CN116023585A - Double-network NIPAM-based ionic gel and preparation method thereof - Google Patents

Double-network NIPAM-based ionic gel and preparation method thereof Download PDF

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CN116023585A
CN116023585A CN202211727087.3A CN202211727087A CN116023585A CN 116023585 A CN116023585 A CN 116023585A CN 202211727087 A CN202211727087 A CN 202211727087A CN 116023585 A CN116023585 A CN 116023585A
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nipam
network
isopropyl acrylamide
ionic gel
based ionic
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王齐华
曹芃锐
张耀明
杨靖
杨增辉
王廷梅
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention provides a double-network NIPAM-based ionic gel and a preparation method thereof, and relates to the technical field of ionic gel. The preparation method of the double-network NIPAM-based ionic gel provided by the invention comprises the following steps: mixing N-isopropyl acrylamide, a copolymer, a cross-linking agent, a photoinitiator and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution to obtain N-isopropyl acrylamide resin; and sequentially carrying out photo-curing and drying on the N-isopropyl acrylamide resin to obtain the double-network NIPAM-based ionic gel. The dual-network NIPAM-based ionic gel provided by the invention not only has excellent mechanical properties, but also does not decrease with increasing stretching speed, and instead shows increasing trend.

Description

Double-network NIPAM-based ionic gel and preparation method thereof
Technical Field
The invention relates to the technical field of ionic gel, in particular to a double-network NIPAM-based ionic gel and a preparation method thereof.
Background
The ionic gel has the function which cannot be realized by the hydrogel material due to the uniqueness of the ionic liquid. This includes a wider usable temperature window, higher ionic conductivity, and more stable performance, among others. However, ionic gels have reduced mechanical properties due to the ionic liquid contained therein, and for this reason how to achieve high mechanical properties of ionic gels has become the biggest obstacle to the current use of ionic gels.
Disclosure of Invention
The invention aims to provide a double-network NIPAM-based ionic gel and a preparation method thereof, and the double-network NIPAM-based ionic gel provided by the invention not only has excellent mechanical properties, but also has the tendency that the mechanical properties are not reduced along with the increase of the stretching speed, and instead, the mechanical properties are increased.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of double-network NIPAM-based ionic gel, which comprises the following steps:
mixing N-isopropyl acrylamide, a copolymer, a cross-linking agent, a photoinitiator and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution to obtain N-isopropyl acrylamide resin; the mass of the 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution is 50-80% of the total mass of the N-isopropyl acrylamide and the 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution;
and sequentially carrying out photo-curing and drying on the N-isopropyl acrylamide resin to obtain the double-network NIPAM-based ionic gel.
Preferably, the copolymer is methacrylamide; the mass of the copolymer is 5-15% of the mass of the N-isopropyl acrylamide.
Preferably, the cross-linking agent is N, N-methylenebisacrylamide; the mass of the cross-linking agent is 5-7% of the mass of the N-isopropyl acrylamide.
Preferably, the photoinitiator is 1-hydroxycyclohexane phenyl ketone; the mass of the photoinitiator is 1-3% of that of the N-isopropyl acrylamide.
Preferably, the temperature of the mixing is 60-80 ℃; the mixing time is 5-60 min.
Preferably, the photocuring is performed under a high-pressure mercury lamp; the ultraviolet wavelength of the high-pressure mercury lamp is 360-420 nm, and the power is 50-100W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The light curing time is 3-10 min.
Preferably, the drying is performed in a vacuum environment; the drying temperature is 40-50 ℃; the drying time is 12-24 hours.
The invention provides the double-network NIPAM-based ionic gel prepared by the preparation method.
The invention provides a preparation method of double-network NIPAM-based ionic gel, wherein a double-network system is built in the ionic gel, and the ionic gel has excellent mechanical properties (mainly represented by tensile strength) through hydrogen bonds in chain segments and hydrogen bonds between ionic liquids, and the mechanical properties of the ionic gel are not reduced along with the increase of the tensile speed, but rather show an increasing trend.
Drawings
FIG. 1 is a graph of tensile strength versus tensile speed for a dual network NIPAM-based ionic gel prepared in example 2;
FIG. 2 is a graph of tensile strength versus tensile speed for a dual network NIPAM-based ionic gel prepared in example 1;
FIG. 3 is a plot of storage modulus as a function of axial force for the dual network NIPAM-based ionic gels prepared in example 2.
