CN113087837B - Supermolecule-polymer double-network eutectic gel and preparation method and application thereof - Google Patents
Supermolecule-polymer double-network eutectic gel and preparation method and application thereof Download PDFInfo
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- CN113087837B CN113087837B CN202110365358.4A CN202110365358A CN113087837B CN 113087837 B CN113087837 B CN 113087837B CN 202110365358 A CN202110365358 A CN 202110365358A CN 113087837 B CN113087837 B CN 113087837B
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- 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
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- 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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- 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
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- 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
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- C08F220/56—Acrylamide; Methacrylamide
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- 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
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- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a supermolecule-polymer double-network eutectic gel and a preparation method and application thereof. The preparation method comprises the following steps: heating a first mixed reaction system containing the diglucosamide amphiphilic molecules, the polymer monomer, the photoinitiator, the cross-linking agent and the eutectic solvent to be completely dissolved, cooling to room temperature to form a first heavy supermolecule gel network, and carrying out photoinitiated polymerization reaction to obtain the supermolecule-polymer double-network eutectic gel. The supermolecule-polymer double-network eutectic gel prepared by the invention has extremely high mechanical toughness, self-healing property and environmental adaptability, and ultra-fast air/underwater/ultra-low temperature in-situ adhesion performance, and can resist extreme temperature and solvent corrosion; meanwhile, the preparation method provided by the invention has the advantages of low cost, environmental protection, quick reaction, mild conditions and suitability for large-scale production, and the prepared double-network eutectic gel has a good application prospect in the fields of novel adhesive materials and soft electronic devices.
Description
Technical Field
The invention belongs to the technical field of gels, relates to a supermolecule-polymer double-network eutectic gel and a preparation method and application thereof, and particularly relates to a supermolecule-polymer double-network eutectic gel soft material based on small molecules and a preparation method and application thereof.
Background
At present, the rapid development in the fields of artificial intelligence and wearable has made higher demands on soft electronic devices (software electronic devices), and there is an urgent need to develop a multifunctional integrated soft material with excellent optical, electrical, magnetic, mechanical processing and physicochemical properties, which is compatible with a high interface of a hard electrode material, to provide a seamless human-computer interaction interface. Gel materials are a class of classical soft materials with "soft" and "soft" properties similar to biological tissues. The development of a high-toughness, stretchable gel soft material integrating multiple functions (such as transparency, conductivity, self-healing, self-adhesion) is a real need to promote the development of wearable electronic devices. Most of the hydrogel materials are reported at present, however, the conventional hydrogel materials are generally weak in mechanical properties, easy to freeze at low temperature and easy to lose water at high temperature, resulting in loss of functions thereof, thereby seriously affecting the stability and durability of the flexible electronic device (ACS sustatin. chem. eng.2014, 2, 1063-.
Deep Eutectic Solvents (DESs) are an emerging class of green sustainable solvents with properties similar to water, such as low cost, environmental friendliness, easy availability, good biocompatibility, biodegradability (ACS Energy Lett.2018, 3, 2875-. Furthermore, DES solvents have properties significantly superior to water, such as low vapor pressure, high thermal stability, good ionic conductivity, wide electrochemical window, and strong solubility for poorly water-soluble fat-soluble compounds (Angew. chem. int. Ed.2020, 59, 18768-minus 18773; J. Phys. chem. B2020, 124, 8465-minus 8478; Angew. chem. int. Ed.2019, 58, 4173-minus 4178, etc.). In addition, the basic physicochemical properties of the DESs solvent, such as viscosity, polarity, surface tension, and charging property, and the multiple interaction sites in the chemical structure thereof, make it possible to perform a variety of interfacial interactions with a variety of different substrates, such as hydrophilic substrates, hydrophobic substrates, porous substrates, and the like, thereby exerting a strong adhesion effect. Due to the bulk properties of the material components, the development of a novel eutectic gel material platform based on a DES solvent system has important theoretical and practical significance. At present, no report is found on eutectic gel soft materials integrating multiple functions such as high stretchability, self-healing property, adhesion, conductivity, extreme temperature resistance and the like.
Disclosure of Invention
The invention mainly aims to provide a supermolecule-polymer double-network eutectic gel based on small molecules, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a supermolecule-polymer double-network eutectic gel, which comprises the following steps:
heating a first mixed reaction system containing the diglucosamide amphiphilic molecules, the polymer monomer, the photoinitiator, the cross-linking agent and the eutectic solvent to be completely dissolved, cooling to room temperature to form a first heavy supermolecule gel network, and carrying out photoinitiated polymerization reaction to obtain the supermolecule-polymer double-network eutectic gel.
Further, the diglucosamide amphiphilic molecule has a structure shown as a formula (I):
wherein n is selected from 6 to 12, preferably 6, 8, 10 or 12.
The embodiment of the invention also provides the supermolecule-polymer double-network eutectic gel prepared by the method.
The embodiment of the invention also provides application of the supramolecular-polymer double-network eutectic gel in preparation of adhesive materials or flexible electrochromic devices.
Further, the adhesive material comprises an ultra-fast underwater in-situ adhesive material and/or an ultra-low temperature in-situ adhesive material.
The embodiment of the invention also provides an adhesion material which comprises the supermolecular-polymer double-network eutectic gel.
