CN115057970A - High-strength high-toughness hydrogel based on ion aggregate crosslinking and preparation method and application thereof - Google Patents
High-strength high-toughness hydrogel based on ion aggregate crosslinking and preparation method and application thereof Download PDFInfo
- Publication number
- CN115057970A CN115057970A CN202210764826.XA CN202210764826A CN115057970A CN 115057970 A CN115057970 A CN 115057970A CN 202210764826 A CN202210764826 A CN 202210764826A CN 115057970 A CN115057970 A CN 115057970A
- Authority
- CN
- China
- Prior art keywords
- aggregate
- toughness
- strength
- ion
- ionic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 109
- 238000004132 cross linking Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 61
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 7
- 229920002521 macromolecule Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229920000083 poly(allylamine) Polymers 0.000 claims description 8
- VLGNTAHJZQOHJE-UHFFFAOYSA-N (6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical group OC1(C(C(=O)C2=CC=CC=C2)C=CC=C1)C VLGNTAHJZQOHJE-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000010382 chemical cross-linking Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 7
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000329 polyazepine Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a high-strength high-toughness hydrogel based on ion aggregate crosslinking and a preparation method and application thereof, which are characterized in that water-soluble amino macromolecules and anionic compounds containing unsaturated C-C bonds are dissolved in deionized water to obtain mixed liquid, and the mixed liquid is stirred at room temperature to obtain an ion aggregate aqueous solution; adding acrylamide and a cross-linking agent into an ionic aggregate aqueous solution, uniformly mixing to obtain a mixed solution, adding a water-soluble photoinitiator into the mixed solution under a deoxygenation condition, and carrying out ultraviolet illumination reaction to obtain the ionic aggregate cross-linked high-strength high-toughness hydrogel. According to the invention, the ion aggregate is formed through the ion aggregation action and is used as a physical cross-linking agent to cross-link the hydrogel, and a small amount of chemical cross-linking agent is introduced to further improve the network cross-linking density, so that the high-strength high-toughness hydrogel with excellent toughness and rebound resilience is obtained.
Description
Technical Field
The invention belongs to the field of hydrogel preparation, and particularly relates to high-strength high-toughness hydrogel based on ion aggregate crosslinking, and a preparation method and application thereof.
Background
The synthetic hydrogel is a hydrated polymer network with a three-dimensional cross-linked network structure, has adjustable physicochemical properties, and is widely used in the fields of tissue engineering, bioengineering, sensors and the like.
In order to solve the problem of poor mechanical properties of synthetic hydrogels, various high-strength and high-toughness hydrogels have been developed in recent years. However, the high performance hydrogels developed today have a conflict between toughness and high resilience. High toughness generally requires materials with excellent energy dissipation capabilities, while high elasticity requires materials with lower energy dissipation, and therefore effective design is needed to improve the mechanical properties of hydrogels while increasing their resilience. Many solutions have been proposed in the industry, such as homogeneous network hydrogels, entangled hydrogels, and slip-ring hydrogels.
Aggregates are commonly used as a non-covalent interaction to prepare high toughness elastomeric materials, exhibiting a broad viscoelastic behavior. Phase separation structures are usually formed in the polymer due to aggregation, which has a significant effect on the properties of the material. Therefore, many researchers have used a cross-linker based on aggregate interactions to make high performance hydrogels. However, most aggregates, although capable of crosslinking the hydrogel, cause uneven distribution of crosslinking points, loose network crosslinking density, and lack of an effective energy dissipation mechanism, and the elasticity and toughness of the hydrogel cannot be effectively improved.
Therefore, the development of high-elasticity and high-toughness hydrogels with excellent comprehensive mechanical properties remains a key issue for the research and development of hydrogel applications in the field.
Disclosure of Invention
Aiming at the problem that the elasticity and the toughness of the hydrogel can not be effectively improved in the prior art, the invention aims to provide the high-strength high-toughness hydrogel based on ion aggregate crosslinking, and the preparation method and the application thereof.
