt-concentration gel unit, a cation selection gel unit and an anion selection gel unit;
(6) Adjusting the injection sequence of each gel unit to obtain different hydrogels.
The cation exchange group material in the cation selective gel unit comprises: (3-acrylamidopropyl) trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
The anion exchange group material in the anion selective gel unit comprises: sodium isethionate, potassium 3-prop-2-enoyloxypropane-1-sulfonate, sodium acrylate, sodium carbonate and 2-acrylamido-2-methylpropanesulfonic acid.
The gel unit has good elasticity, wherein the elastic stiffness coefficient of the low-salt concentration gel unit is 4000-6000N/m, the elastic stiffness coefficient of the high-salt concentration gel unit is 6000-9000N/m, the elastic stiffness coefficient of the cation selection gel unit is 4500-6500N/m, and the elastic stiffness coefficient of the anion selection gel unit is 4000-6000N/m.
The gel unit comprises a test unit consisting of a high salinity gel unit, an anion selective gel unit, a low salt concentration gel unit, a cation selective gel unit, a high salinity gel unit or a high salinity gel unit, a cation selective gel unit, a low salt concentration gel unit, an anion selective gel unit and a high salinity gel unit, and can provide a stable current of 0.1 muA to realize self-power.
The hydrogel is prepared by the preparation method of the hydrogel.
Compared with the prior art, the bionic skin material solves the problem that the existing bionic skin material in the market cannot have both mechanical durability and communication or signal transmission function, and has excellent mechanical durability and skin electronic product communication or signal transmission function.
In addition, the invention realizes the exchange of anions and cations through the selective gel, simulates the nerve signal transmission of human skin, builds a self-powered bionic skin assembly, and has wide prospect in the field of bionic skin, bionic sensors and skin-like electronic products.
In addition, the present invention has excellent mechanical durability and can endure large deformation such as tension or compression or distortion without breaking.
In addition, the invention has the communication or signal transmission function, and particularly, stable current can be provided in the built test unit test; the hydrogel current changes along with the change of the external pressure, and a pressure signal can be converted into a current change signal.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
One or more embodiments are illustrated by way of example in the accompanying drawings, which correspond to the figures in which like reference numerals refer to similar elements and which are not to scale unless otherwise specified.
FIG. 1 is a pictorial representation of a hydrogel product;
FIG. 2 is a mechanical property test chart of the hydrogel;
FIG. 3 is a view showing the composition of hydrogel;
FIG. 4 hydrogel electrical properties;
figure 5 hydrogel current as a function of pressure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, it will be appreciated by those of ordinary skill in the art that numerous technical details are set forth in order to provide a better understanding of the present application in various embodiments of the present invention. However, the technical solution claimed in the present application can be implemented without these technical details and various changes and modifications based on the following embodiments. The following embodiments are divided for convenience of description, and should not constitute any limitation to the specific implementation manner of the present invention, and the embodiments may be mutually incorporated and referred to without contradiction.
Testing the mechanical durability of the hydrogel: applying corresponding mechanical measuring equipment to the hydrogel or the hydrogel
The hydrogel cells were subjected to a compression-recovery test and the elastic coefficient k was measured.
Testing the electrical properties of the hydrogel: measuring the current between two surfaces to be measured of the hydrogel layer by using the built test unit within a specified time; and applying external force to the hydrogel at the measuring point, wherein the measuring current changes along with the change of the external pressure.
In the present embodiment, the low salt concentration gel unit, the high salt concentration gel unit, the cation selective gel unit, and the anion selective gel unit may be simply referred to as: l, H, A and C.
First embodiment
A first embodiment of the present invention relates to a method for preparing a self-powered hydrogel containing zinc chloride electrolyte, specifically as follows:
the hydrogel is formed by at least two gel units of a low-salt-concentration gel unit (L), a high-salt-concentration gel unit (H), a cation-selective gel unit (A) and an anion-selective gel unit (C) in different combination sequences.
The gel unit preparation raw material and the mass composition comprise 0.01-2% of acrylamide, 0.01-5% of N, N ' -methylene bisacrylamide, 0.01-5% of ammonium persulfate, 0.001-10% of potassium persulfate and 0.001-10% of N, N, N ', N ' -tetramethyl ethylenediamine.
When the gel unit is a low-salt-concentration gel unit, the preparation raw material also comprises 0.01-10% of zinc chloride.
When the gel unit is a high-salt-concentration gel unit, the preparation raw material also comprises 10-50% of zinc chloride.
