CN110746614A - Preparation method and application of impact-resistant high-strength physical hydrogel - Google Patents
Preparation method and application of impact-resistant high-strength physical hydrogel Download PDFInfo
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- CN110746614A CN110746614A CN201810821836.6A CN201810821836A CN110746614A CN 110746614 A CN110746614 A CN 110746614A CN 201810821836 A CN201810821836 A CN 201810821836A CN 110746614 A CN110746614 A CN 110746614A
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- chloride
- strength physical
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 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 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
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- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 6
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
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- 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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
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- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 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 3
- 238000004132 cross linking Methods 0.000 claims description 3
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- 230000008018 melting Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 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 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- BQBYBPAPSIWHCE-UHFFFAOYSA-N 5-(dimethylamino)-2-methylpent-2-enoic acid Chemical compound CN(C)CCC=C(C)C(O)=O BQBYBPAPSIWHCE-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
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- 239000011575 calcium Substances 0.000 claims 1
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- VNLHWLYAOHNSCH-UHFFFAOYSA-N methyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[NH+](C)CC=C VNLHWLYAOHNSCH-UHFFFAOYSA-N 0.000 claims 1
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- UIYCCEDAMRKNGT-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate methylazanium chloride Chemical compound [Cl-].C[NH3+].CN(C)CCOC(=O)C=C UIYCCEDAMRKNGT-UHFFFAOYSA-N 0.000 description 2
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 2
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
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- RAOGYKUBTPSORX-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enoyloxyazanium chloride Chemical compound [Cl-].C[N+](C)(CC1=CC=CC=C1)OC(=O)C=C RAOGYKUBTPSORX-UHFFFAOYSA-M 0.000 description 1
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- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- 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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- 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
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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
- 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
- C08J2351/08—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 grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a preparation method of high-strength physical hydrogel with impact resistance. The hydrogel prepared by the method has the advantages of transparency, high modulus, compression resistance, high stretchability, toughness, insensitivity to defects, self-repair and flexible processability. The impact-resistant high-strength physical hydrogel and the composite material containing the hydrogel provided by the invention can be applied to the fields of impact-resistant materials, textiles and sensors.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method and application of an impact-resistant high-strength physical hydrogel.
Background
Hydrogels are a class of polymeric materials with a three-dimensional network structure that contain a large amount of moisture. Because the traditional hydrogel has poor mechanical properties (the stretching capacity is only several times of the original length, and the breaking energy is less than 100J/m-2) The application of the material as a structural material in the engineering field with higher mechanical strength requirement is limited. Therefore, hydrogel materials having unique excellent mechanical properties and tunable multiple functions have been attracting attention as structural materials. The hydrogel material with excellent performance has potential application value in various engineering fields including soft machines, flexible electronics, communication engineering and sensors. The research shows that the combined action of covalent bond and non-covalent bond can be used for preparing high-strength hydrogel. In general, there are four major non-covalent interactions that are widely used to construct high strength hydrogels: hydrogen bonding, hydrophobic interactions, ionic electrostatic interactions, van der waals interactions. The introduction of non-covalent bonds can enable the high strength gel to have multiple functionalities, such as high strength, toughness, self-healing, fatigue resistance, self-healing, and the like. Although various types of hydrogels have been widely used in the biomedical field, they still have certain limitations as structural materials. When the hydrogel is used as a structural material in production and living practices, the hydrogel has defects in the aspects of mechanical property, water retention capacity, transparency, multifunctionality and the like. The above-mentioned disadvantages limit the wide practical value of high strength hydrogels as structural materials. In addition, in the fields of impact-resistant materials, textiles, sensors and the like, the material has no impact resistance, high strength, high toughness and high tensile strengthAnd the application of the hydrogel with better extensibility, self-recovery property, fatigue resistance and self-healing property is reported in documents.
Disclosure of Invention
In order to overcome the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide an impact-resistant, high-strength physical hydrogel.
It is another object of the present invention to provide a method for preparing an impact-resistant high-strength physical hydrogel.
The third purpose of the invention is to provide the application of the impact-resistant high-strength physical hydrogel in the fields of impact-resistant materials, textiles and sensors.