In order to achieve the above purpose, the main concept of the invention is as follows: the water-soluble amino macromolecules and the anionic compounds containing unsaturated C ═ C bonds form ion aggregates in deionized water through ion aggregation, the ion aggregates are used as physical cross-linking agents to cross-link the hydrogel without causing uneven distribution of cross-linking points, and a small amount of chemical cross-linking agents are introduced to further improve the network cross-linking density, so that the elasticity is improved; due to the strong dynamic property of ionic interaction, reversible dissociation and recombination endow the hydrogel with excellent toughness and resilience, so that the prepared hydrogel based on ionic aggregate crosslinking has excellent mechanical properties.
Based on the inventive concept, the invention provides a preparation method of high-strength and high-toughness hydrogel based on ion aggregate crosslinking, which comprises the following steps:
(1) preparation of an aqueous solution of ion aggregates
Dissolving 1-5 parts by mass of water-soluble amino macromolecules and 2-6 parts by mass of anionic compounds containing unsaturated C ═ C bonds in 350-500 parts by mass of deionized water to obtain a mixed solution, and stirring the mixed solution at room temperature for 8-15 min to obtain an ion aggregate aqueous solution; the mass fraction of the ion aggregate is 0.6-3.1%;
the water-soluble amino macromolecule is polyallylamine or polyethyleneimine, and the anionic compound containing unsaturated C ═ C bonds is one of acrylic acid, vinyl sulfonic acid or sodium styrene sulfonate;
(2) preparation of hydrogels
Adding 130-170 parts of acrylamide and 0.01-0.04 part of cross-linking agent into the ionic aggregate aqueous solution obtained in the step (1), uniformly mixing to obtain a mixed solution, adding 0.15-0.30 part of water-soluble photoinitiator into the mixed solution under a deoxygenation condition, and then carrying out ultraviolet illumination reaction to obtain the ionic aggregate cross-linked high-strength high-toughness hydrogel.
In the preparation method of the ionic aggregate crosslinking-based high-strength and high-toughness hydrogel, the polyallylamine is a water-soluble polymer with a large number of polar amino groups, and the molecular weight of the polyallylamine is preferably 1000-90000, and more preferably 3000-25000. The polyethyleneimine is also called polyazepine and is a water-soluble high-molecular polymer, and the molecular weight of the polyethyleneimine is preferably 1000-10000.
In the above method for preparing the high-strength and high-toughness hydrogel based on ionic aggregate crosslinking, in step (2), the crosslinking agent is usually a common crosslinking agent for preparing hydrogels. Preferably, the cross-linking agent is N, N' -methylenebisacrylamide or polyethylene glycol diacrylate.
In the step (2), the deoxidation conditions can be realized by adopting the conventional deoxidation operation in the field, and the deoxidation is preferably realized by one of the following modes: introducing nitrogen into the obtained mixed solution under the condition of stirring to remove dissolved oxygen in the mixed solution; or removing the dissolved oxygen in the mixed liquid by pumping air through a vacuum pump. On the basis of meeting the requirement of complete deoxidation, a person skilled in the art can determine the time for introducing nitrogen or vacuum extraction according to the actual situation, and the time for introducing nitrogen or vacuum extraction is usually 10-15 min so as to meet the deoxidation condition.
In the above method for preparing the hydrogel with high strength and high toughness based on ionic aggregate crosslinking, in step (2), the water-soluble photoinitiator is usually a common water-soluble photoinitiator for preparing hydrogels. Preferably, the water-soluble photoinitiator is 2-hydroxy-2-methylbenzophenone or 1-hydroxycyclohexyl phenyl methanone.
In the preparation method of the high-strength and high-toughness hydrogel based on ion aggregate crosslinking, in the step (2), the ultraviolet wavelength is 10-400 nm, and the ultraviolet irradiation condition can adopt the conventional ultraviolet irradiation condition for preparing the hydrogel. The invention preferably selects the ultraviolet irradiation power of 10-400W and the irradiation time of 20-40 min.