When the gel unit is a cation gel unit, the preparation raw material also comprises 1-50% of cation exchange group compound.
When the gel unit is an anion gel unit, the preparation raw materials also comprise 1-50% of an anion exchange group compound.
The cation exchange group material in the cation selective gel unit comprises: (3-acrylamidopropyl) trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
The anion exchange group material in the anion selective gel unit comprises: sodium isethionate, potassium 3-prop-2-enoyloxypropane-1-sulfonate, sodium acrylate, sodium carbonate and 2-acrylamido-2-methylpropanesulfonic acid.
The preparation method of the hydrogel comprises the following steps:
(1) Fully dispersing the raw materials in a proper amount of deionized water by using a vortex oscillator;
(2) After bubbles are removed by ultrasonic waves, the mixed solution is injected into a mould by a precise injection pump;
(3) Standing at room temperature to obtain gel unit;
(4) Different hydrogels can be prepared by adjusting the raw material type composition and mass ratio, the number of the gel units and the injection sequence of the gel units.
The first embodiment of the invention also relates to a self-powered hydrogel containing zinc chloride electrolyte, a method for preparing said hydrogel as disclosed with reference to the first embodiment.
A concrete example of the hydrogel according to this embodiment is shown in FIG. 1.
Second embodiment
A second embodiment of the invention relates to a self-powered hydrogel containing zinc chloride electrolyte and a method for making the same. The second embodiment is different from the first embodiment mainly in that: in the first embodiment, upper protection is performed; while the second embodiment of the present invention is a lower preferred embodiment. Further, it will be understood by those skilled in the art that the second embodiment of the present invention is a lower example than the first embodiment.
The preferred invention provides an example of a low salt concentration gel unit in a self-powered hydrogel containing zinc chloride electrolyte:
the low-salt concentration gel unit comprises raw materials for preparing the low-salt concentration gel unit and the mass composition of the low-salt concentration gel unit comprises 0.01-0.5% of acrylamide, 0.01-2% of N, N ' -methylene bisacrylamide, 0.01-2% of ammonium persulfate, 0.01-2% of potassium persulfate, 0.001-3% of N, N, N ', N ' -tetramethyl ethylenediamine and 0.01-3% of zinc chloride;
the low-salt concentration gel unit comprises, by mass, 0.5-1.0% of acrylamide, 0.5-1.0% of N, N ' -methylene bisacrylamide, 2-3% of ammonium persulfate, 2-3% of potassium persulfate, 3-6% of N, N, N ', N ' -tetramethylethylenediamine and 3-6% of zinc chloride;
the low-salt-concentration gel unit comprises, by mass, 1.0-2.0% of acrylamide, 1.0-2.0% of N, N ' -methylene bisacrylamide, 3-5% of ammonium persulfate, 3-5% of potassium persulfate, 6-10% of N, N, N ', N ' -tetramethylethylenediamine and 6-10% of zinc chloride.
Preferred embodiments of the present invention also provide an embodiment of high salt concentration gel units in a self-powered hydrogel comprising zinc chloride electrolyte:
the raw materials for preparing the high-salt concentration gel unit and the mass composition of the gel unit comprise 0.01-0.5% of acrylamide, 0.01-2% of N, N ' -methylene bisacrylamide, 0.01-2% of ammonium persulfate, 0.01-2% of potassium persulfate, 0.001-3% of N, N, N ', N ' -tetramethyl ethylenediamine and 10-20% of zinc chloride;
the raw materials for preparing the high-salt-concentration gel unit and the mass composition of the gel unit comprise 0.5-1.0% of acrylamide, 0.5-1.0% of N, N ' -methylene bisacrylamide, 2-3% of ammonium persulfate, 2-3% of potassium persulfate, 3-6% of N, N, N ', N ' -tetramethyl ethylenediamine and 20-30% of zinc chloride;
the raw materials for preparing the high-salt-concentration gel unit and the mass composition of the gel unit comprise 1.0-2.0% of acrylamide, 1.0-2.0% of N, N ' -methylene bisacrylamide, 3-5% of ammonium persulfate, 3-5% of potassium persulfate, 6-10% of N, N, N ', N ' -tetramethyl ethylenediamine and 30-50% of zinc chloride.
