CN114163665B - Hydrogel capable of rapidly forming gel, preparation method and application thereof - Google Patents
Hydrogel capable of rapidly forming gel, preparation method and application thereof Download PDFInfo
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- CN114163665B CN114163665B CN202111591282.3A CN202111591282A CN114163665B CN 114163665 B CN114163665 B CN 114163665B CN 202111591282 A CN202111591282 A CN 202111591282A CN 114163665 B CN114163665 B CN 114163665B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims description 29
- 239000000499 gel Substances 0.000 title description 22
- 239000006249 magnetic particle Substances 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 56
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 29
- 229920001222 biopolymer Polymers 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 34
- 108010022355 Fibroins Proteins 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 13
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 13
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 241000255789 Bombyx mori Species 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
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- 239000006228 supernatant Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000005312 bioglass Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229940057527 ferric sodium citrate Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
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- DGPIGKCOQYBCJH-UHFFFAOYSA-M sodium;acetic acid;hydroxide Chemical compound O.[Na+].CC([O-])=O DGPIGKCOQYBCJH-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical class ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- CLOMYZFHNHFSIQ-UHFFFAOYSA-N clonixin Chemical compound CC1=C(Cl)C=CC=C1NC1=NC=CC=C1C(O)=O CLOMYZFHNHFSIQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002310 elbow joint Anatomy 0.000 description 1
- 238000013265 extended release Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- -1 higher than 197.3 °C Chemical compound 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- POZPMIFKBAEGSS-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;trihydrate Chemical compound O.O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O POZPMIFKBAEGSS-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- 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
- C08K7/00—Use of ingredients characterised by shape
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Medical Uses (AREA)
Abstract
The application provides a method for rapidly preparing functionalized hydrogel at room temperature, which is characterized by comprising the following steps: s1: providing magnetic particles, wherein the particle size of the magnetic particles is 50nm-1000nm; s2: providing titanium carbide nanoplatelets; s3: providing a biopolymer solution; s4: combining the magnetic particles with the titanium carbide nano-sheets to obtain a magnetic particle@titanium carbide composite; s5: adding polymer monomers into the biopolymer solution for mixing, and then sequentially adding inorganic salt and a stabilizer to obtain a first mixed solution; s6: mixing the magnetic particle@titanium carbide composite with the first mixed solution to obtain a second mixed solution; s7: and adding an initiator into the second mixed solution, standing at room temperature, and gelling to form hydrogel, wherein the molding time of the hydrogel is 7-1200 s.
Description
Technical Field
The application relates to the field of hydrogel materials, in particular to a multifunctional hydrogel capable of rapidly forming gel, a preparation method and application thereof.
Background
In recent years, hydrogels with biological tissue-like advantages have been the potential major materials for soft robotics, scalable optoelectronics, electronic skin and tissue engineering, and have been a major source of research for over ten years due to their epidermal compliance, programmable antifatigue, structural and functional adjustability. In the research aspect of the flexible electronic device of the hydrogel, the gravity center of the flexible electronic device is mainly concentrated on the improvement of the multifunctionality of the hydrogel, such as the performances of stretchability, freezing resistance, water retention, temperature sensitivity, shape memory, stimulus response, self-healing property and the like, so that the comprehensive performances of the flexible device, such as mechanics, sensing and the like, are improved. However, rapid, large-scale, ubiquitous preparation of hydrogels is of little interest. Considering that the batch preparation of the hydrogel is a necessary way for the industrialization of the flexible device of the hydrogel, under the drive of the traction and the technical development of the requirement, an additional filler is urgently needed to be searched, the rapid and large-scale preparation of the hydrogel is realized, the rapid and universal gel formation of various precursors is realized, and the multifunction is realized.
In recent years, rapid, large-scale, low-cost preparation of hydrogels has come into the spotlight. A rapid preparation method of a bioglass/hydrogel composite material is provided as in patent publication CN108578764a, and it is pointed out that the bioglass/hydrogel composite solution is crosslinked by adding a gel factor and stirred at room temperature for 1min to form a gel. The method has complex preparation process in the early stage, the rapid preparation method has no universality and the hydrogel has no versatility. In patent publication CN106492279a, a rapid preparation method of a silk fibroin-hyaluronic acid composite gel is provided, and the gel is obtained by adding cross-linking agents of carbodiimide and N-hydroxysuccinimide salt, further vacuumizing, and standing at room temperature for 20min. The process is complex, the speed is low, the additional cross-linking agent is added, and the gel has poor multifunctionality.
Disclosure of Invention
Based on the above, the application aims to provide a rapid preparation method of hydrogel by magnetic particles and titanium carbide nanosheets for synergistically mediating rapid gel formation, which has the advantages of simple process, low cost and capability of rapid preparation, and the prepared hydrogel has good conductivity, excellent flexibility and excellent mechanical properties, can be widely applied to flexible electronic fields such as robots, biomedicine and the like, and has wide application prospects. In addition, the preparation method can be expanded to the preparation of other functional hydrogels by free radical polymerization, so that the universality preparation of the hydrogels is realized, and a foundation is laid for the industrialization of the hydrogel flexible devices.