Detailed Description
The invention provides a preparation method of double-network NIPAM-based ionic gel, which comprises the following steps:
mixing N-isopropyl acrylamide, a copolymer, a cross-linking agent, a photoinitiator and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution to obtain N-isopropyl acrylamide resin; the mass of the 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution is 50-80% of the total mass of the N-isopropyl acrylamide and the 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution;
and sequentially carrying out photo-curing and drying on the N-isopropyl acrylamide resin to obtain the double-network NIPAM-based ionic gel.
The invention mixes N-isopropyl acrylamide, copolymer, cross-linking agent, photoinitiator and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution to obtain N-isopropyl acrylamide resin. In the present invention, the mass of the 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt ion solution is 50 to 80%, preferably 60 to 70% of the total mass of the N-isopropylacrylamide and 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt ion solution.
In the present invention, the copolymer is preferably methacrylamide; the mass of the copolymer is preferably 5 to 15% of the mass of N-isopropylacrylamide, more preferably 13%.
In the present invention, the crosslinking agent is preferably N, N-methylenebisacrylamide; the mass of the cross-linking agent is preferably 5-7% of the mass of the N-isopropyl acrylamide.
In the present invention, the photoinitiator is preferably 1-hydroxycyclohexane phenyl ketone; the mass of the photoinitiator is preferably 1 to 3% of the mass of N-isopropylacrylamide, more preferably 2.5%.
In the present invention, the temperature at which the N-isopropylacrylamide, the copolymer, the crosslinking agent, the photoinitiator and the 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt ion solution are mixed is preferably 60 to 80 ℃, more preferably 70 ℃; the mixing time is preferably 5 to 60 minutes.
After N-isopropyl acrylamide resin is obtained, the N-isopropyl acrylamide resin is sequentially subjected to photo-curing and drying to obtain the double-network NIPAM-based ionic gel. In the present invention, the photo-curing is preferably performed under a high-pressure mercury lamp; the ultraviolet wavelength of the high-pressure mercury lamp is preferably 360-420 nm, and the power is preferably50-100W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time for the photo-curing is preferably 3 to 10 minutes, more preferably 5 minutes. In the photocuring process, the material undergoes photopolymerization.
In the present invention, the photo-curing is preferably performed in a mold; the mold is preferably a polytetrafluoroethylene mold.
In the present invention, the drying is preferably performed in a vacuum environment; the drying temperature is preferably 40-50 ℃, more preferably 40 ℃; the drying time is preferably 12 to 24 hours.
The invention provides the double-network NIPAM-based ionic gel prepared by the preparation method. The tensile strength of the double-network NIPAM-based ionic gel provided by the invention increases with the increase of the tensile speed, and the elongation at break is basically kept unchanged; and the storage modulus of the dual network NIPAM-based ionic gel increases with increasing ambient pressure.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
2-g N-isopropylacrylamide was placed in 5g of 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt ion solution, and heated and stirred at 70℃to dissolve into a uniform liquid, and 259mg of methacrylamide (AAm), 100mg of N, N-Methylenebisacrylamide (MBA) and 50mg of the photoinitiator 1-hydroxycyclohexane phenyl ketone were added thereto, and stirred until a uniform solution was formed, to obtain a photocurable N-isopropylacrylamide resin;
the N-isopropylacrylamide resin was injected into a mold, and the resin was cured in a high-pressure mercury lamp (wavelength of ultraviolet light was 360nm, power was 50W/cm 2 ) Curing for 5min under light; and (3) drying the obtained N-isopropyl acrylamide ionic gel in a 40 ℃ oven for 12 hours in vacuum to obtain the double-network NIPAM-based ionic gel.
Example 2
Placing 2-g N-isopropyl acrylamide into 3g of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide ionic solution, heating and stirring at 70 ℃ to dissolve into uniform liquid, adding 259mg AAm,100mg MBA and 50mg of photoinitiator 1-hydroxycyclohexane phenyl ketone into the uniform liquid, and stirring until uniform solution is formed to obtain photocurable N-isopropyl acrylamide resin;
the N-isopropylacrylamide resin was injected into a mold, and the resin was cured in a high-pressure mercury lamp (wavelength of ultraviolet light was 360nm, power was 50W/cm 2 ) Curing for 5min under light; and (3) drying the obtained N-isopropyl acrylamide ionic gel in a 40 ℃ oven for 12 hours in vacuum to obtain the double-network NIPAM-based ionic gel.
Comparative example 1
2g of N-isopropyl acrylamide is placed in 10g of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution, heated and stirred at 70 ℃ to be dissolved into uniform liquid, 259mg AAm,100mg MBA and 50mg of photoinitiator 1-hydroxycyclohexane phenyl ketone are added into the uniform liquid, and the uniform solution is formed by stirring, so that the photo-curable N-isopropyl acrylamide resin is obtained;
the N-isopropylacrylamide resin was injected into a mold, and the resin was cured in a high-pressure mercury lamp (wavelength of ultraviolet light was 360nm, power was 50W/cm 2 ) Curing for 5min under light; the obtained N-isopropyl acrylamide ionic gel is dried in vacuum in a baking oven at 40 ℃ for 12 hours, and the ionic gel is obtained.
Test case
The ionic gels prepared in examples 1 to 2 and comparative example 1 were tested for the relationship between tensile strength and tensile speed using an electronic universal tester; the change in storage modulus was measured using a rheometer under different axial pressures.
FIG. 1 is a graph of tensile strength versus tensile velocity for a dual network NIPAM-based ionic gel prepared in example 2, with detailed data set forth in Table 1. As can be seen from fig. 1 and table 1, the dual network NIPAM-based ionic gel with an ionic liquid content (the content of 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonyl imide salt ion solution mass accounting for the total mass of the N-isopropylacrylamide and 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonyl imide salt ion solution) of 60% exhibited the characteristic that the tensile strength increased with increasing tensile speed at different tensile rates, while the elongation at break remained substantially unchanged.
TABLE 1 relationship between tensile Strength and tensile speed of double network NIPAM-based ionic gels prepared in example 2
Figure BDA0004030501620000051
FIG. 2 is a graph of tensile strength versus tensile velocity for the dual network NIPAM-based ionic gels prepared in example 1, with detailed data set forth in Table 2. As can be seen from fig. 2 and table 2, the dual network NIPAM-based ionic gel at 71% ionic liquid content exhibited the property that the tensile strength increased with increasing stretching speed, while the elongation at break remained substantially unchanged at different stretching rates.
TABLE 2 relationship between tensile Strength and tensile speed of double network NIPAM-based ionic gels prepared in example 1
Figure BDA0004030501620000052
FIG. 3 is a plot of storage modulus as a function of axial force for the dual network NIPAM-based ionic gels prepared in example 2, with detailed data set forth in Table 3. As can be seen from fig. 3 and table 3, the storage modulus of the dual network NIPAM-based ionic gels provided by the present invention increases with increasing external axial pressure.
TABLE 3 results of storage modulus as a function of axial force for the dual network NIPAM-based ionic gels prepared in example 2
Figure BDA0004030501620000061
The ionic gel prepared in comparative example 1 was softer in structure and failed to perform performance testing under the same tensile test conditions.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. A method for preparing a double network NIPAM-based ionic gel, comprising the steps of:
mixing N-isopropyl acrylamide, a copolymer, a cross-linking agent, a photoinitiator and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution to obtain N-isopropyl acrylamide resin; the mass of the 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution is 50-80% of the total mass of the N-isopropyl acrylamide and the 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ion solution;
and sequentially carrying out photo-curing and drying on the N-isopropyl acrylamide resin to obtain the double-network NIPAM-based ionic gel.
2. The method of claim 1, wherein the copolymer is methacrylamide; the mass of the copolymer is 5-15% of the mass of the N-isopropyl acrylamide.
3. The method of claim 1, wherein the cross-linking agent is N, N-methylenebisacrylamide; the mass of the cross-linking agent is 5-7% of the mass of the N-isopropyl acrylamide.
4. The method of claim 1, wherein the photoinitiator is 1-hydroxycyclohexane phenyl ketone; the mass of the photoinitiator is 1-3% of that of the N-isopropyl acrylamide.
5. The method of claim 1, wherein the temperature of mixing is 60-80 ℃; the mixing time is 5-60 min.
6. The method of claim 1, wherein the photocuring is performed under a high-pressure mercury lamp; the ultraviolet wavelength of the high-pressure mercury lamp is 360-420 nm, and the power is 50-100W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The light curing time is 3-10 min.
7. The method of claim 1, wherein the drying is performed in a vacuum environment; the drying temperature is 40-50 ℃; the drying time is 12-24 hours.
8. The dual network NIPAM-based ionic gel prepared by the method of any one of claims 1-7.
CN202211727087.3A 2022-12-30 2022-12-30 Double-network NIPAM-based ionic gel and preparation method thereof Pending CN116023585A (en)

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