Preferred embodiments of the present invention also provide an embodiment of a cation selective gel unit in a self-powered hydrogel comprising zinc chloride electrolyte:
the cation selective gel unit comprises raw materials for preparing the cation selective gel unit and consists of 0.01-0.5% of acrylamide, 0.01-2% of N, N ' -methylene bisacrylamide, 0.01-2% of ammonium persulfate, 0.001-3% of potassium persulfate, 0.001-3% of N, N, N ', N ' -tetramethyl ethylenediamine and 1-20% of a cation exchange group compound by mass;
the cation selective gel unit comprises raw materials for preparing the cation selective gel unit and a cation exchange group compound, wherein the raw materials comprise, by mass, 0.5% -1.0% of acrylamide, 0.5% -1.0% of N, N ' -methylene bisacrylamide, 2% -3% of ammonium persulfate, 2% -3% of potassium persulfate, 3% -6% of N, N, N ', N ' -tetramethyl ethylenediamine and 20% -30% of the cation exchange group compound;
the cation selective gel unit preparation raw materials comprise, by mass, 1.0% -2.0% of acrylamide, N, N ' -methylene-bisacrylamide, 3% -5% of ammonium persulfate, 3% -5% of potassium persulfate, 6% -10% of N, N, N ', N ' -tetramethylethylenediamine and 30% -50% of a cation exchange group compound;
the cation exchange group material in the cation selective gel unit comprises: (3-acrylamidopropyl) trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
Preferred embodiments of the present invention also provide an embodiment of anion selective gel units in a self-powered hydrogel comprising zinc chloride electrolyte:
the anion selective gel unit preparation raw material and the mass composition comprise 0.01-0.5% of acrylamide, 0.01-2% of N, N ' -methylene-bis-acrylamide, 0.01-2% of ammonium persulfate, 0.01-2% of potassium persulfate, 0.001-3% of N, N, N ', N ' -tetramethyl ethylenediamine and 1-20% of an anion exchange group compound;
the anion selective gel unit comprises 0.5-1.0% of acrylamide, 0.5-1.0% of N, N ' -methylene bisacrylamide, 2-3% of ammonium persulfate, 2-3% of potassium persulfate, 3-6% of N, N, N ', N ' -tetramethylethylenediamine and 20-30% of an anion exchange group compound by mass;
the anion selective gel unit preparation raw material and the mass composition comprise 1.0-2.0% of acrylamide, 1.0-2.0% of N, N ' -methylene-bisacrylamide, 3-5% of ammonium persulfate, 3-5% of potassium persulfate, 6-10% of N, N, N ', N ' -tetramethylethylenediamine and 30-50% of an anion exchange group compound;
said anion exchange group material in said anion selective gel unit comprises: sodium isethionate, potassium 3-prop-2-enoyloxypropane-1-sulfonate, sodium acrylate, sodium carbonate and 2-acrylamido-2-methylpropanesulfonic acid.
The second embodiment discloses a preparation method of self-powered hydrogel containing zinc chloride electrolyte on the basis of the raw materials, two or more gel units are prepared, and the hydrogel is prepared according to different combination sequences:
(1) Fully dispersing the gel unit raw materials in a proper amount of deionized water by using a vortex oscillator;
(2) Removing bubbles by ultrasonic waves, and injecting the mixed solution into a mold by using a precision injection pump;
(3) Standing at room temperature to obtain a gel unit;
(4) Similarly, different combinations of hydrogels can be made by adjusting the gel unit injection sequence.
In some alternative embodiments, the gel units or the hydrogels are tested for good mechanical durability.
In alternative embodiments, the gel may generate a stable current on the surface, the hydrogel current may change with changes in external pressure, and the pressure signal may be converted into a current change signal for use in fabricating a sensor or signal transmission device, which demonstrates the benefits described herein.
The steps of the above methods are divided for clarity, and the implementation may be combined into one step or split some steps, and the steps are divided into multiple steps, so long as the same logical relationship is included, which are all within the protection scope of the present patent; the core design of introducing no significant design, but not changing the raw material composition and preparation method thereof, is within the scope of protection of the patent.
Third embodiment
Based on the examples already disclosed, a third embodiment of the present invention provides a preferred example of a self-powered hydrogel containing zinc chloride electrolyte:
the low-salt concentration gel unit comprises, by mass, 0.01-2.0% of acrylamide, 0.1-0.5% of N, N ' -methylene bisacrylamide, 0.1-0.5% of ammonium persulfate, 0.1-0.5% of potassium persulfate, 0.01-0.1% of N, N, N ', N ' -tetramethylethylenediamine and 0.1-5% of zinc chloride.