The invention also provides the high-strength high-toughness hydrogel based on the ionic aggregate crosslinking prepared by the method. The physical cross-linking agent formed by the hydrogel based on the ion aggregation and a small amount of chemical cross-linking agent act together to form an elastic and tough network structure, the elasticity of the elastic and tough network structure reaches 83 percent, the breaking strength exceeds 1MPa, the toughness reaches 8.2MJ/m3, and the elastic and tough network structure shows excellent mechanical properties.
The invention further provides application of the high-strength high-toughness hydrogel based on ion aggregate crosslinking in the aspects of manufacturing sensors, intelligent wearing or soft robots.
Compared with the prior art, the high-strength high-toughness hydrogel based on ion aggregate crosslinking and the preparation method and application thereof provided by the invention have the following beneficial effects:
(1) the preparation method of the high-strength high-toughness hydrogel based on ion aggregate crosslinking provided by the invention adopts a brand-new method for preparing the ion aggregate, only water-soluble amino macromolecules and anionic compounds containing unsaturated C ═ C bonds are simply mixed in deionized water, and the ion aggregate can be formed through ion aggregation, the size of the ion aggregate is nano-scale, and the preparation technology has breakthrough guiding significance for preparing the nano-scale aggregate as a crosslinking agent.
(2) The high-strength high-toughness hydrogel prepared by the invention uses the ion aggregate formed based on the ion aggregation as the physical cross-linking agent to prepare the high-performance hydrogel, the ion aggregate as the physical cross-linking agent can not cause uneven distribution of cross-linking points while cross-linking the hydrogel, and a small amount of chemical cross-linking agent is introduced to further improve the network cross-linking density, thereby improving the elasticity. The hydrogel has very excellent toughness and resilience through reversible dissociation and recombination under the action of ions with strong dynamic property; therefore, the hydrogel based on ion aggregate crosslinking prepared by the invention has excellent mechanical properties.
(3) The hydrogel material prepared by the invention has the advantages of high strength, high toughness, excellent rebound resilience, puncture resistance and fatigue resistance, and is expected to be widely applied to the aspects of sensors, intelligent wearing, soft robots and the like.
Drawings
FIG. 1 is a schematic representation of an aqueous ion aggregate solution prepared in examples 1-3.
FIG. 2 is a graph showing a distribution of particle sizes of the ion aggregates prepared in examples 1 to 3.
FIG. 3 is a FT-IR plot of the ion aggregate prepared in example 3, the hydrogel prepared in example 7, and polyacrylamide.
FIG. 4 is a tensile stress-strain curve of the high strength and toughness hydrogels prepared in examples 8, 12 and 13.
FIG. 5 is a graph showing the puncture resistance behavior of the high strength, high toughness hydrogel prepared in example 2.
FIG. 6 is a cyclic tensile stress-strain curve of the high strength and high toughness hydrogel prepared in example 9.
FIG. 7 is a cyclic compressive stress recovery curve of the high strength, high toughness hydrogel prepared in example 9.
Detailed Description
So that the technical solutions of the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings, it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, belong to the present invention.
Example 1
The preparation method of the high-strength and high-toughness hydrogel based on ionic aggregate crosslinking provided by the embodiment comprises the following steps:
(1) preparation of an aqueous solution of ion aggregates
Dissolving 3 parts by mass of polyallylamine (with a molecular weight of 15000) and 2 parts by mass of sodium styrene sulfonate in 400 parts by mass of deionized water to obtain a mixed solution, and stirring the mixed solution at room temperature for 10min to obtain an ion aggregate aqueous solution; the mass fraction of the ion aggregate is 1.2%;
(2) preparation of hydrogels
Adding 150 parts of acrylamide and 0.01 part of N, N' -methylene bisacrylamide into the ionic aggregate aqueous solution obtained in the step (1), uniformly mixing to obtain a mixed solution, performing vacuum air suction for 10min under the condition of stirring to remove dissolved oxygen in the solution, adding 0.2 part of 2-hydroxy-2-methyl benzophenone into the mixed solution, and performing illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W to obtain the high-strength high-toughness hydrogel based on ionic aggregate crosslinking.