It is a fourth object of the present invention to provide a composite material comprising an impact resistant high strength physical-physical hydrogel.
In order to achieve the first object, the invention provides an impact-resistant high-strength physical hydrogel, which has a three-dimensional network structure formed by crosslinking more than one polymerizable charged monomer and a neutral high-molecular polymer, wherein the three-dimensional network structure contains metal ions.
Wherein the polymerizable charged monomer is selected from the group consisting of negatively charged monomers Acrylic Acid (AA), methacrylic acid (MAA), Sodium Styrene Sulfonate (SSS), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), or positively charged monomers dimethylaminoethylmethylammonium methacrylate (DMAEMA. MC), dimethylaminoethylmethylammonium acrylate (DMAEAA. MC), diallyldimethylammonium chloride (DADMAC), dimethylaminopropylacrylamidomethylammonium chloride (DMAPMA. MC), dimethyldiallylammonium chloride (DMDAAC), diallyldicarbonylbutoxymethylammonium chloride (DACBMAC), diallylmethylbenzylammonium chloride (DAMABC), diallylethylbenzylammonium chloride (DAEABC), methacryloyloxyethyltrimethylammonium chloride (DMC), acryloyloxyethyltrimethylammonium chloride (DAC), and mixtures thereof, N, N-dimethyl-N-benzyl-acryloyloxy ammonium chloride (DBAAC).
Wherein the neutral high molecular polymer is selected from polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO) and hyperbranched polyglycidyl ether (HPG).
Wherein the metal ions are selected from lithium ions, sodium ions, potassium ions, magnesium ions, aluminum ions, calcium ions or iron ions.
In order to achieve the second object, the invention provides a method for preparing an impact-resistant high-strength physical hydrogel, which comprises the following steps: (a) firstly, adding an initiator into a solution containing monomers with charges and neutral high molecular polymers, standing for a certain time under the initiation condition, and then freezing and melting to obtain primary hydrogel; (b) and (b) immersing the primary hydrogel prepared in the step a into a metal ion salt solution, and reacting for a certain time to obtain the shock-resistant high-strength physical hydrogel.
Wherein the charged monomer is selected from the group consisting of negatively charged monomers Acrylic Acid (AA), methacrylic acid (MAA), Sodium Styrene Sulfonate (SSS), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), or the positively charged monomers dimethylaminoethylmethylammonium methacrylate (DMAEMA. MC), dimethylaminoethylmethylammonium acrylate (DMAEAA. MC), diallyldimethylammonium chloride (DADMAC), dimethylaminopropylacrylamide methylammonium chloride (DMAPMA. MC), dimethyldiallylammonium chloride (DMDAAC), diallyl-N-carbonylbutoxymethylammonium chloride (DACBMAC), diallylmethylbenzylammonium chloride (DAMABC), diallylethylbenzylammonium chloride (DAEABC), methacryloyloxyethyltrimethylammonium chloride (DMC), acryloyloxyethyltrimethylammonium chloride (DAC), N-dimethyl-N-benzyl-acryloyloxyammonium chloride (DBAAC).
Wherein the neutral high molecular polymer is selected from polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO) and hyperbranched polyglycidyl ether (HPG).
Preferably, the mass ratio of the charged monomer to the neutral high molecular polymer is 9: 1-1: 9.
Preferably, the weight ratio of the charged monomer and the neutral high molecular polymer to the hydrogel is 1-90%.
Wherein the initiation mode is photoinitiation, thermal initiation or radiation initiation.
Preferably, the initiator is selected from α -ketoglutaric acid, ammonium persulfate, potassium persulfate, sodium persulfate, 2-hydroxy-2-methyl-1-phenylpropanone, methyl benzoylformate or an alkyl iodonium salt.
More preferably, the initiator is added in an amount of 0.01 to 1% by weight based on the total weight of the hydrogel.
Preferably, the freezing time is 1-24 hours, and the temperature is-80 ℃ to 0 ℃.
Preferably, the ablation time is 1-12 hours, and the temperature is 10-80 ℃.
Wherein the metal ions are selected from lithium ions, sodium ions, potassium ions, magnesium ions, aluminum ions, calcium ions or iron ions.
Preferably, the concentration of the metal ion solution is 1-17mol/L or saturated salt solution.
Preferably, the ratio of the amount of the primary hydrogel to the concentration of the metal ions is 1: 20.
preferably, the primary hydrogel is soaked in metal ion solutions with different concentrations for 1-12 hours.
Preferably, the pH of the soaking solution is 1-14.
Preferably, the soaking temperature is 20-40 ℃.
Lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion or iron ion solution can be used as salting-out agent for preparing high-strength hydrogel. The destructive action of the salting-out agent on the hydrated layer of the primary hydrogel depends mainly on the solvent action of the cation. When the cation radius is smaller, the salification effect is stronger, resulting in greater disruption of the hydration layer. The salt solution of lithium ions is preferred as salting-out agent in the present invention, which has a small radius and a large ion potential. For the same anion, chloride salt is preferably selected as the salting-out agent, and the solubility of the chloride salt is higher than that of other anion salts at the same temperature, so that the requirement of the high-concentration salting-out agent is met, and the influence of a series of cation contents on the performance of the hydrogel is convenient to compare. The effective salting-out effect can greatly improve the mechanical property of the hydrogel, and the tensile strength, the elastic modulus, the self-recovery property and the transparency of the hydrogel material are improved.
Therefore, the impact-resistant high-strength physical hydrogel can adjust the mechanical properties of the hydrogel material by changing the ratio of the polymerizable charged monomer to the neutral high-molecular polymer, the concentration of the metal ions and the soaking time.
In the impact-resistant high-strength physical hydrogel prepared by the method, a rigid molecular chain formed by self polymerization of a charged monomer and a flexible high-molecular polymer are crosslinked through non-covalent bond interaction, a three-dimensional network structure of primary flexible hydrogel is formed firstly, and then the primary flexible hydrogel is immersed in metal ion solutions with different concentrations. During the process, self-assembly and phase separation occur, and the metal ions destroy the hydration layer of the charged polymer to generate salting-out effect, namely, under high osmotic pressure, electrostatic repulsion is shielded, and polymer chains are promoted to be close to each other, so that a chain entanglement network structure with compact hydrogen bonds as cross connection points is formed. The dense charged network polymer macromolecular chains are mutually crosslinked through hydrogen bonds, so that high stress and elasticity of the hydrogel material are endowed, and the sparse neutral polymer is randomly distributed in the hydrogel network, so that the material is endowed with large strain performance. At the same time, the breaking of weak hydrogen bonds and the deformation of flexible polymer chains can consume energy.
Therefore, the physical structure of the prepared shock-resistant high-strength physical hydrogel is closely related to the mechanical properties thereof, and the mechanical properties of the hydrogel material can be adjusted by changing the ratio of the charged monomer to the neutral high-molecular polymer, the concentration of the metal ions, the soaking time and the like.
The impact-resistant high-strength physical hydrogel prepared by the method has high transparency and mechanical properties comparable to those of glass. The toughness of the alloy reaches 54860J/m2The tensile strength is 13MPa (11 times of elongation), the compressive strength is up to 588MPa (85% of fracture strain), the tensile modulus is up to 1.4MPa, the compressive modulus is 1.47MPa, the fracture stress after self-repairing reaches 1.82MPa, the mechanical property is generally higher than that of most high-strength hydrogels, and the hydrogel has recoverable hysteresis energy consumption and self-healing capacity. The invention is madeThe strength and toughness of the prepared shock-resistant high-strength physical hydrogel are not only enough to resist steel balls launched from an air gun, but also have the properties of puncture resistance, self-healing, sewability and fracture insensitivity. This combination of excellent mechanical properties can be attributed to the synergistic effects of unique self-assembly, phase separated structure and high density of hydrogen bonding. Under the salting-out action, the dynamic crosslinking degree between high-density polymer chains formed by reversible hydrogen bonding and high-molecular chain winding is increased to form a compact high-molecular network structure. In addition, because metal ions in the hydrogel have certain moisture absorption performance, the impact-resistant high-strength physical hydrogel prepared by the invention has good water storage capacity, and can keep stable mechanical performance and long service time in the air.