In order to achieve the above object, the present application provides a method for rapidly preparing a functionalized hydrogel at room temperature, comprising the following steps:
s1: providing magnetic particles, wherein the particle size of the magnetic particles is 50nm-1000nm;
s2: providing titanium carbide nanoplatelets;
s3: providing a biopolymer solution;
s4: combining the magnetic particles with the titanium carbide nano-sheets to obtain a magnetic particle@titanium carbide composite;
s5: adding polymer monomers into the biopolymer solution for mixing, and then sequentially adding inorganic salt and a stabilizer to obtain a first mixed solution;
s6: mixing the magnetic particle@titanium carbide composite with the first mixed solution to obtain a second mixed solution;
s7: and adding an initiator into the second mixed solution, standing at room temperature, and gelling to form hydrogel, wherein the molding time of the hydrogel is 7-1200 s.
In one embodiment, the magnetic particles are Fe 3 O 4 -COOH, said step S1 comprising:
s101: mixing ferric chloride hexahydrate and sodium citrate in ethylene glycol to obtain a first clarified liquid, wherein the ratio of the amount of sodium citrate to the amount of the ferric chloride hexahydrate is 1: 4-1: 2;
s102: adding a weakly basic reducing agent to the first clarified liquid to obtain a second clarified liquid, the ratio of the weakly basic reducing agent to the amount of ferric chloride hexahydrate material being 4:1 to 8:1, a step of;
s103: transferring the second transparent liquid into a reaction container, and obtaining a reaction liquid at 190-300 ℃;
s104: and extracting solid precipitate in the reaction liquid to obtain the magnetic particles.
In one embodiment, the weakly basic reducing agent is selected from at least one of sodium acetate, ammonium acetate, urea.
In one embodiment, the step S2 includes:
s201: adding titanium aluminum carbide powder into etching solution, uniformly mixing, reacting for 5-20 min at the rotation speed of 400-1000 rpm to obtain a third mixed solution, wherein the volume of the etching solution is 20-60 mL, and the mass of the titanium aluminum carbide is 1-3 mg;
s202: transferring the third mixed solution into a heater, condensing and refluxing at the temperature of 30-50 ℃, stirring at the speed of 100-600 rpm, and etching to obtain the titanium carbide solution.
In one embodiment, the biopolymer is a silk fibroin, and the step S3 includes:
s301: degumming silkworm cocoons in boiling sodium bicarbonate solution to obtain prefabricated silk fibroin fibers; the mass ratio of the sodium bicarbonate to the silkworm cocoons is 1: 2-2: 1, a step of;
s302: boiling the prefabricated silk fibroin fibers in boiling pure water for 10-30 minutes, taking out and wringing out to obtain silk fibroin fibers;
s303: dissolving the silk fibroin fibers in a lithium bromide solution with the concentration of 8-10M, and dissolving at the temperature of 50-65 ℃ for 30 min-8 h; obtaining a third transparent liquid;
s304: and dialyzing the third transparent liquid for 1-3 days.
In one embodiment, the mass ratio of the magnetic particles to the titanium carbide nanoplatelets is 1: 50-1: 2.
in one embodiment, the biopolymer solution is a silk fibroin solution, and the mass ratio of the biopolymer in the biopolymer solution to the polymer monomer is 1: 3-1: 10.
in one embodiment, the polymer monomer is one or more of acrylamide, acrylic acid, isopropyl acrylamide, and hydroxyethyl methacrylate.
In one embodiment, the inorganic salt is one or more of sodium chloride, lithium chloride, calcium chloride and zinc chloride, and the concentration of the inorganic salt in the first mixed solution is 1mg/mL to 5mg/mL.
In one embodiment, the stabilizer is one or more of sodium dodecyl sulfate and sodium dodecyl sulfonate, and the concentration of the stabilizer in the first mixed solution is 0.1 mg/mL-0.5 mg/mL.
In one embodiment, the initiator is ammonium persulfate, and the concentration of the initiator in the second mixed solution is 0.2 mg/mL-2 mg/mL.
In one embodiment, the step S4 includes:
s401: dispersing the magnetic particles in deionized water, and performing ultrasonic treatment at room temperature to obtain a magnetic particle dispersion liquid, wherein the ultrasonic power of the ultrasonic treatment is 100-300W, and the ultrasonic time is 1-30 min;
s402: dispersing the titanium carbide nano-sheets in deionized water, and performing ultrasonic treatment at room temperature to obtain titanium carbide nano-sheet dispersion liquid, wherein the ultrasonic power of the ultrasonic treatment is 100-300W, and the ultrasonic time is 10-60 min;
s403: adding the magnetic particle dispersion liquid into the titanium carbide nano-sheet dispersion liquid, uniformly mixing, and carrying out ultrasonic treatment at room temperature to obtain the magnetic particle@titanium carbide nano-sheet composite, wherein the ultrasonic power of the ultrasonic treatment is 100-300W, and the ultrasonic time is 5-60 min.
In another aspect of the application, a method of preparing a rapid prototyping hydrogel as described in any of the foregoing is claimed to obtain a rapid prototyping hydrogel.
In a further aspect of the application, the application of the aforementioned rapid prototyping hydrogels is claimed, the application areas of which include: biomedical, intelligent manufacturing, flexible electronics, and intelligent sensing.