Examples 2 to 7
Examples 2 to 7 are different from example 1 in the conditions for preparing the ion aggregate aqueous solution in step (1), and are specifically shown in table 1:
TABLE 1 preparation of aqueous solutions of ion aggregates under different conditions
Examples 8 to 10
Examples 8 to 10 differ from example 2 in the addition amounts of acrylamide, N' -methylenebisacrylamide, and photoinitiator (2-hydroxy-2-methylbenzophenone), the vacuum pumping time, and the uv irradiation time in step (2), which are specifically shown in table 3:
example 12
The preparation method of the high-strength and high-toughness hydrogel based on ionic aggregate crosslinking provided by the embodiment comprises the following steps:
(1) preparation of an aqueous solution of ion aggregates
Dissolving 3 parts by mass of polyallylamine (with a molecular weight of 15000) and 2 parts by mass of sodium styrene sulfonate in 400 parts by mass of deionized water to obtain a mixed solution, and stirring the mixed solution at room temperature for 10min to obtain an ion aggregate aqueous solution; the mass fraction of the ion aggregate is 1.2%;
(2) preparation of hydrogels
Adding 150 parts of acrylamide and 0.02 part of N, N' -methylene bisacrylamide into the ionic aggregate aqueous solution obtained in the step (1), uniformly mixing to obtain a mixed solution, performing vacuum air suction for 10min under the condition of stirring to remove dissolved oxygen in the solution, adding 0.2 part of 2-hydroxy-2-methyl benzophenone into the mixed solution, and performing illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W to obtain the high-strength high-toughness hydrogel based on ionic aggregate crosslinking.
Example 13
The preparation method of the high-strength and high-toughness hydrogel based on ionic aggregate crosslinking provided by the embodiment comprises the following steps:
(1) preparation of an aqueous solution of ion aggregates
Dissolving 3 parts by mass of polyallylamine (with a molecular weight of 15000) and 6 parts by mass of sodium styrene sulfonate in 400 parts by mass of deionized water to obtain a mixed solution, and stirring the mixed solution at room temperature for 10min to obtain an ion aggregate aqueous solution; the mass fraction of the ion aggregate is 2.2%;
(2) preparation of hydrogels
Adding 150 parts of acrylamide and 0.02 part of N, N' -methylene bisacrylamide into the ionic aggregate aqueous solution obtained in the step (1), uniformly mixing to obtain a mixed solution, performing vacuum air suction for 10min under the condition of stirring to remove dissolved oxygen in the solution, adding 0.2 part of 2-hydroxy-2-methyl benzophenone into the mixed solution, and performing illumination reaction for 40min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W to obtain the high-strength high-toughness hydrogel based on ionic aggregate crosslinking.
Example 14
The preparation method of the high-strength and high-toughness hydrogel based on ionic aggregate crosslinking provided by the embodiment comprises the following steps:
(1) preparation of an aqueous solution of ion aggregates
Dissolving 4 parts of polyethyleneimine (with the molecular weight of 5000) and 5 parts of vinylsulfonic acid in 450 parts of deionized water according to parts by weight to obtain a mixed solution, and stirring the mixed solution at room temperature for 10min to obtain an ion aggregate aqueous solution; the mass fraction of the ion aggregate is 2.0%;
(2) preparation of hydrogels
Adding 150 parts of acrylamide and 0.01 part of polyethylene glycol diacrylate into the ionic aggregate aqueous solution obtained in the step (1), uniformly mixing to obtain a mixed solution, removing dissolved oxygen in the solution by vacuum pumping for 12min under the condition of stirring, adding 0.3 part of 1-hydroxycyclohexyl phenyl ketone into the mixed solution, and then carrying out illumination reaction for 20min under an ultraviolet lamp with the wavelength of 365nm and the power of 330W to obtain the high-strength high-toughness hydrogel based on ionic aggregate crosslinking.
The ion aggregates and hydrogels prepared in some of the examples were subjected to the following performance analysis.