The raw materials for preparing the high-salt-concentration gel unit and the mass composition of the gel unit comprise 0.01-2.0% of acrylamide, 0.1-0.5% of N, N ' -methylene bisacrylamide, 0.1-0.5% of ammonium persulfate, 0.1-0.5% of potassium persulfate, 0.01-0.1% of N, N, N ', N ' -tetramethyl ethylenediamine and 30-50% of zinc chloride.
The cation selective gel unit comprises, by mass, 0.01-2.0% of acrylamide, 0.1-0.5% of N, N ' -methylene bisacrylamide, 0.1-0.5% of ammonium persulfate, 0.1-0.5% of potassium persulfate, 0.01-0.1% of N, N, N ', N ' -tetramethylethylenediamine and 30-50% of a cation exchange group compound.
The anion selective gel unit comprises, by mass, 0.01-2.0% of acrylamide, 0.1-0.5% of N, N ' -methylene bisacrylamide, 0.1-0.5% of ammonium persulfate, 0.1-0.5% of potassium persulfate, 0.01-0.1% of N, N, N ', N ' -tetramethylethylenediamine and 30-50% of an anion exchange group compound.
The cation exchange group material in the cation selective gel unit comprises: (3-acrylamidopropyl) trimethylammonium chloride, methacryloyloxyethyl trimethylammonium chloride, acryloyloxyethyl trimethylammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
The anion exchange group material in the anion selective gel unit comprises: sodium isethionate, potassium 3-prop-2-enoyloxypropane-1-sulfonate, sodium acrylate, sodium carbonate and 2-acrylamido-2-methylpropanesulfonic acid.
On the basis of the raw materials disclosed in this embodiment, a method for preparing a self-powered hydrogel containing zinc chloride electrolyte is also disclosed, and different hydrogels can be prepared because the raw material composition of the gel units, the number of the gel units and the combination sequence of the gel units are different:
(1) Fully dispersing the raw materials of the gel unit in a proper amount of deionized water by using a vortex oscillator;
(2) After bubbles are removed by ultrasonic waves, the mixed solution is injected into a mould by a precise injection pump;
(3) Standing at room temperature to obtain a gel unit;
(4) Similarly, the gel units are injected in sequence, and the hydrogel with different combinations can be prepared by adjusting the injection sequence of the gel units.
In some alternative embodiments, the gel units or the hydrogels as described are tested for good mechanical durability.
In some alternative embodiments, the gel can generate a stable current on the surface, the hydrogel current changes along with the change of the external pressure, and the pressure signal can be converted into a current change signal for manufacturing a sensor or a signal transmission device. The above demonstrates the benefits described herein.
A third embodiment of the invention relates to a self-powered hydrogel containing zinc chloride electrolyte and a method for making the same. The third embodiment is substantially the same as the second embodiment, and mainly differs in that: in the second embodiment, upper protection is performed; in the third embodiment of the present invention, the following preferred embodiments are provided. Further, it will be understood by those skilled in the art that the third embodiment of the present invention is a lower preferred embodiment of the second embodiment.
It is to be noted that the gel unit and the gel according to the present embodiment may be implemented by any one gel unit or a combination of a plurality of gel units in practical use. In addition, in order to highlight the innovative part of the present invention, elements that are not so closely related to solving the technical problems proposed by the present invention are not introduced in the present embodiment, but this does not indicate that other elements are not present in the present embodiment.
Fourth embodiment
A fourth embodiment of the invention relates to an example of a low salt concentration gel unit in a self-powered hydrogel containing zinc chloride electrolyte:
the low-salt-concentration gel unit comprises, by mass, acrylamide, 0.1% of N, N ' -methylene bisacrylamide, 0.2% of ammonium persulfate, 0.2% of potassium persulfate, 0.01% of N, N, N ', N ' -tetramethylethylenediamine and 0.5% of zinc chloride.
The preparation method comprises the following specific steps:
(1) Fully dispersing the raw materials in a proper amount of deionized water by using a vortex oscillator;
(2) Removing bubbles by ultrasonic waves, and injecting the mixed solution into a mold by using a precision injection pump;
(3) Standing at room temperature to obtain the product.
The gel unit described in this example has good mechanical properties and can prepare hydrogel with good mechanical properties, the test method is shown in FIG. 2, and the elastic coefficient k of the hydrogel can be calculated according to Hooke's law to be about 5130.0N. M -1 . The above demonstrates the beneficial effect described herein of having good mechanical durability.