In order to achieve the third purpose, the technical scheme adopted by the invention is to apply the prepared impact-resistant high-strength physical hydrogel to the aspects of impact-resistant materials, textiles and sensors.
Furthermore, the impact-resistant material is protective equipment such as bulletproof glass, anti-theft glass, special protective glass, toughened glass or an interlayer thereof, bulletproof clothes, sports wristbands, knee pads and the like.
Further, the textile material is selected from flame retardant materials, fire-fighting clothing.
Further, the sensor material is selected from wearable devices, flexible robots, conductivity sensors, anti-shock sensors.
To achieve the fourth object, the present invention also provides a high-strength physical hydrogel composite comprising impact resistance. The composite material provided by the invention also comprises another material component with different chemical and physical properties.
Further, another material component contained in the composite material is silicon dioxide.
Compared with the prior art, the invention has the advantages that the impact-resistant high-strength physical hydrogel prepared by a simple, environment-friendly and non-toxic method has the advantages of greatly improving the production and preparation operation efficiency of the hydrogel, simultaneously having low raw material cost, being free from complex modification treatment and being green and safe in preparation process, and the prepared hydrogel three-dimensional network structure is formed by micro-phase separation, has the glass properties of transparency, high modulus, compression resistance and the like, and has the advantages of high stretchability, high toughness, high restorability, insensitivity and self-repair. The impact-resistant high-strength physical hydrogel and the composite material containing the hydrogel provided by the invention can be applied to the fields of impact-resistant materials, textiles and sensors.
Drawings
FIG. 1 is a graph of tensile stress-strain curves of hydrogels containing metal ions of different valence states.
Figure 2 is a tensile stress-strain curve of a hydrogel soaked in a lithium chloride solution for various periods of time.
FIG. 3 is a graph of tensile stress-strain curves of hydrogels soaked in lithium chloride solutions of different concentrations.
Figure 4 is a tensile stress-strain curve for hydrogels of charged monomers and neutral polymers at different ratios.
FIG. 5 is a graph of tensile stress-strain curves for hydrogels containing varying proportions of initiator content.
Figure 6 is a tensile stress-strain curve for hydrogels containing different proportions of silica.
FIG. 7 is a graph of the energy to break of hydrogels soaked in lithium chloride solutions of different concentrations.
Figure 8 is a tensile stress-strain curve of the time recovery performance of an impact resistant high strength physical hydrogel.
Figure 9 is a tensile stress-strain curve of the self-healing performance of an impact resistant high strength physical hydrogel.
Figure 10 is a compressive stress-strain curve for hydrogels of different ratios of charged monomers to neutral polymers.
FIG. 11 is a plot of water retention versus time for a high strength physical hydrogel that impacted at 25 deg.C, 30% humidity.
Figure 12 is a plot of transparency versus wavelength for an impact resistant, high strength physical hydrogel.
FIG. 13 is a Scanning Electron Microscope (SEM) photograph of an impact resistant, high strength physical hydrogel.
FIG. 14 is an Atomic force microscope-Infrared (AFM) with an intrinsic capability (IR) profile of an impact resistant, high strength physical hydrogel.
FIG. 15 is a graph of an Atomic Force Microscopy (AFM) with an in-free (IR), AFM-IR, hydrogel without and with added metal ions.
FIG. 16 is a schematic diagram of the preparation of impact resistant high strength physical hydrogel
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
Example 1
The preparation method comprises the following steps of firstly dissolving 3g of hyperbranched polyglycidyl ether (HPG) powder in 70mL of deionized water under the condition of 90 ℃ water bath, then adding 7g of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 0.135g of α -ketoglutaric acid, and uniformly dissolving at 37 ℃ under room temperature, pouring the prepared solution into a glass mold, standing at room temperature for 12 hours for complete defoaming, then placing under an ultraviolet lamp for 6 hours, finally placing the material in an environment at-20 ℃ for freezing for 2 hours, and then melting at room temperature for 3 hours, wherein the mass ratio of the 3g of hyperbranched polyglycidyl ether (HPG) to the methacryloyloxyethyl trimethyl ammonium chloride (DMC) and the deionized water accounts for 80% of the total mass of the mixed solution.