The used test method comprises the following steps:
DLS test
The particle size of the prepared ionic aggregates was measured by a NANO ZS Zetasizer type nanosizer.
FT-IR test
And (3) carrying out infrared spectrum detection on the polyacrylamide, the prepared ion aggregate and the high-strength high-toughness hydrogel sample by a Thermo Scientific Nicolet iS50 type Fourier infrared spectrometer.
3. Mechanical Property test
Mechanical properties of the high strength and toughness hydrogels were tested by an Instron model 5567 tester. Stretching the high-strength high-toughness hydrogel sample at a stretching rate of 100mm/min until the sample is broken, and recording a stress-strain curve; in order to investigate the elastic behavior of the high-strength and high-toughness hydrogel, the high-strength and high-toughness hydrogel is continuously subjected to cyclic stretching for 3 times under 500% strain, and a cyclic tensile stress-strain curve is recorded; in order to investigate the fatigue resistance of the high-strength and high-toughness hydrogel, 150 times of cyclic compression loading and unloading tests are continuously carried out on a high-strength and high-toughness hydrogel sample, the maximum strain of compression is constant at 60%, and the compression rate is 100 mm/min.
(ii) ion aggregate size
The aqueous ion aggregate solutions prepared in examples 1 to 3 were photographed at room temperature, and the results are shown in FIG. 1. As can be seen from FIG. 1, the dispersion of ion aggregates appears as an opaque emulsion, indicating that the ion aggregates self-assemble into nano-sized structures due to ionic action. And the opacity of the solution gradually increases with the increase of the anion proportion. The results demonstrate the formation of ionic aggregates.
The aqueous ion aggregate solutions prepared in examples 1 to 3 were subjected to particle size measurement using a dynamic light scattering instrument, and the results are shown in FIGS. 2a to 2 c. As can be seen from fig. 2(a), (b), (c), the particle size distribution of the aqueous solution of ion aggregates is consistent with the macroscopic results of fig. 1, with the aggregate size increasing from 191nm to 225nm and then to 777nm as the opacity of the solution gradually increases, which is caused by the enhancement of ionic interactions.
(di) ion aggregates and hydrogel structural characterization
Infrared spectroscopy tests were performed on the ionic aggregates prepared in example 3, the high strength and high toughness hydrogel prepared in example 13, and pure polyacrylamide, and the test results are shown in FIG. 3. As can be seen from FIG. 3, 1033cm is the ion aggregate -1 The characteristic peak is attributed to SO of sodium styrene sulfonate 3 - This characteristic peak is also present on the prepared hydrogel, but not on the polyacrylamide, which demonstrates successful crosslinking of the hydrogel by the ionic aggregates. Meanwhile, between 1600 and 1700cm -1 The asymmetric stretching vibration between the two groups of carbonyl also indicates the successful synthesis of the hydrogel.
(III) characterization of mechanical Properties of hydrogel
In order to study the influence of the ionic aggregates on the mechanical properties of the high-strength and high-toughness hydrogel, tensile tests were performed on the high-strength and high-toughness hydrogels prepared in examples 8, 12 and 13 with different addition amounts of the ionic aggregates, and the test results are shown in fig. 4. As can be seen from FIG. 4, the hydrogel crosslinked by the ionic aggregates all show excellent mechanical properties, the elongation at break exceeds 2400%, the breaking strength is close to 1MPa, and the toughness exceeds 7MJ/m 3 . The young's modulus of the hydrogel gradually increased with the increase of the added amount of the ionic aggregate, the tensile strength and the elongation at break were increased and then decreased, and the comprehensive mechanical properties reached the optimum values when the ionic aggregate prepared in example 2 was used. Mainly because of followingThe increase of the ion aggregates forms more ionic bonds, so that the ion aggregates have gradually enhanced effect, and the modulus and the strength of the hydrogel are improved while the change of the breaking strain is small.