Fifth embodiment
A fifth embodiment of the invention is directed to an example of a high salt concentration gel unit in a self-powered hydrogel containing zinc chloride electrolyte:
the high-salt-concentration gel unit comprises, by mass, acrylamide, 0.1% of N, N ' -methylene bisacrylamide, 0.1% of ammonium persulfate, 0.1% of potassium persulfate, 0.01% of N, N, N ', N ' -tetramethylethylenediamine and 50% of zinc chloride.
The preparation method comprises the following specific steps:
(1) Fully dispersing the raw materials in a proper amount of deionized water by using a vortex oscillator;
(2) After bubbles are removed by ultrasonic waves, the mixed solution is injected into a mould by a precise injection pump;
(3) Standing at room temperature to obtain the product.
The gel unit described in this example has good mechanical properties and can prepare hydrogel with good mechanical properties, the test method is shown in FIG. 2, and the elastic coefficient k of the hydrogel can be calculated according to Hooke's law to be about 7877.5N. M -1 . The above demonstrates the beneficial effect described herein of having good mechanical durability.
Sixth embodiment
A sixth embodiment of the invention is directed to an example of a cation selective gel unit in a self-powered hydrogel containing zinc chloride electrolyte:
the cation selective gel unit comprises, by mass, 0.1% of acrylamide, 0.5% of N, N ' -methylene-bisacrylamide, 0.5% of ammonium persulfate, 0.5% of potassium persulfate, 0.01% of N, N, N ', N ' -tetramethylethylenediamine and 40% of (3-acrylamidopropyl) trimethylammonium chloride.
The preparation method comprises the following specific steps:
(1) Fully dispersing the raw materials in a proper amount of deionized water by using a vortex oscillator;
(2) After bubbles are removed by ultrasonic waves, the mixed solution is injected into a mould by a precise injection pump;
(3) Standing at room temperature to obtain the product.
The gel unit described in this example has good mechanical properties and can prepare hydrogel with good mechanical properties, the test method is shown in FIG. 2, and the elastic coefficient k of the hydrogel can be calculated according to Hooke's law to be about 5542.5N. M -1 . The above demonstrates the beneficial effect described herein of having good mechanical durability.
Seventh embodiment
A seventh embodiment of the invention relates to an example of an anion selective gel unit in a self-powered hydrogel containing zinc chloride electrolyte:
the anion selective gel unit comprises 0.2% of acrylamide, 0.4% of N, N ' -methylene bisacrylamide, 0.4% of ammonium persulfate, 0.4% of potassium persulfate, 0.1% of N, N, N ', N ' -tetramethyl ethylenediamine and 40% of hydroxyethyl sodium sulfonate.
The preparation method comprises the following specific steps:
(1) Fully dispersing the raw materials in a proper amount of deionized water by using a vortex oscillator;
(2) After bubbles are removed by ultrasonic waves, the mixed solution is injected into a mould by a precise injection pump;
(3) Standing at room temperature to obtain the product.
The gel unit described in this example has good mechanical properties and can prepare hydrogel with good mechanical properties, the test method is shown in FIG. 2, and the elastic coefficient k of the hydrogel can be calculated according to Hooke's law to be about 5037.5N. M -1 . The above description demonstrates that the compositions described herein have good mechanical durabilityHas the beneficial effects.
The fourth, fifth, sixth and seventh embodiments are respectively specific optimization schemes of the single gel unit in the third embodiment.
Eighth embodiment
An eighth embodiment of the invention relates to an example of low salt gel units in a self-powered hydrogel containing zinc chloride electrolyte, as a comparative example to example four:
the low-salt-concentration gel unit comprises, by mass, 0.01% of acrylamide, 0.01% of N, N ' -methylene-bisacrylamide, 0.01% of ammonium persulfate, 0.01% of potassium persulfate, 0.001% of N, N, N ', N ' -tetramethylethylenediamine and 0.01% of zinc chloride.
This example did not allow the production of a formable hydrogel because the raw material mass ratio was below the range as claimed. The above demonstrates that the claimed raw material species and ratio ranges are within reasonable ranges.
Ninth embodiment
The ninth embodiment of the invention relates to a self-powered hydrogel containing zinc chloride electrolyte and a preparation method thereof, wherein the gel units prepared in the first to seventh embodiments are optionally selected from two or more, and the preparation method comprises the following specific steps:
(1) Using a vortex oscillator to respectively place the raw materials of each gel unit in different reaction containers and fully disperse the raw materials in a proper amount of deionized water;
(2) After bubbles are removed by ultrasonic waves, the mixed solution of each gel unit is sequentially injected into a mould by a precise injection pump;
(3) Standing at room temperature to obtain hydrogel product.