The second step is that: in a 100mL volumetric flask, 54.868g of LiCl was dissolved in deionized water to obtain a LiCl salt solution with a concentration of 12 mol/L.
The third step: and completely soaking the hydrogel prepared in the first step in the LiCl salt solution with the concentration of 12mol/L prepared in the second step, and standing at room temperature for 12 hours to obtain the shock-resistant high-strength physical hydrogel. The specific preparation process and principle are shown in fig. 16.
An electronic tensile machine is used for carrying out tensile and compression tests on the dumbbell-shaped hydrogel, the ultra-strong and ultra-tough physical hydrogel obtained when the concentration of the LiCl salt solution is 12mol/L can be stretched to 10 times of the original length, the tensile breaking strength reaches 13MPa, and the breaking energy is 54860J/m2And the fracture stress after self-repairing reaches 1.82 MPa. The hydrogel gel exhibits an average light transmittance of 90% from 380 to 720nm at visible wavelengths as measured by an ultraviolet spectrophotometer. The water-retaining capacity of the gel is at least over 100h at the room temperature of 25 ℃ and in the environment of 30% humidity.
Example 2
The embodiment comprises the following steps: firstly, under the condition of water bath at 90 ℃, 15g of polyvinyl alcohol is dissolved in 70mL of deionized water, then 5g of diallyl methyl benzyl ammonium chloride is added, and the solution is uniformly dissolved at room temperature of 37 ℃. The mass ratio of the polyvinyl alcohol powder to the diallyl methyl benzyl ammonium chloride is 3:1, the deionized water accounts for 30% of the total mass of the mixed solution, and the addition amount of the initiator alkyl iodonium salt accounts for 0.05% of the total weight of the hydrogel. Pouring the prepared solution into a glass mold, standing at room temperature for 12h, defoaming completely, and placing under an ultraviolet lamp for 6 h. Finally, the material is frozen for 2h at-70 ℃, and then ablated for 5h at the temperature of 60 ℃.
The second step is that: MgCl was prepared in a 100mL volumetric flask at a concentration of 5mol/L2A salt solution.
The third step: completely soaking the hydrogel prepared in the first step in MgCl prepared in the second step and having the concentration of 5mol/L2In the salt solution, the pH of the soaking solution is 3, the soaking temperature is 20 ℃, and after soaking for 10 hours, an impact-resistant high-strength physical hydrogel is formed.
Example 3
The embodiment comprises the following steps: firstly, dissolving 12g of polyethylene glycol powder in 70mL of deionized water under the condition of 90 ℃ water bath, then adding 2g of sodium styrene sulfonate, and uniformly dissolving at 37 ℃ at room temperature. The mass ratio of the polyvinyl alcohol powder to the sodium styrene sulfonate is 6:1, the deionized water accounts for 20% of the total mass of the mixed solution, and the addition amount of the initiator ammonium persulfate accounts for 0.05% of the total weight of the hydrogel. Pouring the prepared solution into a glass mold, standing for 12 hours at room temperature, and defoaming completely. Finally, the material was frozen at-25 ℃ for 8h and then thawed at 40 ℃ for 7 h.
The second step is that: in a 100mL volumetric flask, 17mol/L AlCl was prepared3A salt solution.
The third step: completely soaking the hydrogel prepared in the first step in the AlCl prepared in the second step and having the concentration of 17mol/L3In the salt solution, the pH of the soaking solution is 9, the soaking temperature is 60 ℃, and after soaking for 3 hours, an impact-resistant high-strength physical hydrogel is formed.
Example 4
The embodiment comprises the following steps: firstly, dissolving 3g of polyethylene oxide powder in 70mL of deionized water under the condition of a water bath at 90 ℃, then adding 18g of dimethylaminoethylacrylate methyl ammonium chloride, and uniformly dissolving at room temperature of 37 ℃. The mass ratio of the polyvinyl alcohol powder to the dimethylaminoethylacrylate methyl ammonium chloride is 1:6, the deionized water accounts for 80% of the total mass of the mixed solution, and the addition amount of the initiator sodium persulfate accounts for 0.5% of the total weight of the hydrogel. Pouring the prepared solution into a glass mold, standing for 12 hours at room temperature, and defoaming completely. Finally, the material is frozen for 5h at-50 ℃ and then ablated for 1h at 80 ℃.