In addition, the hydrogel prepared in example 2 was subjected to a puncture resistance behavior test in order to macroscopically exhibit the toughness of the hydrogel. As shown in fig. 5, the hydrogel was cut with a blade without being cut and immediately restored to the original shape after the external force was removed, and no damage was observed on the surface, which also macroscopically demonstrates the strong toughness of the hydrogel.
(IV) elastic Properties of high Strength and toughness hydrogels
To investigate the resilience of the high strength and toughness hydrogel, the high strength and toughness hydrogel prepared in example 9 was subjected to a cyclic tensile test at a strain of 500%, and the test results are shown in fig. 6. As can be seen from fig. 6, the hydrogel showed very low energy dissipation after the first cycle, with good coincidence of the loading curve with the unloading curve. Elasticity is defined as the ratio of the work done during unloading to the work done during loading. The hydrogel has elasticity reaching 79 percent after the first circulation and extremely high resilience. While after two consecutive cycles, the elasticity further increased to 93% and 94% because the inelastic structure was destroyed after the first cycle, so that it increased in elasticity in the subsequent cycles. The above results indicate that the hydrogel has very excellent resilience.
(V) fatigue resistance of high-strength high-toughness hydrogel
In order to investigate the fatigue resistance of the high strength and toughness hydrogel, the high strength and toughness hydrogel prepared in example 9 was subjected to continuous 150 cycles of compression at 60% strain, and the test results are shown in FIG. 7. As can be seen from FIG. 7, after the high-strength high-toughness hydrogel is subjected to 150 times of cyclic compression loading-unloading tests, the stress corresponding to the maximum compressive strain is almost kept unchanged, no damage occurs, and the high-strength high-toughness hydrogel is proved to have excellent fatigue resistance.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (9)
1. A preparation method of high-strength and high-toughness hydrogel based on ion aggregate crosslinking is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of an aqueous solution of ion aggregates
Dissolving 1-5 parts by mass of water-soluble amino macromolecules and 2-6 parts by mass of anionic compounds containing unsaturated C ═ C bonds in 350-500 parts by mass of deionized water to obtain a mixed solution, and stirring the mixed solution at room temperature for 8-15 min to obtain an ion aggregate aqueous solution; the mass fraction of the ion aggregate is 0.6-3.1%;
the water-soluble amino macromolecule is polyallylamine or polyethyleneimine, and the anionic compound containing unsaturated C ═ C bonds is one of acrylic acid, vinyl sulfonic acid or sodium styrene sulfonate;
(2) preparation of hydrogels
Adding 130-170 parts of acrylamide and 0.01-0.04 part of cross-linking agent into the ionic aggregate aqueous solution obtained in the step (1), uniformly mixing to obtain a mixed solution, adding 0.15-0.30 part of water-soluble photoinitiator into the mixed solution under a deoxygenation condition, and then carrying out ultraviolet illumination reaction to obtain the ionic aggregate cross-linked high-strength high-toughness hydrogel.
2. The method for preparing high-strength high-toughness hydrogel based on ionic aggregate crosslinking according to claim 1, wherein the method comprises the following steps: the molecular weight of the polyallylamine is 1000-90000, and the molecular weight of the polyethyleneimine is 1000-10000.
3. The method for preparing high-strength high-toughness hydrogel based on ionic aggregate crosslinking according to claim 1, wherein the method comprises the following steps: the cross-linking agent is N, N' -methylene bisacrylamide or polyethylene glycol diacrylate.
4. The method for preparing high-strength high-toughness hydrogel based on ionic aggregate crosslinking according to claim 1, wherein the method comprises the following steps: in the step (2), the deoxidation condition is realized by one of the following modes: introducing nitrogen into the obtained mixed solution under the condition of stirring to remove dissolved oxygen in the mixed solution; or removing the dissolved oxygen in the mixed liquid by pumping air through a vacuum pump.
5. The method for preparing high-strength high-toughness hydrogel based on ionic aggregate crosslinking according to claim 4, wherein the method comprises the following steps: and introducing nitrogen or vacuumizing for 10-15 min.