Further, the adhesive material comprises an ultra-fast underwater in-situ adhesive material and/or an ultra-low temperature in-situ adhesive material.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the preparation method of the supermolecule-polymer double-network eutectic gel, raw materials for synthesizing the glucosamine amide amphiphilic molecules, the polymer and the eutectic solvent are all commercial sources, are low in price, are green and environment-friendly, have mild reaction conditions, do not need complicated synthesis and purification steps, and are suitable for large-scale production;
(2) the supermolecule-polymer double-network eutectic gel prepared by the invention realizes the effect that 1+1 is more than 2 of two material components, has better mechanical properties (high stretchability, excellent self-healing property and crack insensitivity) than single supermolecule gel or polymer gel, and solves the problems of poor mechanical properties of the supermolecule gel and poor self-healing properties of the polymer gel; the supermolecule-polymer double-network eutectic gel prepared by the invention has excellent mechanical strength and toughness and excellent self-healing performance, the area strain of biaxial stretching can reach 20000%, and the fracture strain of uniaxial stretching can reach 8000%; in the case of mechanical perforation, a high degree of stretchability can still be maintained, with crack insensitivity. After cutting, the sample has excellent spontaneous self-healing performance, and the self-healing efficiency can reach 41%;
(3) the supermolecule polymer-double-network eutectic gel prepared by the invention has excellent ultra-fast in-situ adhesion, extremely fast adhesion speed (3-5 s), high bonding strength (MPa level), resistance to extreme temperature (-196 ℃ to 200 ℃) and various solvents (strong acid/strong base/organic solvent and the like), and ultra-fast (3-5 s) underwater and ultra-low temperature (as low as-80 ℃) in-situ adhesion performance;
(4) the supermolecule-polymer double-network eutectic gel prepared by the invention also has excellent conductivity and temperature tolerance, can still maintain the flexible mechanical property at the low temperature of-40 ℃ to the high temperature of 100 ℃, and solves the problems that the traditional hydrogel material is easy to freeze at low temperature and lose water at high temperature;
(5) electrochromic devices based on the supramolecular-polymer double-network eutectic gel prepared by the invention have excellent flexible electrochromic performance under unfavorable mechanical conditions (such as bending and folding) or temperature environment (such as-30 ℃ to 60 ℃), and have good durability under extreme conditions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a photograph of a BGA-12/PHEAA supramolecular-polymer double-network eutectic gel prepared in example 2 of the present invention;
FIG. 2 is a confocal microscope of a BGA-12/PHEAA supramolecular-polymer double-network eutectic gel prepared in example 2 of the present invention;
FIGS. 3 a-3 b are XRD patterns of a PHEAA polymer single-network eutectic gel prepared in comparative example 1, a supramolecular single-network eutectic gel prepared in comparative example 2, and a BGA-12/PHEAA supramolecular-polymer double-network eutectic gel prepared in example 2 according to the present invention;
FIG. 4 is a graph of tensile stress-strain curves for BGA-12/PHEAA supramolecular-polymer double-network eutectic gel in example 2 of the present invention and PHEAA polymer single-network eutectic gel in comparative example 1;
FIG. 5 is a photograph of the supramolecular single-network eutectic gel of comparative example 2 of the present invention before and after pressing;
FIG. 6 is a graph of tensile stress-strain curves for samples after cutting and self-healing of the BGA-12/PHEAA supramolecular-polymer double-network eutectic gel of example 2 of the present invention and the PHEAA polymer single-network eutectic gel of comparative example 1;
FIG. 7 is a biaxial drawing of a BGA-12/PHEAA supramolecular-polymer double-network eutectic gel in example 2 of the present invention;
FIG. 8 is a graph of the tensile properties of a notched BGA-12/PHEAA supramolecular-polymer double-network eutectic gel in example 2 of the present invention;
FIGS. 9 a-9 b are the tensile stress-strain curve and the compressive stress-strain curve of the BGA-12/PHEAA supramolecular-polymer double-network eutectic gel of example 2 of the present invention after being stored at 60 ℃ and-30 ℃ for 24 hours, respectively;
FIG. 10 is a flow chart of preparation of an adhesion sample in example 11 of the present invention;
11 a-11 b are graphs of the load-bearing capacity test and adhesion strength, respectively, for various substrates of adhered samples of the invention prepared in accordance with example 11;
FIGS. 12 a-12 d are graphs of the load-bearing capacity and adhesion strength after soaking a sample prepared according to example 11 of the present invention (the substrate is quartz glass) in various solvents for 24 h;
FIG. 13 is a graph showing the adhesion performance of an adhesion sample (quartz glass as a substrate) prepared according to example 11 of the present invention after being immersed in liquid nitrogen (-196 ℃) for 1 hour;
FIG. 14 is a graph showing the adhesion properties of an adhesion sample (substrate is quartz glass) prepared according to example 11 of the present invention after boiling in boiling water at 100 ℃ for 1 hour;
FIG. 15 is a graph showing underwater in situ adhesion performance tests of adhesion samples (quartz glass substrate) prepared in situ in an underwater environment according to the method of example 11;
FIG. 16 is a graph showing the ultra-low temperature (-80 ℃) in-situ adhesion performance test of an adhesion sample (quartz glass substrate) prepared in situ in an ultra-low temperature (-80 ℃) environment according to the method of example 11;
FIG. 17 is a graph showing adhesion performance test of an adhesion sample (quartz glass substrate) prepared according to example 11 of the present invention after being stored at a high temperature of 200 ℃ for 12 hours;
FIG. 18 is a graph of adhesion strength of adhered samples (quartz glass substrate) made in accordance with the method of example 11 under various extreme environmental conditions in accordance with the present invention;
FIG. 19 shows the application of BGA-12/PHEAA supramolecular-polymer double-network eutectic gel prepared by the invention as an underwater adhesive in-situ repairing blue and white porcelain underwater;
FIG. 20 is a graph showing the conductivity, self-healing and adhesion properties of the BGA-12/PHEAA supramolecular-polymer double-network eutectic gel in example 2 of the present invention;
fig. 21 is a graph showing the flexible electrochromic properties of an electrochromic device based on BGA-12/PHEAA supramolecular-polymer double-network eutectic gel constructed in example 12 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor in the case provides a technical scheme of the invention through long-term research and a great deal of practice, the invention firstly introduces a polymer network and a small molecular-based supramolecular network into a eutectic solvent system, and designs and synthesizes a brand-new supramolecular-polymer double-network eutectic gel material through directional synergistic assembly between the two, the material shows high strength and high toughness which are obviously superior to polymer single-network gel, and shows good self-healing property, ultra-fast (3-5 s) in-situ adhesion property, conductivity and temperature tolerance, and the material shows wide application prospects in the fields of underwater in-situ adhesion, flexible electronic devices and the like.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a preparation method of a supramolecular-polymer double-network eutectic gel based on small molecules, which includes:
heating a first mixed reaction system containing the diglucosamide amphiphilic molecules, the polymer monomer, the photoinitiator, the cross-linking agent and the eutectic solvent to be completely dissolved, cooling to room temperature to form a first heavy supermolecule gel network, and carrying out photoinitiated polymerization reaction to obtain the supermolecule-polymer double-network eutectic gel.
In some more specific embodiments, the preparation method comprises: mixing the dual-glucose-amide amphiphilic molecules, the polymer monomer, the photoinitiator, the cross-linking agent and the eutectic solvent to form the first mixed reaction system, heating the first mixed reaction system to be completely dissolved, cooling the first mixed reaction system to room temperature, and standing for 5-60 min to form the first heavy supermolecule gel network.
In some more specific embodiments, the bisglucamide amphiphiles (BGA-n, n being 6, 8, 10 or 12, i.e., BGA-6, BGA-8, BGA-10, BGA-12) have a structure according to formula (I):
wherein n is selected from 6-12, preferably 6, 8, 10 or 12, (noted as BGA-n, n is 6, 8, 10 or 12, i.e. BGA-6, BGA-8, BGA-10, BGA-12).
In some more specific embodiments, the method for preparing the bisglucamide amphiphilic molecule comprises: dissolving delta-gluconolactone in methanol, refluxing and stirring for 1-3h, then adding diamine compound, refluxing and stirring for 8-24h again, and then filtering, washing and drying to obtain the diglucosamide amphiphilic molecule.
Further, the bisglucamide amphiphilic molecule is a white solid.
Further, the diamine compound has a structure shown in a formula (II):
wherein n is selected from 6 to 12, preferably 6, 8, 10 or 12.
Further, the diamine compound includes any one of 1, 6-diaminohexane, 1, 8-diaminooctane, 1, 10-diaminodecane, and 1, 12-diaminododecane, but is not limited thereto.
Further, the preparation method of the diglucosamide amphiphilic molecule specifically comprises the following steps: mixing the mixture containing delta-gluconolactone and methanol, stirring and refluxing for 1h at 70 ℃, then adding diamine compounds to form the second mixed reaction system, reacting for 2h at 70 ℃, filtering the mixture while hot, repeatedly washing the filter cake with cold methanol and diethyl ether in turn, and drying in a vacuum drying oven to obtain the diglucosamide amphiphilic molecule (BGA-n) as a white solid.
Further, the molar ratio of the delta-gluconolactone to the diamine compound is 1-2: 2.
In some specific embodiments, the light wavelength used for the photo-initiated polymerization reaction is 365nm, and the illumination time is 3 s-5 min.
In some more specific embodiments, the eutectic solvent includes a hydrogen bond acceptor including choline chloride and a hydrogen bond donor including any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, sorbitol, glycerol, xylitol, and urea, but not limited thereto.
Further, the polymer monomer includes any one of acrylamide (AAm), N- (2-hydroxyethyl) acrylamide (HEAA), N' N-dimethylacrylamide (DMAAm), 4-Hydroxybutylacrylate (HBA), and is not limited thereto.
Further, the photoinitiator includes any one of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (Irgacure 2959), and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (Irgacure 819), without being limited thereto.
Further, the crosslinking agent includes any one of N, N' -Methylenebisacrylamide (MBA), 1, 6-hexanediol diacrylate (HDDA), and is not limited thereto.
In some more specific embodiments, the mass ratio of the bisglucamide amphiphilic molecules to the eutectic solvent is 2.5-10: 100.
Further, the mass ratio of the polymer monomer to the eutectic solvent is 50-150: 100.
Furthermore, the mass ratio of the cross-linking agent to the eutectic solvent is 0.01-1: 100.
Further, the mass ratio of the photoinitiator to the eutectic solvent is 1-10: 100.
In another aspect of the embodiments of the present invention, there is also provided a supramolecular-polymer double-network eutectic gel prepared by the aforementioned method.
Further, the use temperature of the supermolecule-polymer double-network eutectic gel is-40 ℃ to 100 ℃.
Further, the conductivity of the supermolecule-polymer double-network eutectic gel is 0.1-5.0 mS/cm.
Further, the supermolecule-polymer double-network eutectic gel has excellent mechanical strength and toughness and excellent self-healing performance, wherein the area strain of biaxial stretching is 1000-20000%, and the fracture strain of uniaxial stretching is 100-8000%; under the condition of mechanical perforation, high stretchability can still be maintained, and the flexible mechanical property can still be maintained at a low temperature of-40 ℃ to a high temperature of 100 ℃; after cutting, the sample has excellent self-healing performance, and the self-healing efficiency can reach 41%.
Furthermore, the supramolecular-polymer double-network eutectic gel has ultra-fast strong adhesion to different material substrates, has strong adhesion capability even under water and extreme conditions (-196 ℃ to 200 ℃, strong acid/strong base/organic solvent and the like), and has potential application as an underwater in-situ adhesion material and an ultralow temperature (-80 ℃) in-situ adhesion material.
Further, the supramolecular-polymer double-network eutectic gel also has excellent electrical conductivity, and an electrochromic device based on the supramolecular-polymer double-network eutectic gel prepared by the invention still has excellent electrochromic performance under unfavorable mechanical conditions (such as bending and folding) or temperature environment (such as-30 ℃ to 60 ℃), and has good durability under extreme conditions.
Another aspect of the embodiments of the present invention also provides a use of the supramolecular-polymer double-network eutectic gel in the field of adhesive materials or flexible electrochromic devices.
Further, the adhesive material includes an underwater in-situ adhesive material, and is not limited thereto.
Further, the adhesive material includes an ultra-fast underwater in-situ adhesive material and/or an ultra-low temperature in-situ adhesive material, and is not limited thereto.
Another aspect of an embodiment of the present invention also provides an adhesive material comprising the aforementioned supramolecular-polymer double-network eutectic gel.
Further, the adhesive material comprises an ultra-fast underwater in-situ adhesive material and/or an ultra-low temperature in-situ adhesive material.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Dissolving delta-gluconolactone in methanol, then refluxing and stirring at 70 ℃ for 1h, then adding 1, 12-diaminododecane, refluxing and stirring the reaction mixture at 70 ℃ for 2h again, filtering the mixture while hot, repeatedly washing a filter cake with cold methanol and diethyl ether in sequence, and drying in a vacuum drying oven to obtain the glucosamine amide amphiphilic molecule BGA-12;
the 25mg of BGA-12, 1000mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure2959, 10. mu.L (10mg/mL) of MBA and 1000mg of choline chloride-ethylene glycol solution were weighed accurately in a glass vial, heating to dissolve completely, injecting into 2mm dumbbell-shaped mold while hot, naturally cooling to room temperature and standing for 30min to form a first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 2min, obtaining a BGA-12/PHEAA supermolecule-polymer double-network eutectic gel sample, in the BGA-12/PHEAA supermolecule-polymer double-network eutectic gel, the mass of the BGA-12 accounts for 2.5 percent of the mass of the choline chloride-glycol solution, and the mass ratio of the N- (2-hydroxyethyl) acrylamide (HEAA) to the choline chloride-glycol solution is 100: 100; the conductivity of the prepared BGA-12/PHEAA supermolecule-polymer double-network eutectic gel sample is 0.70 mS/cm.
Example 2
40.0mg of BGA-12 prepared in example 1, 1000mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure2959, 46. mu.L (10mg/mL) of MBA, 1000mg of choline chloride-ethylene glycol solution were weighed accurately in a glass vial, heating to dissolve completely, injecting into dumbbell-shaped mold with thickness of 2mm, naturally cooling to room temperature, standing for 30min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 1min, obtaining a BGA-12/PHEAA supermolecule-polymer double-network eutectic gel sample, in the BGA-12/PHEAA supermolecule-polymer double-network eutectic gel, the mass of the BGA-12 accounts for 4% of the mass of the choline chloride-glycol solution, and the mass ratio of the N- (2-hydroxyethyl) acrylamide (HEAA) to the choline chloride-glycol solution is 100: 100; the conductivity of the prepared BGA-12/PHEAA supermolecule-polymer double-network eutectic gel sample is 0.47 mS/cm.
Example 3
40.0mg of BGA-12 prepared in example 1, 500mg of acrylamide (AAm), 44.8mg of Irgacure2959, 46. mu.L (10mg/mL) of MBA, 1000mg of choline chloride-ethylene glycol solution were weighed accurately in a glass vial, heating to dissolve completely, injecting into dumbbell-shaped mold with thickness of 2mm, naturally cooling to room temperature, standing for 30min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 1min, obtaining the BGA-12/PAAm supermolecule-polymer double-network eutectic gel sample, in the BGA-12/PAAm supermolecule-polymer double-network eutectic gel, the mass of the BGA-12 accounts for 4% of that of the choline chloride-glycol solution, and the mass ratio of acrylamide (AAm) to the choline chloride-glycol solution is 50: 100; the conductivity of the prepared BGA-12/PAAm supermolecule-polymer double-network eutectic gel sample is 1.20 mS/cm.
Example 4
40.0mg of BGA-12 prepared in example 1, 500mg of N' N-dimethylacrylamide (DMAAm), 22.4mg of Irgacure2959, 46. mu.L (10mg/mL) of MBA, 1000mg of choline chloride-ethylene glycol solution were accurately weighed in a glass vial, heating to dissolve completely, injecting into dumbbell-shaped mold with thickness of 2mm, naturally cooling to room temperature, standing for 30min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 1min, obtaining a BGA-12/PDMAAm supermolecule-polymer double-network eutectic gel sample, in the BGA-12/PDMAAm supermolecule-polymer double-network eutectic gel, the mass of the BGA-12 accounts for 4% of that of the choline chloride-glycol solution, and the mass ratio of the N' N-dimethylacrylamide (DMAAm) to the choline chloride-glycol solution is 50: 100; the conductivity of the prepared BGA-12/PDMAAm supermolecule-polymer double-network eutectic gel sample is 0.85 mS/cm.
Example 5
Dissolving delta-gluconolactone in methanol, then refluxing and stirring for 1h at 70 ℃, then adding 1, 10-diaminodecane, refluxing and stirring the reaction mixture for 2h at 70 ℃, filtering the mixture while hot, repeatedly washing a filter cake with cold methanol and diethyl ether in sequence, and drying in a vacuum drying oven to obtain the glucosamine-based amphiphilic molecule BGA-10;
accurately weigh 40.0mg of BGA-10, 500mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure 819, 46. mu.L (10mg/mL) of MBA, 1000mg of choline chloride-xylitol solution in a glass vial, heating to dissolve completely, injecting into 2mm dumbbell-shaped mold while it is hot, naturally cooling to room temperature, standing for 20min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 60s, obtaining a BGA-10/PHEAA supermolecule-polymer double-network eutectic gel sample, in the BGA-10/PHEAA supermolecule-polymer double-network eutectic gel, the mass of the BGA-10 accounts for 4% of the mass of the choline chloride-xylitol solution, and the mass ratio of the N- (2-hydroxyethyl) acrylamide (HEAA) to the choline chloride-xylitol solution is 50: 100; the conductivity of the prepared BGA-10/PHEAA supermolecule-polymer double-network eutectic gel sample is 0.30 mS/cm.
Example 6
25.0mg of BGA-10 prepared in example 5, 800mg of 4-Hydroxybutylacrylate (HBA), 22.4mg of Irgacure2959, 30. mu.L (10mg/mL) of MBA, 1000mg of choline chloride-ethylene glycol solution were weighed out accurately in a glass vial, heating to dissolve completely, injecting into dumbbell-shaped mold with thickness of 2mm, naturally cooling to room temperature, standing for 20min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 5min, obtaining the BGA-10/PHBA supermolecule-polymer double-network eutectic gel sample, in the BGA-10/PHBA supermolecule-polymer double-network eutectic gel, the mass of the BGA-10 accounts for 2.5 percent of the mass of the choline chloride-glycol solution, and the mass ratio of the 4-hydroxybutyl acrylate (HBA) to the choline chloride-glycol solution is 80: 100; the conductivity of the prepared BGA-10/PHBA supermolecule-polymer double-network eutectic gel sample is 0.98 mS/cm.
Example 7
Accurately weighing 40.0mg of BGA-10, 1500mg of acrylamide (AAm), 10mg of Irgacure 819, 40 mu L (10mg/mL) of HDDA and 1000mg of choline chloride-xylitol solution prepared in example 5 into a glass vial, heating until the solutions are completely dissolved, injecting the solution into a dumbbell-shaped mold with the thickness of 2mm while the solution is hot, naturally cooling the solution to room temperature, standing the solution for 30min to form a first heavy supermolecule gel network, and irradiating the solution for 2min under an ultraviolet lamp with the wavelength of 365nm to obtain the BGA-10/PAAm supermolecule-polymer double-network eutectic gel sample. In the BGA-10/PAAm supermolecule-polymer double-network eutectic gel, the mass of the BGA-10 accounts for 4% of the mass of the choline chloride-xylitol solution, and the mass ratio of acrylamide (AAm) to the choline chloride-xylitol solution is 150: 100; the conductivity of the prepared BGA-10/PAAm supermolecule-polymer double-network eutectic gel sample is 0.16 mS/cm.
Example 8
Dissolving 6-gluconolactone in methanol, then refluxing and stirring at 70 ℃ for 1h, then adding 1, 6-diaminohexane, refluxing and stirring the reaction mixture at 70 ℃ for 2h again, filtering the mixture while hot, repeatedly washing a filter cake with cold methanol and diethyl ether in sequence, and drying in a vacuum drying oven to obtain the glucosamine-based amphiphilic molecule BGA-6;
40.0mg of BGA-6, 500mg of 4-Hydroxybutylacrylate (HBA), 44.8mg of Irgacure2959, 22.4. mu.L (10mg/mL) of MBA, 1000mg of choline chloride-sorbitol solution were weighed out accurately in a glass vial, heating to dissolve completely, injecting into 2mm dumbbell-shaped mold while hot, naturally cooling to room temperature, standing for 40min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 5min, obtaining the BGA-6/PHBA supermolecule-polymer double-network eutectic gel sample, in the BGA-6/PHBA supermolecule-polymer double-network eutectic gel, the mass of the BGA-6 accounts for 4% of that of the choline chloride-sorbitol solution, and the mass ratio of the 4-hydroxybutyl acrylate (HBA) to the choline chloride-sorbitol solution is 50: 100; the conductivity of the prepared BGA-6/PHBA supermolecule-polymer double-network eutectic gel sample is 0.20 mS/cm.
Example 9
Dissolving delta-gluconolactone in methanol, then refluxing and stirring for 1h at 70 ℃, then adding 1, 8-diaminooctane, refluxing and stirring the reaction mixture for 5h at 70 ℃, filtering the mixture while hot, repeatedly washing a filter cake with cold methanol and diethyl ether in sequence, and drying in a vacuum drying oven to obtain the glucosamine amphiphilic molecule BGA-8;
80.0mg of BGA-8, 500mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure2959, 46. mu.L (10mg/mL) of MBA and 1000mg of choline chloride-urea solution prepared above were accurately weighed in a glass vial, heating to dissolve completely, injecting into 2mm dumbbell-shaped mold while hot, naturally cooling to room temperature, standing for 10min to form first double supramolecular gel network, irradiating under 365nm ultraviolet lamp for 2min, obtaining a BGA-8/PHEAA supermolecule-polymer double-network eutectic gel sample, in the BGA-8/PHEAA supermolecule-polymer double-network eutectic gel, the mass of the BGA-8 accounts for 8% of that of the choline chloride-urea solution, and the mass ratio of the N- (2-hydroxyethyl) acrylamide (HEAA) to the choline chloride-urea solution is 50: 100; the conductivity of the prepared BGA-8/PHEAA supermolecule-polymer double-network eutectic gel sample is 0.12 mS/cm.
Example 10
100.0mg of BGA-8, 500mg of 4-Hydroxybutylacrylate (HBA), 50mg of Irgacure2959, 50. mu.L (10mg/mL) of HDDA, 1000mg of choline chloride-urea solution prepared in example 9 were weighed out accurately in a glass vial, heating to dissolve completely, injecting into dumbbell-shaped mold with thickness of 2mm, naturally cooling to room temperature, standing for 20min to form first heavy supramolecular gel network, then irradiating for 5min under an ultraviolet lamp with the wavelength of 365nm to obtain a BGA-8/PHBA supermolecule-polymer double-network eutectic gel sample, in the BGA-8/PHBA supermolecule-polymer double-network eutectic gel, the mass of the BGA-8 accounts for 10% of that of the choline chloride-urea solution, and the mass ratio of the 4-Hydroxybutylacrylate (HBA) to the choline chloride-urea solution is 50: 100; the conductivity of the prepared BGA-8/PHBA supermolecule-polymer double-network eutectic gel sample is 0.15 mS/cm.
Example 11 preparation of adherent samples
40.0mg of BGA-12 prepared in example 1, 1000mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure2959, 46 μ L (10mg/mL) of MBA and 1000mg of choline chloride-ethylene glycol solution are accurately weighed in a glass vial, and after being heated to be completely dissolved, the solution is naturally cooled to room temperature and stands for 30min to form a first heavy supramolecular gel network. Adding it dropwise into the solution by using a liquid-transfering gunOn substrates made of different materials, after covering quartz glass on the upper layer, pressing for 10s, irradiating for 3-5 s under an ultraviolet lamp with the wavelength of 365nm, and immediately sticking the upper and lower layers of substrates by the formed supermolecule-polymer double-network eutectic gel. The adhered samples were used to perform various adhesion performance tests. The sample preparation process is shown in FIG. 10, and the content of the gel sample (adhesive) on the substrate is about 3-4 mg-cm-2。
EXAMPLE 12 construction of Flexible electrochromic device
40.0mg of BGA-12 prepared in example 1, 1000mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure2959, 46 μ L (10mg/mL) of MBA, 25mg of ethyl viologen, 30mg of 1, 1' -dimethylferrocene and 1000mg of choline chloride-ethylene glycol solution are accurately weighed in a glass vial, heated to be completely dissolved, naturally cooled to room temperature and kept stand for 30min to form a first heavy supramolecular gel network. And dropwise adding the gel on an ITO/PET substrate by using a liquid-transferring gun, covering the upper layer with another ITO/PET substrate, pressing for 10s, and irradiating for 3-5 s under an ultraviolet lamp with the wavelength of 365nm to obtain the flexible electrochromic device taking the supermolecule-polymer double-network eutectic gel as the quasi-solid electrolyte.
Comparative example 1
Accurately weighing 1000mg of N- (2-hydroxyethyl) acrylamide (HEAA), 44.8mg of Irgacure2959, 46 mu L (10mg/mL) of MBA and 1000mg of choline chloride-ethylene glycol solution into a glass vial, injecting the glass vial into a dumbbell-shaped mold with the thickness of 2mm, naturally cooling the glass vial, and irradiating the glass vial for 1min under an ultraviolet lamp with the wavelength of 365nm to obtain a PHEAA polymer single-network eutectic gel sample, wherein the mass ratio of the N- (2-hydroxyethyl) acrylamide (HEAA) to the choline chloride-ethylene glycol solution in the eutectic solvent polymer gel is 100: 100.
Comparative example 2
Accurately weighing 40.0mg of BGA-12 prepared in example 1 and 1000mg of choline chloride-ethylene glycol solution in a glass vial, heating until the choline chloride-ethylene glycol solution is completely dissolved, naturally cooling until supramolecular network gelatinizes, and obtaining a BGA-12 supramolecular single-network eutectic gel sample, wherein the mass of BGA-12 in the eutectic solvent supramolecular gel accounts for 4% of that of the choline chloride-ethylene glycol solution.
And (3) performance characterization:
(1) FIG. 1 is a photograph of a supramolecular-polymer double-network eutectic gel prepared in example 2 of the present invention; FIG. 2 is a confocal laser microscope of the supramolecular-polymer double-network eutectic gel prepared in example 2 of the invention;
fig. 3 a-3 b are XRD patterns of PHEAA polymer single-network eutectic gels prepared in comparative example 1, supramolecular single-network eutectic gels prepared in comparative example 2, and supramolecular-polymer double-network eutectic gels prepared in example 2 according to the present invention.
(2) Mechanical and self-healing properties
FIG. 4 is a tensile stress-strain graph of the supramolecular-polymer double-network eutectic gel prepared in example 2 of the invention and the PHEAA polymer single-network eutectic gel prepared in comparative example 1, showing significantly enhanced tensile stress at break and strain at break, whereas the supramolecular single-network eutectic gel in comparative example 2 is too weak to withstand tensile testing due to its mechanical properties;
fig. 5 is a picture of the supramolecular single-network eutectic gel of comparative example 2 before and after pressing, the supramolecular single-network eutectic gel was broken after light pressing, and the mechanical properties were weak.
FIG. 6 is a graph of tensile stress-strain curves for samples after cutting and self-healing of the supramolecular-polymer dual-network eutectic gel prepared in example 2 of the present invention and the PHEAA polymer single-network eutectic gel in comparative example 1, showing significantly enhanced self-healing performance compared to the polymer single-network eutectic gel; compared with the original sample, the self-healing efficiency (area under the tensile stress-strain curve of the sample after healing/area under the tensile stress-strain curve of the sample before and after healing) of the polymer single-network eutectic gel is only 2.5%, while the healing efficiency of the supramolecular-polymer double-network eutectic gel is as high as 41%.
FIG. 7 is a biaxial drawing of a supramolecular-polymer double-network eutectic gel prepared in example 2 of the invention, which can be drawn from 2X 2cm2Stretching to 26X 28cm2Tensile strain in area greater than 18000%, (Table)The supermolecule-polymer double-network eutectic gel has very excellent mechanical toughness.
Fig. 8 is a graph showing the tensile properties of the notched supramolecular-polymer double-network eutectic gel prepared in example 2 of the present invention, which indicates that the supramolecular-polymer double-network eutectic gel has high toughness and is effective in resisting crack propagation.
(3) Temperature resistance
Fig. 9 a-9 b are tensile stress-strain curves (fig. 9a) and compressive stress-strain curves (fig. 9b) of the supramolecular-polymer double-network eutectic gel prepared in example 2 of the invention after being stored in an oven at 60 ℃ and a refrigerator at-30 ℃ for 24 hours, respectively, showing excellent flexibility and freeze and dry resistances.
(4) Adhesion Properties
FIG. 10 is a flow chart showing the preparation of a sample for adhesion in example 11 of the present invention.
Fig. 11a to 11b are a load-bearing capacity test and an adhesion strength graph of adhesion samples prepared according to the method of example 11, respectively, showing that the supramolecular-polymer double-network eutectic gel shows excellent adhesion effect on various surfaces, which can easily endure a weight of 2 to 10kg without falling off, including hydrophilic glass, wood, metal plates (stainless steel, zinc, iron, copper, aluminum) and highly hydrophobic PET plates, plastic plates, teflon, etc., in accordance with the present invention, wherein the supramolecular-polymer double-network eutectic gel shows the best adhesion effect on the glass surface, and the adhesion strength can be as high as 1.25 MPa.
Fig. 12a to 12d are graphs showing the load-bearing capacity and adhesive strength after soaking a sample prepared according to example 11 (quartz glass as a substrate) in various solvents for 24 hours, and the results show that the sample can still maintain strong adhesive capacity and can easily bear the weight of 2-10kg without falling after soaking the sample in various solvents such as water, strong alkali, strong acid (even aqua regia), organic solvent and the like for 24 hours, and the supramolecular-polymer double-network eutectic gel adhesive prepared by the invention has excellent water, acid, alkali and organic solvent resistance.
FIG. 13 is a graph showing the adhesion properties of an adhesion sample (quartz glass as a substrate) prepared according to example 11 of the present invention under an ultra-low temperature (-196 ℃ C.). The results show that after the sample is completely immersed in liquid nitrogen (-196 ℃) for 1h, the sample can still hang easily with a weight of 5 kg.
FIG. 14 is a graph showing the adhesion properties of an adhesion sample (substrate is quartz glass) prepared according to example 11 of the present invention after boiling with boiling water at 100 ℃ for 1 hour. The result shows that the sample can still be hung easily by 10kg after being boiled in water for 1h, and the supermolecule-polymer double-network eutectic gel adhesive prepared by the invention has excellent water resistance and high temperature resistance.
FIG. 15 is a graph showing underwater in situ adhesion performance tests of adhesion samples (quartz glass substrate) prepared in situ in an underwater environment according to the method of example 11. After the precursor hot solution (mixed solution formed by BGA-12, N- (2-hydroxyethyl) acrylamide, Irgacure2959, MBA and choline chloride-ethylene glycol, the method is the same as that in example 11) is cooled, the formed pre-gel material is dropwise coated on underwater quartz glass by a liquid transfer gun, after the upper layer is covered with another layer of quartz glass, the pressing is carried out for 10 seconds, an ultraviolet lamp irradiates for 3-5 seconds, the glass is immediately stuck, and a sample can easily bear a weight of 5kg without falling off. In-situ underwater bonding cannot be realized in comparative examples 1 and 2, which shows that the supermolecular-polymer double-network eutectic gel adhesive prepared by the invention has ultra-fast in-situ underwater bonding performance.
FIG. 16 is a graph showing the ultra-low temperature in-situ adhesion performance test of an adhesion sample (quartz glass substrate) prepared in situ in a dry ice (-80 ℃) environment according to the method of example 11. After a precursor hot solution (a mixed solution formed by BGA-12, N- (2-hydroxyethyl) acrylamide, Irgacure2959, MBA and choline chloride-ethylene glycol, the method is the same as that in example 11), a formed pre-gel material is dropwise coated on quartz glass in a dry ice (-80 ℃) environment by using a liquid transfer gun, after the upper layer is covered with another layer of quartz glass, the quartz glass is pressed for 10 seconds, an ultraviolet lamp irradiates for 3-5 seconds, the glass is immediately stuck, and a sample can easily bear a weight of 10kg without falling off, so that the supermolecular-polymer double-network eutectic gel adhesive prepared by the invention has the ultra-fast ultra-low temperature (-80 ℃) in-situ adhesive property.
FIG. 17 is a graph showing the adhesion performance test of an adhesion sample (quartz glass as a substrate) prepared according to example 11 of the present invention after being stored at a high temperature of 200 ℃ for 12 hours. After the sample is placed in an oven at 200 ℃ for 12 hours, the sample can still be easily hung by 10kg, which shows that the supramolecular-polymer double-network eutectic gel adhesive prepared by the invention has excellent high-temperature-resistant bonding performance.
FIG. 18 is a graph of the adhesion strength of adhered samples (quartz glass substrate) prepared according to the method of example 11 under various extreme conditions in accordance with the present invention. Wherein the adhesive strength under ultralow temperature (-196 ℃) is 0.73MPa, the adhesive strength after boiling in water for 1h or baking in an oven at 200 ℃ overnight respectively reaches 0.81MPa and 2.44MPa, and the underwater in-situ adhesive strength and the ultralow temperature in-situ adhesive strength are 0.47MPa and 0.76MPa respectively.
Fig. 19 shows the application of the supramolecular-polymer double-network eutectic gel prepared by the invention as an underwater adhesive in-situ repairing blue and white porcelain underwater. The broken blue and white porcelain can be rapidly repaired in situ (5 s) under water, and the supramolecular-polymer double-network eutectic gel adhesive prepared by the invention has potential application in repairing cultural relics at original sites under water.
Fig. 20 is a graph showing the conductivity, self-healing and adhesion properties of the supramolecular-polymer double-network eutectic gel in example 2 of the present invention. The supermolecule-polymer double-network eutectic gel is adhered to the aluminum electrode and communicated with a loop, and a small bulb can be easily lightened even in a stretching state, so that the supermolecule-polymer double-network eutectic gel has excellent conductivity and stretchability; the cut supermolecule-polymer double-network eutectic gel can self-heal and be connected with a circuit again, and a healed sample can bear tensile deformation and is firmly attached to an aluminum electrode, so that the supermolecule-polymer double-network eutectic gel has excellent self-healing performance and adhesion performance. The results show that the supermolecule-polymer double-network eutectic gel prepared by the invention has excellent multifunctional performance and can be used as a novel electronic adhesive to be applied to the construction of various flexible devices.
Fig. 21 is a graph of the flexible electrochromic properties of an electrochromic device prepared in example 12 of the present invention. The result shows that the supermolecule-polymer double-network eutectic gel prepared by the invention has excellent adhesion performance to an ITO/PET electrode, so that the constructed flexible electrochromic device has good conformal deformability, and has excellent reversible cycle coloring (blue) and fading (light yellow) performances even in a bent state.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained desirable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (8)
1. The preparation method of the supermolecule-polymer double-network eutectic gel is characterized by comprising the following steps:
heating a first mixed reaction system containing the diglucosamide amphiphilic molecules, the polymer monomers, the photoinitiator, the cross-linking agent and the eutectic solvent to be completely dissolved, cooling to room temperature to form a first heavy supermolecule gel network, and carrying out photoinitiated polymerization reaction to obtain a supermolecule-polymer double-network eutectic gel;
the glucosamine amide amphiphilic molecule has a structure shown in a formula (I):
formula (I)
Wherein n is selected from 6-12;
the preparation method of the dual-glucose amide amphiphilic molecule comprises the following steps: dissolving delta-gluconolactone in methanol, refluxing and stirring for 1-3h, then adding diamine compound, refluxing and stirring for 8-24h again, and then filtering, washing and drying to obtain the diglucosamide amphiphilic molecules; the diamine compound has a structure shown in a formula (II):
formula (II)
Wherein n is selected from 6-12;
the molar ratio of the delta-gluconolactone to the diamine compound is 1-2: 2;
the eutectic solvent comprises a hydrogen bond receptor and a hydrogen bond donor, wherein the hydrogen bond receptor is selected from choline chloride, and the hydrogen bond donor is selected from any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, sorbitol, glycerol, xylitol and urea;
the polymer monomer is selected from any one of acrylamide, N- (2-hydroxyethyl) acrylamide, N' N-dimethylacrylamide and 4-hydroxybutyl acrylate;
the photoinitiator is selected from 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and/or phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide;
the cross-linking agent is selected from N, N' -methylene bisacrylamide and/or 1, 6-hexanediol diacrylate;
the mass ratio of the dual-glucose amide amphiphilic molecules to the eutectic solvent is 2.5-10: 100;
the mass ratio of the polymer monomer to the eutectic solvent is 50-150: 100;
the mass ratio of the cross-linking agent to the eutectic solvent is 0.01-1: 100;
the mass ratio of the photoinitiator to the eutectic solvent is 1-10: 100.
2. The production method according to claim 1, characterized by comprising:
mixing the dual-glucose-amide amphiphilic molecules, the polymer monomer, the photoinitiator, the cross-linking agent and the eutectic solvent to form the first mixed reaction system, heating the first mixed reaction system to be completely dissolved, cooling the first mixed reaction system to room temperature, and standing the first mixed reaction system for 5-30 min to form the first heavy supramolecular gel network.
3. The method according to claim 1, wherein the diamine compound is any one selected from the group consisting of 1, 6-diaminohexane, 1, 8-diaminooctane, 1, 10-diaminodecane, and 1, 12-diaminododecane.
4. The method of claim 1, wherein: the light wavelength adopted by the photo-initiated polymerization reaction is 365nm, and the illumination time is 3 s-5 min.
5. A supramolecular-polymer double-network eutectic gel prepared by the method of any one of claims 1 to 4;
the area strain of biaxial stretching of the supermolecule-polymer double-network eutectic gel is 1000-20000%, and the breaking strain of uniaxial stretching is 100-8000%;
the conductivity of the supermolecule-polymer double-network eutectic gel is 0.1-5.0 mS/cm.
6. Use of the supramolecular-polymer double-network eutectic gel as claimed in claim 5 for the preparation of adhesive materials or flexible electrochromic devices.
7. Use according to claim 6, characterized in that: the adhesive material is selected from ultra-fast underwater in-situ adhesive material and/or ultra-low temperature in-situ adhesive material.
8. An adhesive material characterized by comprising the supramolecular-polymer double-network eutectic gel of claim 5; the adhesive material is selected from ultra-fast underwater in-situ adhesive material and/or ultra-low temperature in-situ adhesive material.
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