According to the preparation method, the magnetic particles and the titanium carbide nanosheets cooperatively mediate the guiding agent to generate free radicals, so that the functional hydrogel can be rapidly prepared at room temperature, the preparation method is simple and rapid, the gel can be formed within 7-1200 s, the process cost is low, the prepared functional hydrogel has good conductivity and excellent mechanical properties, meanwhile, the functional hydrogel can be used as a strain sensor to sense 1-40% of strain, and tiny changes of different parts of a human body, such as finger bending, elbow bending and facial smile expression changes, can be monitored. The method for rapidly preparing the hydrogel at room temperature through the synergic mediation of the magnetic particles and the titanium carbide nanosheets is expected to be expanded to the preparation of other free radical polymerized hydrogels, realizes the large-scale preparation of the hydrogels, provides an important reference for the industrialized preparation of flexible hydrogel devices, and has wide application prospects in various fields such as biomedicine, intelligent manufacturing, flexible electronics, intelligent sensing and the like.
Drawings
The following describes the embodiments of the present application in further detail with reference to the accompanying drawings:
FIG. 1 is a schematic view showing a method for rapidly preparing a hydrogel at room temperature according to one embodiment of the present application;
FIG. 2 shows a scanning electron microscope image and a catalytic activity data image of the magnetic particles used in examples 1 to 5 of the present application;
FIG. 3 shows a scanning electron microscope image of titanium carbide nanoplatelets used in examples 1 to 5 of the present application;
FIG. 4 shows a scanning electron microscope image of the hydrogel of example 2 of the present application;
FIG. 5 is a photograph showing the preparation process of hydrogels of comparative examples 1, 2 and 3 according to the present application;
FIG. 6 is a graph showing gel formation time data of the rapid preparation of hydrogels of examples 1 to 5 of the present application;
FIGS. 7a and 7b show tensile test pictures and data for hydrogels prepared in examples 1 to 5 of the present application, respectively; FIGS. 7c and 7d show compression test pictures and data for hydrogels prepared in examples 1 to 5 of the present application, respectively;
FIG. 8 shows conductivity data graphs of functional hydrogels prepared according to examples 1 to 5 of the present application, wherein FIG. 8a is a graph of prepared hydrogels in series with LEDs and illuminating LED light bulbs, and FIG. 8b is a graph of conductivity data;
fig. 9a shows a graph of sensing data of embodiment 1 of the present application under a strain of 1% -40%, and fig. 9b shows a graph of data of embodiment 1 of the present application for monitoring changes in different parts of the human body.
Detailed Description
In order to clarify the application in more detail, a further explanation of the technical solution of the application will be provided below in connection with a preferred embodiment and a drawing.
As shown in fig. 1, the present application provides a method for rapidly preparing a functionalized hydrogel at room temperature, comprising the following steps:
s1: providing magnetic particles, wherein the particle size of the magnetic particles is 50nm-1000nm; s2: providing titanium carbide nanoplatelets; s3: providing a biopolymer solution; s4: combining the magnetic particles with the titanium carbide nanosheets (MXene) to obtain a magnetic particle@titanium carbide composite; s5: adding polymer monomers into the biopolymer solution for mixing, and then sequentially adding inorganic salt and a stabilizer to obtain a first mixed solution; s6: mixing the magnetic particle@titanium carbide composite with the first mixed solution to obtain a second mixed solution; s7: and adding an initiator into the second mixed solution, standing at room temperature for gelation to form hydrogel (named as FM@SF-PAAM), wherein the molding time of the hydrogel is 7-1200 s.
In some preferred embodiments, the above steps S1-S7 are performed in the order shown in FIG. 1. The preparation method can rapidly prepare the functional hydrogel at room temperature by a simple free radical polymerization method, the gel forming time of the hydrogel can be as low as 7 seconds, and the hydrogel has excellent mechanical properties and good conductivity, and has wide application prospects in various fields such as biomedicine, intelligent manufacturing, flexible electronics, intelligent sensing and the like.
In some preferred embodiments, the magnetic particles have a particle size of 50nm to 300nm.
Preferably, the magnetic particles are Fe 3 O 4 -COOH, fe in the present application 3 O 4 the-COOH may be a substance known in the art, or may be a substance prepared by known methods, and may be self-adjusting as desired by one skilled in the art, in some preferred embodiments, fe 3 O 4 -COOH is prepared by the steps of said step S1 preferably comprising:
s101: mixing ferric chloride hexahydrate and sodium citrate in ethylene glycol to obtain a first clarified liquid, wherein the ratio of the amount of sodium citrate to the amount of the ferric chloride hexahydrate is 1: 4-1: 2;
s102: adding a weakly basic reducing agent to the first clarified liquid to obtain a second clarified liquid, the ratio of the weakly basic reducing agent to the amount of ferric chloride hexahydrate material being 4:1 to 8:1, a step of;
s103: transferring the second transparent liquid into a reaction container, and obtaining a reaction liquid at 190-300 ℃;
s104: and extracting solid precipitate in the reaction liquid to obtain the magnetic particles.
In some more preferred embodiments, the steps S101 to S104 are sequentially performed in order.
It should be noted that in step S101, sodium citrate is selected to react with ferric chloride hexahydrate to increase the content of carboxylic acid in the product. Ethylene glycol is used as a solvent in a reaction system, provides a weak alkaline environment for the reaction, and is used as a reducing agent for the reaction.