The second step is that: FeCl was prepared in a 100mL volumetric flask at a concentration of 3mol/L3A salt solution.
The third step: completely soaking the hydrogel prepared in the first step in FeCl with the concentration of 3mol/L prepared in the second step3In the salt solution, the pH of the soaking solution is 7, the soaking temperature is 30 ℃, and after soaking for 6 hours, an impact-resistant high-strength physical hydrogel is formed.
Example 5
Steel ball impact test
A steel ball impact test was conducted using the impact-resistant high-strength physical hydrogel prepared in example 1, the speed of a steel ball (diameter 10mm, mass 4.1g) was controlled by the pressure of an air chamber to 150m/s, 170m/s, and 200m/s, and then the specific initial velocity and residual velocity of the steel ball were measured using a laser velocimeter. In order to record the entire process of deformation of the target material, two high-speed cameras are placed behind the target material. The energy absorbed by the target material is the energy dissipation (Ep), the energy dissipation of the target material (100 x 2mm) affects the kinetic energy change of the steel ball (diameter 10mm, 4.1g), and the following is the test standard ballistic performance introduction: it is widely believed that the energy is conserved and the kinetic energy lost by the steel ball is equal to the dissipated energy of the sample. The energy dissipation (Ep) of the sample can be calculated by the following equation:
wherein Vi147.35m/s is the ball incident velocity, VrThe remaining speed of the steel ball is 2.89m/s, and the mass of the steel ball is 4.1g, which is the mass of the sample. The kinetic energy lost by the steel ball is equal to the energy dissipation of the hydrogel (E)p) The energy dissipation value of the hydrogel per unit mass is as high as 1.54J/g.
Example 6
FIG. 1 is a tensile stress-strain curve of an impact-resistant, high-strength physical hydrogel prepared in an ion salting-out agent of different valencies, and it can be seen that lithium salt has the strongest effect in forming a super-strong and super-tough gel. This is largely related to the solvating power and ion size of the metal salt ions, Li+The solvating power of the ion is highest (-3.01) and the radius is smallest (176 pm). In contrast, the solvating power of the other ions is lower (-2.71 Na)+,-2.92K+,-2.37Mg2+,-2.87Ca2 +) The ionic radius is larger (102 Na)+,138K+,72Mg2+And 100pm Ca2+). Generally, the metal salt ions with small ionic radius and monovalent charges can promote the diffusion in the gaps of the molecular chains of the salt ion polymer and reduce the obstacle of electrostatic action; on the other hand, more solvated metal ions can extract more free water molecules from the hydrogel.
Example 7
FIG. 2 shows that the mechanical properties of the impact-resistant physical hydrogel can be adjusted by adjusting the soaking time according to the mechanical properties of the physical hydrogel with different soaking times during the preparation process. Taking PVA/PAA (soft water gel) soaked in LiCl solution with the concentration of 12mol/L as an example, when the soaking time is prolonged from 0 hour to 24 hours, the mechanical property is obviously changed. The breaking stress increased from 75. + -. 2.36kPa to 13. + -. 1.8 MPa.
Example 8
The mechanical property test of the impact-resistant high-strength physical hydrogel prepared by soaking LiCl salts with different concentrations shows that the tensile strength of Gel-12M (PVA/PAA-12M LiCl) is 13MPa, which is 160 times higher than that of PVA/PAA hydrogel (82kPa), as shown in figure 3. The toughness is from 0.89 +/-0.02 MJ/m3(PVA/PAA hydrogel) increase was 48.97. + -. 5.52MJ/m3(Gel-12M hydrogel).
Example 9
Mechanical property testing of impact-resistant, high-strength physical hydrogels prepared with different ratios of PVA and PAA, FIG. 4 shows that PVA/PAA-LiCl hydrogels have a PVA and PAA ratio of 1:9 the PVA/PAA-LiCl hydrogel prepared shows more remarkable mechanical properties.
Example 10
As can be seen from FIG. 5, the mechanical properties of PVA/PAA-LiCl hydrogels prepared with initiator contents of 0.05 wt%, 0.1 wt% and 0.5 wt%, respectively, were relatively high. Particularly, when the initiator content is 0.5 wt%, the mechanical properties of the PVA/PAA-LiCl hydrogel are improved most obviously.
Example 11
In order to improve the energy consumption of the impact-resistant high-strength physical hydrogel and meet the requirements of the bulletproof field, SiO with different proportions is used2Nanoparticles (30 nm) were dispersed into the polymer network to prepare a gel composite. FIG. 6 shows that when the SiO is nano-sized2The content of the (b) is 3 percent, the tensile strength of the composite hydrogel material reaches 30.0MPa, the stretching length reaches 8 times of the original stretching length, and the corresponding energy dissipation is 102MJ/m3。
Example 12
In order to study the fracture energy of the impact-resistant high-strength physical hydrogel, the fracture energy of the gel after soaking in LiCl salt solutions of different concentrations was characterized. As can be seen from FIG. 7, the PVA/PAA-LiCl gel soaked in LiCl solution at a concentration of 12mol/L has an ultra-high breaking energy of 54860J/m2。
Example 13
The tensile stress-strain test results of the recovery properties of the impact resistant high strength physical hydrogel are shown in fig. 8. After various relaxation times, the recovery behavior of the stretched hydrogels was further tested. The second test started after 30 minutes and the sample returned almost to the original tensile stress.
Example 14
The tensile stress-strain test results for the self-healing properties of the impact resistant high strength physical hydrogel are shown in figure 9. Since hydrogen bond rupture repair is reversible, impact resistant, high strength physical hydrogels that are cut in half can self-heal and resist loading after self-healing. At room temperature, the two pieces of broken gel are recombined together and self-healing is not easy, probably because the high hardness of the material hinders the mobility of the polymer chains. However, the two pieces can be combined together to form a whole after being heated at 60 ℃ for 8 hours, and a considerable bearing capacity can be maintained. When the self-cured impact-resistant high-strength physical hydrogel is loaded to fracture, the fracture stress reaches 1.82 MPa.
Example 15
The compressive stress-strain results of impact-resistant high-strength physical hydrogels prepared by soaking different ratios of PVA and PAA with LiCl salt solution are shown in fig. 10, and the compressive modulus of the high-strength gel reaches MPa level, and the modulus increases with the increase of the PAA ratio.
Example 16
As can be seen from FIG. 11, the impact-resistant high-strength physical hydrogel prepared from PVA/PAA loses water rapidly and decreases in quality rapidly under the conditions of a temperature of 25 ℃ and a relative humidity of 30%. But the PVA/PAA-LiCl hydrogel sample remained of relatively stable quality. Calculating the mass ratio (W/W) of the hydrogel in the dehydration process0) The mass at time n is recorded using an electronic balance, and the water holding efficiency thereof is calculated.
W/W0Mass (hydrogel, time n)/Mass (hydrogel, time 0),
mass (hydrogel, time ═ 0) was calculated from the Mass of the raw materials used. In hydrogels, water molecules bound to ions must break chemical bonds to evaporate, while free water molecules evaporate naturally.
Example 17
Transparency test of impact-resistant high-strength physical hydrogel, FIG. 12 shows that a PVA/PAA soft film with a thickness of 2mm is soaked in the solution to shrink the soft film and gradually become more transparent, thereby forming a PVA/PAA-LiCl film with a thickness of 1.5 mm. It can be seen that the transmittance (T) of the PVA/PAA-LiCl gel is as high as 90% from 380nm to 720nm, significantly higher than that of the PVA/PAA hydrogel sample (83%).
Example 19
The scanning electron microscope test result of the impact-resistant high-strength physical hydrogel prepared by the invention is shown in figure 13, the gel surface forms a branch-shaped structure, and the infrared-atomic force microscope test result is combined, so that the impact-resistant high-strength physical hydrogel has a phase separation structure shown in figure 14.