One structural mode of the hydrogel is shown in figure 3, and is H-C-L-A-H or H-A-L-C-H; as shown in fig. 4, the hydrogel electrical test result shows that two surfaces to be tested of the hydrogel can provide a stable current of 0.1 μ a, thereby realizing self-power supply; as the current of the hydrogel in FIG. 5 changes along with the change of the external pressure, "A, B, C" and "a, b and c" are points for applying external force, respectively, it can be known from the change of the current signal of the points for applying force in the figure that the hydrogel can convert the pressure signal into the changed current signal, which proves that the hydrogel has the beneficial effect of sensing communication or signal transmission function.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (4)
1. A preparation method of self-powered hydrogel containing zinc chloride electrolyte is characterized in that,
the self-powered hydrogel consists of gel units, namely a high salinity gel unit, an anion selective gel unit, a low salt concentration gel unit, a cation selective gel unit and a high salinity gel unit or a high salinity gel unit, a cation selective gel unit, a low salt concentration gel unit, an anion selective gel unit and a high salinity gel unit;
the low-salt concentration gel unit preparation raw materials comprise, by mass, 0.01% -2.0% of acrylamide, 0.1% -0.5% of N, N ' -methylene-bis-acrylamide, 0.1% -0.5% of ammonium persulfate, 0.1% -0.5% of potassium persulfate, 0.01% -0.1% of N, N, N ', N ' -tetramethyl-ethylenediamine and 0.1% -5% of zinc chloride;
the raw materials for preparing the high-salt concentration gel unit and the mass composition of the gel unit comprise 0.01-2.0% of acrylamide, 0.1-0.5% of N, N ' -methylene bisacrylamide, 0.1-0.5% of ammonium persulfate, 0.1-0.5% of potassium persulfate, 0.01-0.1% of N, N, N ', N ' -tetramethyl ethylenediamine and 30-50% of zinc chloride;
the cation selective gel unit comprises raw materials for preparing the cation selective gel unit and a cation exchange group compound 30-50%, wherein the raw materials comprise, by mass, acrylamide, N, N ' -methylene bisacrylamide 0.01-2.0%, ammonium persulfate 0.1-0.5%, potassium persulfate 0.1-0.5%, N, N, N ', N ' -tetramethyl ethylenediamine 0.01-0.1%, and the cation exchange group compound 30-50%;
the anion selective gel unit preparation raw material and the mass composition comprise 0.01-2.0% of acrylamide, 0.1-0.5% of N, N ' -methylene-bis-acrylamide, 0.1-0.5% of ammonium persulfate, 0.1-0.5% of potassium persulfate, 0.01-0.1% of N, N, N ', N ' -tetramethyl ethylenediamine and 30-50% of an anion exchange group compound;
the preparation method comprises the following steps:
fully dispersing the raw materials of the gel unit in a proper amount of deionized water by using a vortex oscillator;
after bubbles are removed by ultrasonic wave, injecting the mixed solution into a mould by using a precise injection pump;
standing at room temperature to obtain a gel unit;
step (4), injecting the gel units in sequence, and adjusting the injection sequence of the gel units to prepare hydrogels with different combinations;
the current of the hydrogel changes along with the change of the external pressure, and the pressure signal is converted into a current change signal for manufacturing a sensor or a signal transmission device;
the elastic stiffness coefficient of the low-salt-concentration gel unit is 4000-6000N/m, the elastic stiffness coefficient of the high-salt-concentration gel unit is 6000-9000N/m, the elastic stiffness coefficient of the cation selection gel unit is 4500-6500N/m, and the elastic stiffness coefficient of the anion selection gel unit is 4000-6000N/m.
2. A method of preparing a self-powered hydrogel containing zinc chloride electrolyte as defined in claim 1 wherein said cation selective gel unit said cation exchange group material comprises: (3-acrylamidopropyl) trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, 4-vinylpyridine and N, N-dimethylaminoethyl acrylate.
3. A method of preparing a self-powered hydrogel containing zinc chloride electrolyte as defined in claim 1 wherein said anion exchange group material of said anion selective gel unit comprises: sodium isethionate, potassium 3-prop-2-enoyloxypropane-1-sulfonate, sodium acrylate, sodium carbonate and 2-acrylamido-2-methylpropanesulfonic acid.
4. A self-powered hydrogel containing zinc chloride electrolyte, wherein said hydrogel is prepared by the method of any one of claims 1 to 3.
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