In some preferred embodiments, the weakly basic reducing agent in step S102 is selected from sodium acetate, ammonium acetate, urea, further providing sufficient OH to the reaction system - The reduction reaction is further carried out to produce Fe 3 O 4 -COOH。
Preferably, the weakly basic reducing agent in step S102 may be selected from the group consisting of sodium acetate, and weakly basic salts of urea, and as such, these salts may be present as hydrated salts when added, for example sodium acetate may be sodium acetate monohydrate or sodium acetate trihydrate. More preferably, the ratio of the amount of weakly basic reducing agent to the amount of ferric chloride hexahydrate material in the second clarified liquid is 6:1.
preferably, the reaction temperature in step S103 is higher than the boiling point of ethylene glycol, i.e. higher than 197.3 ℃, so that the reaction temperature is preferably 200-240 ℃, and the reaction is performed for more than 15min within the temperature range to obtain a dark brown reaction solution, and at this time, the reaction solution is no longer clear and is dark brown, thus obtaining the magnetic particles. In order to obtain a sufficient reaction and to ensure the reaction, the reaction time in this step is preferably 30 to 60 minutes. And then separating the precipitate in the reaction liquid through step S104 to obtain the magnetic nano particles for standby.
In some preferred embodiments, the step of preparing the magnetic particles may further comprise S105: the solid precipitate is washed with at least two solvents. To obtain pure magnetic particles. Further preferably, the solid precipitate may be alternately washed with at least two solvents, for example, the solid precipitate is alternately washed with pure water and ethanol each at least 2 times. More preferably, each washing step may be performed by a centrifuge, and the magnetic particles may be placed in a centrifuge tube and centrifuged at 6000rpm to 14000rpm for 3min to 10 min. When the magnetic particles are Fe 3 O 4 When in use, the catalyst has better catalytic activity, and the interaction between groups can lead the magnetic particles and the nano-sheets to be better combined, have better compatibility with the biopolymer material and the polymer, and have better dispersibility in the liquid phase taking the polymer and the biopolymer solution as main bodies, so that the catalyst can be better played with smaller amount in the process of preparing the hydrogel, the hydrogel can be rapidly formed at room temperature without external heating or irradiation, and the good conductivity and mechanical property of the hydrogel are ensured.
The titanium carbide nano-sheets in the application can be known in the art or can be prepared by a known method, and can be self-adjusted according to the requirements of the person skilled in the art, and in some preferred embodiments, the titanium carbide nano-sheets are prepared by the following steps, namely, preferably, the step S2 comprises:
s201: adding titanium aluminum carbide powder into etching solution, uniformly mixing, reacting for 5-20 min at the rotation speed of 400-1000 rpm to obtain a third mixed solution, wherein the volume of the etching solution is 20-60 mL, and the mass of the titanium aluminum carbide is 1-3 mg;
s202: transferring the third mixed solution into a heater, condensing and refluxing at the temperature of 30-50 ℃, stirring at the speed of 100-600 rpm, and etching to obtain the titanium carbide solution.
Further preferably, step S2 further comprises washing and dispersing the product, in particular step S203: transferring the titanium carbide solution into a centrifuge tube, centrifuging at 3000 rpm-5000 rpm for 3 min-15 min, pouring out supernatant, dispersing the precipitate with deionized water, centrifuging and washing for 5-10 times until the supernatant becomes neutral, wherein the pH value is 6.5-pH 7.5, and the precipitate at the moment is the titanium carbide material; s204: dispersing the titanium carbide material in deionized water, carrying out ultrasonic stripping, wherein the ultrasonic power is 150-300W, the ultrasonic time is 10-60 min, and the vacuum drying is carried out at the vacuum degree of 1-5 Pa and the temperature is-30-50 ℃ to obtain the single-layer titanium carbide nano-sheet.
Preferably, the etching solution is hydrogen fluoride solution or mixed solution of lithium fluoride and hydrochloric acid; more preferably, the etching solution is a mixed solution of lithium fluoride and hydrochloric acid, further preferably, the concentration of the hydrochloric acid solution is 8-10M, the mass of the lithium fluoride is 3-6 g, and even more preferably, after the lithium fluoride is added into the hydrochloric acid solution, the stirring and mixing time is 5-20 min in order to obtain a sufficient reaction and ensure the reaction.
Preferably, the biopolymer is a silk fibroin, and the biopolymer in the present application may be a substance known in the art, or may be a substance prepared by a known method, and may be self-adjusted according to the needs of those skilled in the art, and in some preferred embodiments, the biopolymer is prepared by the following steps, that is, step S3 may further include the following steps:
s301: degumming silkworm cocoons in boiling sodium bicarbonate solution to obtain prefabricated silk fibroin fibers; the mass ratio of the sodium bicarbonate to the silkworm cocoons is 1: 2-2: 1, a step of;
s302: boiling the prefabricated silk fibroin fibers in boiling pure water for 10-30 minutes, taking out and wringing out to obtain silk fibroin fibers;
s303: dissolving the silk fibroin fibers in a lithium bromide solution with the concentration of 8-10M, and dissolving at the temperature of 50-65 ℃ for 30 min-8 h; obtaining a third transparent liquid;
s304: and dialyzing the third transparent liquid for 1-3 days.
Preferably, the mass ratio of the magnetic particles to the titanium carbide nano-sheets is 1: 50-1: 2.
preferably, the step S4 includes:
s401: dispersing the magnetic particles in deionized water, and obtaining a magnetic particle dispersion liquid at the temperature of 20-30 ℃ with ultrasonic power of 150-300W and ultrasonic time of 10-60 min;
s402: dispersing the titanium carbide nano-sheets in deionized water, and obtaining titanium carbide nano-sheet dispersion liquid at the temperature of 20-30 ℃ with ultrasonic power of 150-300W and ultrasonic time of 10-60 min;
s403: adding the magnetic particle dispersion liquid into the titanium carbide nano-sheet dispersion liquid, uniformly mixing, and obtaining the magnetic particle@titanium carbide nano-sheet compound at the temperature of 20-30 ℃ under the ultrasonic power of 150-300W and the ultrasonic time of 10-60 min.
Preferably, the polymer monomer is one or more of acrylamide, acrylic acid, isopropyl acrylamide and hydroxyethyl methacrylate. Likewise, preferably, the biopolymer solution is a silk fibroin solution, and the mass ratio of silk fibroin in the silk fibroin solution to the polymer monomer is 1: 3-1: 10, more preferably, the mass ratio of the silk fibroin to the polymer monomer is 1:6.25.
preferably, the polymer monomer is one or more of acrylamide, acrylic acid, isopropyl acrylamide and hydroxyethyl methacrylate; more preferably, the polymer monomer is polyacrylamide.
Preferably, the inorganic salt is one or more of sodium chloride, lithium chloride, calcium chloride and zinc chloride, more preferably, the inorganic salt is calcium chloride, and even more preferably, the inorganic salt is added in a mass of 5 mg-20 mg.
Preferably, the stabilizer is one or more of sodium dodecyl sulfate and sodium dodecyl sulfonate, more preferably, the stabilizer is sodium dodecyl sulfate, and even more preferably, the mass of the stabilizer is 1 mg-5 mg.
Preferably, the initiator is ammonium persulfate, and the mass of the initiator is 2 mg-15 mg.
Preferably, the preparation process may further comprise:
s8, step: and (3) reacting for 7-1200 s at room temperature, and cleaning the residual solvent on the surface of the sample by using deionized water to obtain the functionalized hydrogel.
The functionalized hydrogel rapidly prepared at room temperature by the above method comprises: magnetic particles, titanium carbide nano-sheets, biological macromolecules, polymer monomers, inorganic salts and stabilizers; the magnetic particles, the titanium carbide nano-sheets, the polymer monomer, the inorganic salt and the stabilizer are dispersed in the biopolymer; the particle size of the magnetic particles is 50nm-1000nm, and the mass ratio of the magnetic particles to the titanium carbide nano-sheets is 1: 50-1: 2; the mass ratio of the biopolymer to the polymer monomer is 1: 3-1: 10; the functional hydrogel can be rapidly glued within 7-1200 s at room temperature, does not need additional heating or irradiation, has good conductivity and mechanical property, can be used as a strain sensor, senses 1-40% strain, and monitors the changes of different parts of a human body. By Fe 3 O 4 The method for preparing the hydrogel by the free radical polymerization method with MXene synergistic catalysis has the advantages of simplicity, rapidness and low cost, is expected to be expanded to the preparation of other functional hydrogels by free radical polymerization, has universality, is expected to be prepared in a large area, lays a foundation for industrialization of functional hydrogel flexible devices, and has wide application value.
The method for rapidly preparing functionalized hydrogels at room temperature in the present application is further described below with reference to the examples:
example 1
1.35g of ferric chloride hexahydrate (FeCl) 3 ·6H 2 O) and 0.5882g of trisodium citrate trihydrate (NaCt) 3 ·3H 2 O) adding 40mL ethylene glycol, ultrasonic treatment for 5min, so that ferric chloride is completely dissolved, and stirring and reacting for 1h to obtain yellow first clear solution; next, 3.9813g of sodium acetate monohydrate was added to the above-mentioned first clear solution, and strong stirring was continued for 30 minutes, to obtain a brown second mixed solution. And transferring the second mixed solution into a sealed hydrothermal reaction kettle, reacting for 12 hours at 200 ℃, naturally cooling to room temperature after the reaction is finished to obtain a dark brown precipitate product, performing magnetic separation on the reacted reaction solution by using a magnetic frame to remove supernatant, and continuously performing alternating magnetic separation and washing on the obtained dark brown precipitate for at least 3 times by using pure water and ethanol. Drying the obtained brown precipitate sample in vacuum freeze drying oven, and finally obtaining brown powder which is Fe 3 O 4 -COOH。
4.8g of LiF was added to 60mL of a 9M hydrochloric acid solution, and the mixture was stirred at room temperature for 10 minutes to obtain an etching solution. Then slowly add 3g of Ti 3 AlC 2 The powder was added to the etching solution, and the reaction was stirred at 35℃for 24 hours. After the reaction is finished, a black reactant is obtained, the obtained black reaction product is centrifuged at 350 rpm for 5min, the supernatant is poured off, and the precipitate is repeatedly centrifugally washed with deionized water for 5-6 times until the pH of the supernatant is neutral. And then dispersing the precipitate with pure water, carrying out ultrasonic stripping for 30min under the ultrasonic power of 250W, and finally, drying by a vacuum freeze drying box to obtain stripped MXene powder, and storing in a refrigerator at the temperature of 4 ℃ for later experiments.
Taking 30g of purchased cocoons, shearing the cocoons, putting the cocoons into 2.5L of sodium bicarbonate boiling water containing 30g, boiling for 30min, taking out the cocoons, wringing the cocoons, and washing and wringing the cocoons by using ultrapure water; the above steps are repeated at least 3 times. Then, the sodium bicarbonate was changed to ultrapure water, and the boiling was repeated three times as well to suck the residual sodium bicarbonate, and then the wrung sample was put into a 40 ℃ oven overnight to obtain silk fibroin fiber. 7g of the obtained silk fibroin fiber is taken and added into 49mL of newly prepared 9.3M lithium bromide (LiBr) aqueous solution for dissolution, the solution is kept stand for 1h at 60 ℃ to obtain pale yellow transparent solution, the obtained solution is transferred into a dialysis bag with molecular retention of 3500kDa for 3 days of dialysis to remove the lithium bromide, and finally 5wt% SF solution is obtained.
30mg of MXAdding ene into 1mL of ultrapure water, performing ultrasonic treatment for 30min under the ultrasonic power of 250W to obtain MXene dispersion liquid, and simultaneously taking 2mg of Fe 3 O 4 adding-COOH into 0.2mL of ultra-pure water, and performing ultrasonic treatment at ultrasonic power of 250W for 10min to obtain Fe 3 O 4 -COOH dispersion, to obtain Fe 3 O 4 Adding the-COOH dispersion into the MXene dispersion, and performing ultrasonic treatment for 10min under the ultrasonic power of 250W to obtain uniformly dispersed Fe 3 O 4 @ MXene complex. Next, 2.5g of acrylamide was added to 4mL of a 5wt% SF solution and mixed uniformly, then 0.1mL of 0.1g/mL of calcium chloride and 0.1mL of 0.01g/mL of sodium dodecyl sulfate were added to the above mixed solution, and after mixing uniformly, fe was added 3 O 4 The @ MXene complex is uniformly mixed to obtain a hydrogel precursor solution. Finally, 0.5mL of ammonium persulfate with the concentration of 0.014g/mL is added into the precursor liquid, and after being quickly and uniformly mixed, the precursor liquid is stood at room temperature without additional heating, ultraviolet or infrared exposure to autonomously complete the gelation process. Finally, washing the obtained hydrogel with a large amount of deionized water to remove unreacted chemical substances and obtain Fe 3 O 4 @ MXene @ SF-PAAM hydrogel, noted F2M30.
Example 2
Example 2 differs from example 1 only in that the mass of the MXene used is 50mg and the sample is designated F2M50.
Example 3
Example 3 differs from example 1 only in that the mass of the MXene used is 100mg and the sample is designated F2M100.
Example 4
Example 4 differs from example 1 only in that Fe was used 3 O 4 The mass of-COOH was 5mg, and the sample was designated F5M30.
Example 5
Example 5 differs from example 1 only in that Fe was used 3 O 4 The mass of-COOH was 10mg, and the sample was designated F10M30.
Example 6
The catalytic activity of the magnetic particles used in examples 1 to 5 was tested: taking 2 mu L concentrationFe of 1mg/mL 3 O 4 Nanoparticle addition to 100. Mu.L TMB/H 2 O 2 In the substrate solution, after the reaction is finished, the reaction is stopped by magnetic separation, 50 mu L of HCl with the concentration of 1M is added into the supernatant, and then the absorbance at 450nm is measured by an enzyme-labeled instrument.
Comparative example 1
Comparative example 1 differs from example 1 only in that Fe was not used 3 O 4 -COOH and MXene, samples named SF-PAAM.
Comparative example 2
Comparative example 2 differs from example 1 only in that Fe was not used 3 O 4 -COOH, sample designated F0M30.
Comparative example 3
Comparative example 3 differs from example 1 only in that MXene was not used and the sample was designated F2M0.
Comparative example 4
Comparative example 4 differs from example 6 only in that no magnetic particles are used.
Fig. 2a and 2b show scanning electron microscopy images and catalytic activity data of the magnetic particles described in examples 1 to 5, and it can be seen that the magnetic particles are uniformly dispersed, have uniform sizes, and have an average particle diameter of about 160 nm. Meanwhile, the magnetic particles have catalytic activity and can be used in H 2 O 2 In the presence of the catalytic substrate 3,3', 5' -Tetramethylbenzidine (TMB) turns from colorless to blue.
Fig. 3 shows scanning electron microscope images of the etched multi-layered titanium carbide nanoplatelets described in examples 1 to 5, and it can be seen that the titanium carbide nanoplatelets have a layered structure.
The surface morphology of the hydrogel of fig. 4 shows that the hydrogel has a cellular porous structure, and the magnetic particles and the titanium carbide nano-sheets do not have obvious accumulation, which indicates that the magnetic particles and the titanium carbide nano-sheets are uniformly dispersed in the hydrogel.
The thermal profile of the FM@SF-PAAM hydrogel during gelation was captured in real time using a hand-held thermal infrared imager to understand the rapid gelation process. By comparing temperature change with reaction time, e.g. by curve formationFIG. 5 is a graph showing the gel forming rate data of the hydrogels of examples 1 to 5, and it can be seen that the polymerization process occurs rapidly and releases a large amount of heat with Fe 3 O 4 An increase in the content of-COOH or MXene, the shorter the time to reach the maximum temperature, indicating Fe 3 O 4 both-COOH and MXene have promotion effect on gel formation, and both the gel formation speed of the hydrogel can be increased, and the gel formation time can be shortened.
FIG. 6 shows a picture of the gelling process of comparative example 1, comparative example 2 and comparative example 3, it can be seen that there is no Fe 3 O 4 Under the conditions of-COOH and MXene, the gel formation started on the third day and required 2 days of complete gel formation. In the presence of Fe alone 3 O 4 Hydrogels also do not gel rapidly under the conditions of-COOH or MXene, but gel after 2 days, forming heterogeneous gels, which indicate Fe 3 O 4 -COOH and MXene have a promoting effect on the gelling.
Referring to national standards, mechanical tensile experiments and compression experiments are carried out on samples F2M30, F2M50, F2M100, F5M30 and F10M30 by a universal tester. Fig. 7a shows a mechanical tensile photograph of the hydrogel of example 2, and fig. 7b shows mechanical tensile stress-strain data graphs of the hydrogels of examples 1 to 5, and it can be seen that the prepared hydrogels have better tensile properties with tensile strain ranging from 803% to 1660%. Fig. 7c shows a mechanical compression photograph of the hydrogel of example 2, and fig. 7d shows a mechanical compression stress-strain data graph of the hydrogels of examples 1 to 5, and it can be seen that the prepared hydrogels have better compressibility, the hydrogels are not crushed and can be recovered even under the condition that the compression strain is 70% and the compression strength is about 500KPa, and the inventors found that the hydrogels remain intact even after the compression strain is increased to 90% and can be recovered to the original shape after the external force is released by continuously increasing the compression strain to the hydrogels. These results show that the prepared hydrogel samples have excellent flexibility and mechanical properties.
Fig. 8a shows a conductivity picture of the hydrogel of example 2, fig. 8b shows conductivity data graphs of the hydrogels of examples 1 to 5, the conductivities being calculated according to formula (1):
wherein R (Ω) represents the resistance of the hydrogel sample, S (cm) 2 ) And l (cm) are the cross-sectional area and length of the sample (l is also the length between two adjacent electrodes), respectively. The application of 3V dc voltage to the circuit shown in fig. 7a shows that the obtained hydrogel can be used as a wire and an LED lamp to form a simple loop, so that the LED is lighted, and the conductivity is 0.04S/m to 0.06S/m, which indicates that the obtained hydrogel has good conductivity.
The hydrogel is applied to strain sensing in view of excellent tensile elongation and good conductivity of the prepared hydrogel. FIG. 9a shows a graph of strain sensing data for the hydrogel of example 2 showing ΔR/R in a continuous cycle tensile test 0 Evolution of the signal, the maximum strain increases gradually from 1% to 40%. DeltaR/R 0 The signal intensity varies non-negligibly and shows a reversible and repeatable ΔR/R over 5 uninterrupted extended release periods 0 A signal. These results indicate that current fm@sf-PAAM hydrogels have high sensitivity and reliability for a wide range of strain sensing. Thus, the sensor is designed to further serve as a wearable sensor for monitoring complex human movements. In these experiments, the hydrogel was cut into thin sheets and attached to the body of the volunteer. The hydrogel sensor of example 1, shown in FIGS. 9b and 9c, produces a pronounced and reversible ΔR/R with repeated flexion-release movements of the finger, elbow joint, respectively 0 A signal. Likewise, the hydrogel was glued to the volunteer's cheek and smiles were made as shown in fig. 9d, with the rate of change of the hydrogel all showing periodic signs. The results show that the obtained FM@SF-PAAM hydrogel can rapidly and stably monitor different signals, and has potential application prospects in various flexible electronic fields such as robots, biomedicine and the like.
The room temperature Fe proposed in the present application 3 O 4 Medium @ MXeneThe rapid preparation method of the functionalized hydrogel can be expanded to the preparation of other functionalized hydrogels polymerized by free radicals, and the prepared functionalized hydrogel can be widely applied to the fields of flexible electronic devices such as strain sensing, medical health monitoring and the like.
Finally, it should be noted that: the foregoing examples are merely illustrative of the present application and are not intended to limit the embodiments of the present application, and it should be understood by those skilled in the art that the technical features of the foregoing embodiments may be combined in any desired manner, and other modifications and equivalent substitutions of some technical features may be made on the basis of the specific embodiments, and thus, it is not intended to be exhaustive of all embodiments, and all modifications, improvements, equivalent substitutions and the like which belong to the technical scope of the present application are included in the spirit and principle of the present application.
Claims (12)
1. The preparation method of the quick-setting hydrogel is characterized by comprising the following steps of:
s1: providing magnetic particles with a particle size of 50nm-1000nm, wherein the magnetic particles are Fe 3 O 4 -COOH, said step S1 comprising:
s101: mixing ferric chloride hexahydrate with sodium citrate in ethylene glycol to obtain a first clarified liquid, wherein the ratio of the amount of sodium citrate to the amount of the ferric chloride hexahydrate is 1: 4-1: 2;
s102: adding a weakly basic reducing agent to the first clarified liquid to obtain a second clarified liquid, the ratio of the weakly basic reducing agent to the amount of ferric chloride hexahydrate material being 4:1 to 8:1, a step of;
s103: transferring the second clarified liquid into a reaction vessel, and obtaining reaction liquid at 190-300 ℃;
s104: extracting solid precipitate in the reaction liquid to obtain the magnetic particles;
s2: providing titanium carbide nanoplatelets;
s3: providing a biopolymer solution, wherein the biopolymer is silk fibroin;
s4: combining the magnetic particles with the titanium carbide nano-sheets to obtain a magnetic particle@titanium carbide composite;
s5: adding a polymer monomer into the biopolymer solution for mixing, wherein the polymer monomer is one or more of acrylamide, acrylic acid, isopropyl acrylamide and hydroxyethyl methacrylate, and then sequentially adding inorganic salt and a stabilizer to obtain a first mixed solution;
s6: mixing the magnetic particle@titanium carbide composite with the first mixed solution to obtain a second mixed solution;
s7: and adding an initiator into the second mixed solution, standing at room temperature, and gelling to form hydrogel, wherein the molding time of the hydrogel is 7-1200 s.
2. The method for preparing a rapidly gelling hydrogel according to claim 1, wherein the weakly basic reducing agent is at least one selected from sodium acetate, ammonium acetate and urea.
3. The method for preparing a rapid prototyping hydrogel according to claim 1, wherein the step S2 comprises:
s201: adding titanium aluminum carbide powder into etching solution, uniformly mixing, reacting for 5-20 min at the rotation speed of 400-1000 rpm to obtain a third mixed solution, wherein the volume of the etching solution is 20-60 mL, and the mass of the titanium aluminum carbide is 1-3 mg;
s202: transferring the third mixed solution into a heater, condensing and refluxing at the temperature of 30-50 ℃, stirring at the speed of 100-600 rpm, and etching to obtain the titanium carbide solution.
4. The method for preparing a rapid prototyping hydrogel according to claim 1, wherein the step S3 comprises:
s301: degumming silkworm cocoons in boiling sodium bicarbonate solution to obtain prefabricated silk fibroin fibers; the mass ratio of the sodium bicarbonate to the silkworm cocoons is 1: 2-2: 1, a step of;
s302: boiling the prefabricated silk fibroin fibers in boiling pure water for 10-30 minutes, taking out and wringing out to obtain silk fibroin fibers;
s303: dissolving the silk fibroin fibers in a lithium bromide solution with the concentration of 8-10M, and dissolving at the temperature of 50-65 ℃ for 30 min-8 h; obtaining a third transparent liquid;
s304: and dialyzing the third transparent liquid for 1-3 days.
5. The method for preparing the rapidly gelling hydrogel according to claim 1, wherein the mass ratio of the magnetic particles to the titanium carbide nanoplatelets is 1: 50-1: 2.
6. the method for preparing a rapidly gelling hydrogel according to claim 1, wherein the biopolymer solution is a silk fibroin solution, and the mass ratio of the biopolymer in the biopolymer solution to the polymer monomer is 1: 3-1: 10.
7. the method for preparing the rapid prototyping hydrogel according to claim 1, wherein the inorganic salt is one or more of sodium chloride, lithium chloride, calcium chloride and zinc chloride, and the concentration of the inorganic salt in the first mixed solution is 1mg/mL to 5mg/mL.
8. The method for preparing the rapidly gelling hydrogel according to claim 1, wherein the stabilizer is one or more of sodium dodecyl sulfate and sodium dodecyl sulfonate, and the concentration of the stabilizer in the first mixed solution is 0.1mg/mL to 0.5mg/mL.
9. The method for preparing the rapidly-forming hydrogel according to claim 1, wherein the initiator is ammonium persulfate, and the concentration of the initiator in the second mixed solution is 0.2mg/mL to 2mg/mL.
10. The method for preparing a rapid prototyping hydrogel according to claim 1, wherein the step S4 comprises:
s401: dispersing the magnetic particles in deionized water, and performing ultrasonic treatment at room temperature to obtain a magnetic particle dispersion liquid, wherein the ultrasonic power of the ultrasonic treatment is 100-300W, and the ultrasonic time is 1-30 min;
s402: dispersing the titanium carbide nano-sheets in deionized water, and performing ultrasonic treatment at room temperature to obtain titanium carbide nano-sheet dispersion liquid, wherein the ultrasonic power of the ultrasonic treatment is 100-300W, and the ultrasonic time is 10-60 min;
s403: adding the magnetic particle dispersion liquid into the titanium carbide nano-sheet dispersion liquid, uniformly mixing, and carrying out ultrasonic treatment at room temperature to obtain the magnetic particle@titanium carbide nano-sheet composite, wherein the ultrasonic power of the ultrasonic treatment is 100-300W, and the ultrasonic time is 5-60 min.
11. A rapid prototyping hydrogel, characterized in that it is obtained by the method for preparing a rapid prototyping hydrogel according to any one of claims 1 to 10.
12. Use of the rapid prototyping hydrogel according to claim 11, characterized in that the application areas are: intelligent manufacturing, flexible electronics and intelligent sensing.
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