As shown in fig. 15, an Atomic Force Microscope (AFM) with Infrared (IR) capability clearly distinguished the two samples. In particular, the topographic image of the hydrogel with added metal ions (FIG. B) corresponds well to those trunk branch structures observed from the SEM, indicating a non-uniform mixing of PAA (-COOH groups, white) and PVA (-OH groups, black). In contrast, no significant difference was shown in those images of the hydrogel without added metal ions (panel A), indicating that PAA (-COOH groups, white) and PVA (-OH groups, black) were homogeneously mixed. Additional evidence was found in the IR spectrum, in which the carbonyl group (C ═ O) of PAA in a hydrogel without added metal ions showed two intense oscillations (panel C), one at 1750cm-1The other is 1680cm-1Respectively, PAA in a PAA-rich area and PAA in a PVA-rich environment.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An impact-resistant high-strength physical hydrogel, the structure of which is a three-dimensional network formed by mutual crosslinking of a polymerizable charged monomer and a neutral high-molecular polymer, and the three-dimensional network structure contains metal ions.
2. The impact-resistant, high-strength physical hydrogel of claim 1, wherein said polymerizable charged monomer is selected from the group consisting of negatively charged monomers Acrylic Acid (AA), methacrylic acid (MAA), Sodium Styrene Sulfonate (SSS), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), and positively charged monomers dimethylaminoethylmethylammonium methacrylate (DMAEMA-MC), dimethylaminoethylmethylacrylate (DMAEAA-MC), diallyldimethylammonium chloride (DADMAC), dimethylaminopropylacrylamidomethylammonium chloride (DMAPMA-MC), dimethyldiallylammonium chloride (DMDAAC), diallyl-N-carboxybutoxymethylammonium chloride (DACBMAC), diallylmethylammonium chloride (DAMABC), diallylethylbenzylammonium chloride (DAEABC), methacryloyloxyethyltrimethylammonium chloride (DMC), Acryloyloxyethyltrimethylammonium Chloride (DAC), N-dimethyl-N-benzyl-acryloyloxyammonium chloride (DBAAC).
3. The impact-resistant, high-strength physical hydrogel of claim 1, wherein said neutral polymer is selected from the group consisting of polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO), and hyperbranched polyglycidyl ether (HPG), and said metal ion is selected from the group consisting of lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion, calcium ion, and iron ion.
4. A method for preparing an impact-resistant, high-strength physical hydrogel, comprising the steps of:
(a) firstly, adding an initiator into a solution containing charged monomers and neutral high molecular polymers, standing under an initiation condition, and freezing and melting to obtain primary hydrogel; (b) and (b) immersing the primary hydrogel obtained in the step a into a metal ion salt solution, and reacting to obtain the impact-resistant high-strength physical hydrogel.
5. The method for preparing an impact-resistant high-strength physical hydrogel according to claim 5, wherein the mass ratio of the charged monomer to the neutral high-molecular polymer is 9: 1-1: 9.
6. The method of claim 5, wherein the initiation is photoinitiated, thermally initiated, or radiation initiated.
7. The method of claim 5, wherein the metal ions are lithium, sodium, potassium, magnesium, aluminum, calcium, or iron ions; the metal ion concentration is 1-17mol/L or saturated salt solution, and the primary hydrogel is soaked in the metal ion solution for 1-24 hours.
8. A composite comprising the impact-resistant, high-strength physical hydrogel of claim 1.
9. Composite material according to claim 8, characterized in that another material component comprised is silica.
10. Use of the impact resistant high strength physical hydrogel of claim 1 in impact resistant materials, textiles and sensors.
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| CN115181313A (en) * | 2022-06-23 | 2022-10-14 | 南京水凝科技有限公司 | Multifunctional hydrogel sensor capable of being adhered in humid environment and preparation thereof |
| CN115181313B (en) * | 2022-06-23 | 2023-05-12 | 南京水凝科技有限公司 | Multifunctional hydrogel sensor capable of being adhered in humid environment and preparation thereof |
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