6. The method for preparing high-strength high-toughness hydrogel based on ionic aggregate crosslinking according to claim 1, wherein the method comprises the following steps: in the step (2), the water-soluble photoinitiator is 2-hydroxy-2-methylbenzophenone or 1-hydroxycyclohexyl phenyl ketone.
7. The method for preparing high-strength high-toughness hydrogel based on ionic aggregate crosslinking according to any one of claims 1 to 6, wherein: in the step (2), the ultraviolet irradiation conditions are as follows: the wavelength of the ultraviolet light is 10-400 nm, the irradiation power of the ultraviolet light is 10-400W, and the irradiation time is 20-40 min.
8. A high strength and high toughness hydrogel based on ionic aggregate crosslinks prepared by the method of any one of claims 1 to 7.
9. Use of the high strength and high toughness hydrogel based on ionic aggregate crosslinking according to claim 8 for the manufacture of sensors, smart wear or soft robots.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210764826.XA CN115057970B (en) | 2022-06-29 | 2022-06-29 | High-strength high-toughness hydrogel based on ion aggregate crosslinking and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210764826.XA CN115057970B (en) | 2022-06-29 | 2022-06-29 | High-strength high-toughness hydrogel based on ion aggregate crosslinking and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115057970A true CN115057970A (en) | 2022-09-16 |
| CN115057970B CN115057970B (en) | 2023-09-22 |
Family
ID=83205409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210764826.XA Active CN115057970B (en) | 2022-06-29 | 2022-06-29 | High-strength high-toughness hydrogel based on ion aggregate crosslinking and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115057970B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023116060A1 (en) * | 2021-12-23 | 2023-06-29 | 中国科学院兰州化学物理研究所 | Structured hydrogel, and preparation method for hydrogel heart and valves |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030232895A1 (en) * | 2002-04-22 | 2003-12-18 | Hossein Omidian | Hydrogels having enhanced elasticity and mechanical strength properties |
| WO2007063046A1 (en) * | 2005-12-01 | 2007-06-07 | Wacker Chemie Ag | Ionically and/or organometallically functionalized silicone polymers crosslinkable to high-strength elastomers |
| CN105732999A (en) * | 2016-04-18 | 2016-07-06 | 北京师范大学 | High-strength crosslinked hydrogel, elastomer and preparation method of high-strength crosslinked hydrogel and elastomer |
| CN110804145A (en) * | 2019-11-28 | 2020-02-18 | 黄春美 | Hydrogel composite material with high thermal conductivity and electric conductivity and preparation method thereof |
| CN111363106A (en) * | 2020-03-24 | 2020-07-03 | 四川大学 | High-strength high-toughness nano composite hydrogel and preparation method and application thereof |
| CN113150208A (en) * | 2021-03-31 | 2021-07-23 | 四川大学 | High-toughness hydrogel preparation method based on high-molecular-initiation crosslinking integrated technology and hydrogel |
-
2022
- 2022-06-29 CN CN202210764826.XA patent/CN115057970B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030232895A1 (en) * | 2002-04-22 | 2003-12-18 | Hossein Omidian | Hydrogels having enhanced elasticity and mechanical strength properties |
| WO2007063046A1 (en) * | 2005-12-01 | 2007-06-07 | Wacker Chemie Ag | Ionically and/or organometallically functionalized silicone polymers crosslinkable to high-strength elastomers |
| CN105732999A (en) * | 2016-04-18 | 2016-07-06 | 北京师范大学 | High-strength crosslinked hydrogel, elastomer and preparation method of high-strength crosslinked hydrogel and elastomer |
| CN110804145A (en) * | 2019-11-28 | 2020-02-18 | 黄春美 | Hydrogel composite material with high thermal conductivity and electric conductivity and preparation method thereof |
| CN111363106A (en) * | 2020-03-24 | 2020-07-03 | 四川大学 | High-strength high-toughness nano composite hydrogel and preparation method and application thereof |
