CN114015075B - Preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation - Google Patents
Preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 138
- 239000001913 cellulose Substances 0.000 title claims abstract description 138
- 239000000017 hydrogel Substances 0.000 title claims abstract description 110
- 238000001338 self-assembly Methods 0.000 title claims abstract description 78
- 230000033228 biological regulation Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 52
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000000977 initiatory effect Effects 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims description 110
- 239000000243 solution Substances 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 18
- -1 N-dimethylacrylamide Chemical compound 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 230000001939 inductive effect Effects 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 238000007605 air drying Methods 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 238000003892 spreading Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 8
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 8
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
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- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 claims description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 2
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- XIYUIMLQTKODPS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CC[N+]=1C=CN(C)C=1 XIYUIMLQTKODPS-UHFFFAOYSA-M 0.000 claims 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- 229920000875 Dissolving pulp Polymers 0.000 abstract 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003938 response to stress Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
Abstract
The invention discloses a preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation and control, and belongs to the technical field of hydrogel preparation. Dissolving cellulose in the ionic liquid, and heating to dissolve to obtain cellulose-ionic liquid solution; the cellulose solution is subjected to moisture-induced self-assembly to obtain cellulose gel; and (3) immersing the cellulose gel in an acrylamide solution containing a photoinitiator for treatment, and then initiating polymerization by ultraviolet irradiation to obtain the tough and transparent hydrogel. The invention provides the self-assembly behavior of the cellulose induced by the water, so that the mechanical property of the hydrogel can be regulated and controlled, the problem that the strength, the stretching and the toughness cannot be taken into consideration in the traditional hydrogel strengthening and toughening strategy is solved, and the ionic liquid in the system also enables the hydrogel to have good mechanical property and conductivity at the same time, so that the hydrogel is expected to be applied to the fields of flexible wearable equipment and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogel preparation, and particularly relates to a preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation.
Background
The hydrogel is a material containing water and having a three-dimensional cross-linked network, has soft and wet characteristics, and has wide application prospects in various fields of biomedicine, water treatment, wearable electronic equipment and the like. However, the homogeneous structure of hydrogels on the one hand makes them lack crosslinking, and on the other hand, the high water content results in low solids content, etc., which make them lack mechanical properties, which limits their application range to some extent.
Currently, there are many methods in literature report for designing hydrogels to improve their strength and toughness, such as designing dual networks, designing physical-chemical hybrid crosslinks, introducing slip crosslinkers, designing highly oriented hierarchies, and introducing strong/weak fibers to build composite networks, etc. However, the improvement of mechanical properties by the above method is limited. In addition, the increase in strength of hydrogels tends to sacrifice their toughness and vice versa. It is a great challenge to compromise the strength, strain and toughness of hydrogels.
As the most abundant natural polysaccharide on earth, cellulose is widely used in the fields of preparing biocompatible and biodegradable materials, etc. With the sequential development and application of a series of cellulose solvents including ionic liquids, alkali/urea aqueous systems, and N-methylmorpholine-N-oxide, the construction of hydrogels based on cellulose has also become a current focus of research. Cellulose is first dissolved by a solvent, then regenerated with ethanol or water, and then cellulose hydrogels having different structures and properties are one of the strategies currently in wide use. However, hydrogels prepared from regenerated cellulose tend to have poor light transmission properties, which limits their application in wearable devices and the like to some extent.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation, and the method induces the self-assembly behavior of cellulose through moisture, so that the mechanical property of the hydrogel can be regulated, the problem that the strength, the stretching and the toughness cannot be taken into consideration in the traditional hydrogel strengthening and toughening strategy is solved, and the existence of ionic liquid in a system enables the hydrogel to have good mechanical property and conductivity at the same time, so that the hydrogel is expected to be used in the fields of flexible wearable equipment and the like.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the dried cellulose in the step 1) with an ionic liquid, and heating and dissolving to obtain a cellulose-ionic liquid mixed solution;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, and inducing cellulose self-assembly in an environment with certain humidity through moisture to obtain cellulose gel;
4) Mixing a monomer, a crosslinking agent and a photoinitiator, and fully dissolving to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking liquid prepared in the step 4);
6) And (3) after soaking, weighing back the soaking solution, and polymerizing under the initiation of ultraviolet light to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation comprises the steps that the ionic liquid is any one of 1-butyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole bromide salt, 1-ethyl-3-methylimidazole bromide salt, 1-allyl-3-methylimidazole chloride salt or 1-ethyl-3-methylimidazole acetate, and the ionic liquid is salt composed of anions and cations; the temperature of heating and dissolving is 60-150 ℃ and the dissolving time is 6-72 h; the mass fraction of the cellulose in the cellulose-ionic liquid mixed solution is 0.5-15 wt%.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the ionic liquid is 1-butyl-3-methylimidazole chloride or 1-ethyl-3-methylimidazole acetate; the temperature of the cellulose is 80-110 ℃ and the dissolution time is 24-60 h; the mass fraction of the cellulose in the cellulose-ionic liquid mixed solution is 2.5-10wt%.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the environmental humidity induced by water is 5-95% RH, and the self-assembly induction time is 2-48 h.
The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation comprises the following steps that the moisture-induced environmental humidity is 50-90% RH; the time for self-assembly of the cellulose by the water induction is 6-24 hours.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the monomer is any one of acrylic acid, acrylamide, methacrylic acid, methacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-vinylcaprolactam, hydroxyethyl acrylate or hydroxyethyl methacrylate, and the monomers can form a polymer network; the cross-linking agent is N, N' -methylene bisacrylamide or polyethylene glycol diacrylate, and the cross-linking agent is a molecule capable of being cross-linked to form a network structure; the photoinitiator is any one of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide or 1-hydroxycyclohexyl phenyl ketone, and can release free radical molecules.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the monomer is acrylamide, the cross-linking agent is N, N' -methylene bisacrylamide, and the photoinitiator is 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the concentration of the monomer is 2.8-11.2 mol/L, the addition amount of the crosslinking agent is 0.07-1.12 wt/percent of the mass of the monomer, and the addition amount of the photoinitiator is 0.15-2.7 wt% of the mass of the monomer.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the concentration of the monomer is 5.6-8.4 mol/L, and the addition amounts of the crosslinking agent and the photoinitiator are 0.14-0.84 wt% and 0.45-1.35 wt% of the monomer respectively.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the mass ratio of the soaking solution to the cellulose gel is 0.5:1-5:1, and the soaking time is 6-48 h.
According to the preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation, the mass ratio of the soaking solution to the cellulose gel is 1.5:1-4.5:1; the soaking time is 24-48 h.
The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation is characterized in that the mass ratio of the soaking liquid to the soaking liquid used for soaking is 4.8:100-47.7:100.
The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation is characterized in that the mass ratio of the soaking liquid to the soaking liquid used for soaking is 14.3:100-42.9:100.
The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation has the ultraviolet power of 6-48W and the polymerization time initiated by ultraviolet light of 0.5-2 h.
The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation and control has the ultraviolet power of 36W; the polymerization time initiated by ultraviolet light is 1-2 h.
The beneficial effects are that: compared with the prior art, the invention has the advantages that:
(1) The self-assembly behavior of cellulose is induced by water to form a cellulose skeleton, so that the strength of the hydrogel is provided.
(2) The invention can regulate and control the mechanical property of the hydrogel by inducing the self-assembly behavior of cellulose through moisture.
(3) The invention uses acrylamide as elastic matrix to form strong hydrogen bond connection with cellulose skeleton, which provides flexibility for hydrogel.
(4) The existence of the ionic liquid in the system can not only improve the mechanical property and the transparency of the hydrogel, but also provide conductivity for the hydrogel.
(5) Compared with common hydrogel, the hydrogel disclosed by the invention has the advantages of high strength, high toughness and good stretchability.
(6) The hydrogel provided by the invention has good mechanical properties and transparency, and is expected to be used in the fields of wearable electronic equipment and the like.
Drawings
FIG. 1 is an XRD pattern of cellulose and cellulose gel of example 1;
FIG. 2 is an SEM image of the hydrogel obtained in example 1;
FIG. 3 is a stress response curve of the hydrogel obtained in example 1;
FIG. 4 shows the electrical conductivity of the hydrogels obtained in example 1;
FIG. 5 is a graph showing the light transmittance of the hydrogel obtained in example 1;
FIG. 6 is a stress-strain curve of the hydrogel obtained in example 1 at 150% strain for 300 cycles of stretching.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-butyl-3-methyl-imidazole chloride ([ BMim ] Cl) ionic liquid, and heating to 110 ℃ to dissolve for 36h to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 7.5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 90% RH for 12 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) 8.4mol/L acrylamide, N' -methylene bisacrylamide with the mass fraction of 0.28wt% and 0.90wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone are mixed and stirred to be fully dissolved, so as to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 36 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 1.5:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 14.3:100, and polymerizing for 1h under the initiation of ultraviolet light with the power of 36W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
Fig. 1 shows XRD patterns of cellulose and cellulose gel, and as can be seen from fig. 1, the crystal structure of cellulose changes from form i to form ii after dissolution in an ionic liquid. Fig. 2 is an SEM image of the hydrogel, and as can be seen from fig. 2, the microstructure of the hydrogel is dense. Fig. 3 shows stress response curves of the hydrogel, and as can be seen from fig. 3, the hydrogel has good mechanical properties, the tensile strain of the hydrogel can reach 1291%, and the tensile strength of the hydrogel can reach 2.3MPa. Fig. 4 shows the conductivity of the hydrogel, and as can be seen from fig. 4, the hydrogel has good conductivity, and the conductivity is 1.58S/m. Fig. 5 shows the light transmittance curve of the hydrogel, and as can be seen from fig. 5, the hydrogel has good transparency, and the light transmittance at 600nm is 86%. Fig. 6 is a stress-strain curve of a hydrogel stretched 300 times at 150% strain, and as can be seen from fig. 6, the hydrogel has good cycling stability, and the strain remains substantially stable after 300 times of cycling at 150% strain.
Example 2
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-butyl-3-methyl-imidazole chloride ([ BMim ] Cl) ionic liquid, heating to 80 ℃ and dissolving for 24 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 2.5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 50% RH for 12 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) 8.4mol/L acrylamide, N' -methylene bisacrylamide with the mass fraction of 0.28wt% and 0.90wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone are mixed and stirred to be fully dissolved, so as to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 36 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 3:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 28.6:100, and polymerizing for 2 hours under the initiation of ultraviolet light with the power of 6W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 0.3MPa and the tensile strain was 1100%.
Example 3
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-ethyl-3-methylimidazole acetate ([ Emim ] [ OAc ]) ionic liquid, heating to 110 ℃ and dissolving for 24 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 2.5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 50% RH for reaction for 6 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) 8.4mol/L acrylamide, N' -methylene bisacrylamide with the mass fraction of 0.84wt% and 1.35wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone are mixed and stirred to be fully dissolved, so as to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 36 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 4.5:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 42.9:100, and polymerizing for 1h under the initiation of ultraviolet light with the power of 24W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 1.6MPa, and the tensile strain was 480%.
Example 4
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-butyl-3-methyl-imidazole chloride ([ BMim ] Cl) ionic liquid, and heating to 110 ℃ to dissolve for 24 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 2.5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 50% RH for 48 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) 8.4mol/L acrylamide, N' -methylene bisacrylamide with the mass fraction of 0.14wt% and 0.45wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone are mixed and stirred to be fully dissolved, so as to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 36 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 1.5:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 14.3:100, and polymerizing for 1h under the initiation of ultraviolet light with the power of 36W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 1.5MPa, and the tensile strain was 980%.
Example 5
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-ethyl-3-methylimidazole acetate ([ Emim ] [ OAc ]) ionic liquid, heating to 100 ℃ and dissolving for 48 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 10 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 70% RH for 12 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) Mixing 5.6mol/L acrylamide, 0.28wt% of N, N' -methylene bisacrylamide and 0.90wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, and stirring to fully dissolve the mixture to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 48 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 3:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 28.6:100, and polymerizing for 1h under the initiation of ultraviolet light with the power of 48W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 0.7MPa and the tensile strain was 500%.
Example 6
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the dried cellulose in the step 1) with 1-butyl-3-methyl-imidazole chloride ([ BMim ] Cl) ionic liquid, and heating to 100 ℃ to dissolve for 60 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 7.5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 50% RH for 12 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) Mixing 5.6mol/L acrylamide, 0.84wt% of N, N' -methylene bisacrylamide and 1.35wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, and stirring to fully dissolve the mixture to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 24 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 3:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 28.6:100, and polymerizing for 2 hours under the initiation of ultraviolet light with the power of 6W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 0.1MPa and the tensile strain was 937%.
Example 7
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-butyl-3-methyl-imidazole chloride ([ BMim ] Cl) ionic liquid, heating to 100 ℃ and dissolving for 36h to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 70% RH for 12 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) Mixing 5.6mol/L acrylamide, 0.42wt% of N, N' -methylene bisacrylamide and 1.575wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, and stirring to fully dissolve the mixture to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 24 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 4.5:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 42.9:100, and polymerizing for 1.5 hours under the initiation of ultraviolet light with the power of 24W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 0.9MPa and the tensile strain was 750%.
Example 8
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) The cellulose was dried in a forced air drying oven to remove moisture and obtain dried cellulose ready for use.
2) Mixing the dried cellulose in the step 1) with 1-ethyl-3-methylimidazole acetate ([ Emim ] [ OAc ]) ionic liquid, heating to 90 ℃ and dissolving for 24 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 10 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 70% RH for 6 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) 8.4mol/L acrylamide, N' -methylene bisacrylamide with the mass fraction of 0.14wt% and 0.45wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone are mixed and stirred to be fully dissolved, so as to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 24 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 1.5:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 14.3:100, and polymerizing for 1.5 hours under the initiation of ultraviolet light with the power of 36W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 1.6MPa and the tensile strain was 780%.
Example 9
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-ethyl-3-methylimidazole acetate ([ Emim ] [ OAc ]) ionic liquid, heating to 90 ℃ and dissolving for 48 hours to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 90% RH for 24 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) Mixing 5.6mol/L acrylamide, 0.42wt% of N, N' -methylene bisacrylamide and 1.35wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, and stirring to fully dissolve the mixture to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 24 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 3:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 28.6:100, and polymerizing for 1.5 hours under the initiation of ultraviolet light with the power of 48W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 1.2MPa, and the tensile strain was 800%.
Example 10
A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation specifically comprises the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the cellulose dried in the step 1) with 1-ethyl-3-methylimidazole acetate ([ Emim ] [ OAc ]) ionic liquid, heating to 80 ℃ and dissolving for 36h to obtain a cellulose-ionic liquid mixed solution with the mass fraction of cellulose of 2.5 wt%;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, then placing the culture dish in an environment with 70% RH for 6 hours, and inducing cellulose self-assembly by water vapor to obtain cellulose gel;
4) 8.4mol/L acrylamide, N' -methylene bisacrylamide with the mass fraction of 0.14wt% and 1.575wt% of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone are mixed and stirred to be fully dissolved, so as to obtain a soaking solution;
5) Soaking the cellulose gel prepared in the step 3) in the soaking solution prepared in the step 4) for 24 hours, wherein the mass ratio of the soaking solution to the cellulose gel is 4.5:1;
6) And after the soaking is finished, weighing the mass ratio of the returned soaking liquid to the soaking liquid used for soaking to be 42.9:100, and polymerizing for 2 hours under the initiation of ultraviolet light with the power of 6W to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
The tensile stress of the hydrogel was 1.4MPa, and the tensile strain was 980%.
Claims (15)
1. A preparation method of tough and transparent hydrogel based on cellulose self-assembly regulation is characterized by comprising the following steps:
1) Drying cellulose in a forced air drying oven to remove water and obtain dried cellulose for later use;
2) Mixing the dried cellulose in the step 1) with an ionic liquid, and heating and dissolving to obtain a cellulose-ionic liquid mixed solution;
3) Spreading the cellulose-ionic liquid mixed solution prepared in the step 2) in a culture dish, and inducing cellulose self-assembly in an environment with certain humidity through moisture to obtain cellulose gel; the humidity of the environment induced by the water is 5-95% RH;
4) Mixing a monomer, a crosslinking agent and a photoinitiator, and fully dissolving to obtain a soaking solution; the monomer is any one of acrylic acid, acrylamide, methacrylic acid, methacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-vinylcaprolactam, hydroxyethyl acrylate or hydroxyethyl methacrylate;
5) Soaking the cellulose gel prepared in the step 3) in the soaking liquid prepared in the step 4);
6) And (3) after soaking, weighing back the soaking solution, and polymerizing under the initiation of ultraviolet light to obtain the tough and transparent hydrogel based on cellulose self-assembly regulation.
2. The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1, wherein the ionic liquid is any one of 1-butyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole bromide salt, 1-ethyl-3-methylimidazole bromide salt, 1-allyl-3-methylimidazole chloride salt or 1-ethyl-3-methylimidazole acetate; the temperature of heating and dissolving is 60-150 ℃ and the dissolving time is 6-72 h; the mass fraction of the cellulose in the cellulose-ionic liquid mixed solution is 0.5-15 wt%.
3. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1 or 2, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride or 1-ethyl-3-methylimidazolium acetate; the temperature of the cellulose is 80-110 ℃ and the dissolution time is 24-60 h; the mass fraction of the cellulose in the cellulose-ionic liquid mixed solution is 2.5-10wt%.
4. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1, wherein the water-induced self-assembly time is 2-48 h.
5. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1, wherein the environmental humidity induced by water is 50-90% RH; the time for self-assembly of the cellulose by the water induction is 6-24 hours.
6. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1, wherein the cross-linking agent is N, N' -methylenebisacrylamide or polyethylene glycol diacrylate; the photoinitiator is any one of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide or 1-hydroxycyclohexyl phenyl ketone.
7. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly control according to claim 1, wherein the monomer is acrylamide, the cross-linking agent is N, N' -methylenebisacrylamide, and the photoinitiator is 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
8. The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1, wherein the concentration of the monomer is 2.8-11.2 mol/L, the adding amount of the cross-linking agent is 0.07-1.12 wt/percent of the mass of the monomer, and the adding amount of the photoinitiator is 0.15-2.7 wt% of the mass of the monomer.
9. The method for preparing a tough and transparent hydrogel based on cellulose self-assembly control according to claim 1 or 8, wherein the concentration of the monomer is 5.6-8.4 mol/L, and the addition amounts of the crosslinking agent and the photoinitiator are 0.14wt% to 0.84wt% and 0.45wt% to 1.35wt% of the monomer, respectively.
10. The preparation method of the tough and transparent hydrogel based on cellulose self-assembly regulation and control, according to claim 1, wherein the mass ratio of the soaking solution to the cellulose gel is 0.5:1-5:1, and the soaking time is 6-48 h.
11. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1 or 10, wherein the mass ratio of the soaking solution to the cellulose gel is 1.5:1-4.5:1; the soaking time is 24-48 h.
12. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly control according to claim 1, wherein the mass ratio of the soaking solution to the soaking solution used for soaking is 4.8:100-47.7:100.
13. The method for preparing a tough, transparent hydrogel based on cellulose self-assembly control according to claim 1 or 12, wherein the mass ratio of the soaking solution to the soaking solution used for soaking is 14.3:100-42.9:100.
14. The method for preparing the tough and transparent hydrogel based on cellulose self-assembly regulation and control according to claim 1, wherein the ultraviolet light power is 6-48W, and the polymerization time initiated by ultraviolet light is 0.5-2 h.
15. The method for preparing a tough, transparent hydrogel based on cellulose self-assembly control according to claim 1 or 14, wherein the ultraviolet light power is 36W; the polymerization time initiated by ultraviolet light is 1-2 h.
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