| CN113150208A (en) * | 2021-03-31 | 2021-07-23 | 四川大学 | High-toughness hydrogel preparation method based on high-molecular-initiation crosslinking integrated technology and hydrogel |
Non-Patent Citations (4)
| Title |
|---|
| CAO, ZX等: "Tough and Resilient Hydrogels Enabled by a Multifunctional Initiating and Cross-Linking Agent", 《GELS》, vol. 7, no. 4, pages 177 * |
| JUNQI SUN等: "One-Step Synthesis of Healable Weak-Polyelectrolyte-Based Hydrogels with High Mechanical Strength, Toughness, and Excellent Self-Recovery", 《ACS MACRO LETTERS》, vol. 8, no. 5, pages 500 - 505 * |
| 吴奕璇等: "基于超支化聚合物水凝胶的研究进展", 《现代化工》, vol. 42, no. 01, pages 35 - 39 * |
| 李江波等: "基于自组装行为的微球复合水凝胶制备及性能", 《高分子材料科学与工程》, vol. 37, no. 10, pages 30 - 37 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023116060A1 (en) * | 2021-12-23 | 2023-06-29 | 中国科学院兰州化学物理研究所 | Structured hydrogel, and preparation method for hydrogel heart and valves |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115057970B (en) | 2023-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108276522B (en) | Preparation method of iron ion double-crosslinked alginate-polyacrylamide acrylic acid high-performance hydrogel capable of being printed in 3D mode | |
| CN107556423B (en) | Preparation method of high-strength and high-toughness double-physical-crosslinking polyacrylic acid hydrogel | |
| Jiang et al. | A self-healable and tough nanocomposite hydrogel crosslinked by novel ultrasmall aluminum hydroxide nanoparticles | |
| CN108440772A (en) | A kind of selfreparing conduction dual network structure hydrogel and preparation method thereof | |
| CN108409997B (en) | Preparation method of ultrahigh-strength anisotropic hydrogel containing cellulose nanowhiskers | |
| CN110551296B (en) | Pectin-based double-physical crosslinked hydrogel and preparation method and application thereof | |
| CN111393675B (en) | Rapid-forming self-healing hydrogel and preparation method thereof | |
| CN110452395B (en) | Tough antistatic double-network silicon hydrogel and preparation method thereof | |
| CN115057970B (en) | High-strength high-toughness hydrogel based on ion aggregate crosslinking and preparation method and application thereof | |
| CN112480312B (en) | Preparation method of high-elasticity high-strength double-crosslinking porous hydrogel | |
| Ren et al. | Super-tough, ultra-stretchable and strongly compressive hydrogels with core–shell latex particles inducing efficient aggregation of hydrophobic chains | |
| Wang et al. | Synthesis and characterization of multi-sensitive microgel-based polyampholyte hydrogels with high mechanical strength | |
| CN114957550B (en) | Deep profile control and re-adhesion supermolecule gel particles and preparation method thereof | |
| CN110724282A (en) | Super-long stretching self-repairing hydrogel bonding material and preparation method thereof | |
| Wang et al. | An interfacially polymerized self-healing organo/hydro copolymer with shape memory | |
| Sun et al. | Extremely stretchable and tough hybrid hydrogels based on gelatin, κ-carrageenan and polyacrylamide | |
| CN106519152A (en) | Polymer nanoparticle, composite hydrogel, and preparation method thereof | |
| CN111303348A (en) | Photocuring waterborne polyurethane emulsion and preparation method and application thereof | |
| CN109180965A (en) | A kind of hydrogel and preparation method thereof of multiple physical crosslinking | |
| CN112538172B (en) | Poly (N-acryloyl glycinamide) microgel self-reinforced hydrogel and preparation method thereof | |
| CN115141316B (en) | Nanocellulose enhanced supermolecular gel particles for deep profile control and preparation method thereof | |
| CN108329422B (en) | Water-in-water type microsphere profile control agent and preparation method thereof | |
| CN113024844B (en) | Small-molecule cross-linking agent toughened hydrogel and preparation method thereof | |
| CN113150319B (en) | Cellulose nanocrystal reinforced efficient self-healing hydrogel and preparation method thereof | |
| CN109054273B (en) | Double-network hydrogel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |