CN115010862A - Preparation method of cellulose-based ionic conductive elastomer - Google Patents
Preparation method of cellulose-based ionic conductive elastomer Download PDFInfo
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- CN115010862A CN115010862A CN202210780602.8A CN202210780602A CN115010862A CN 115010862 A CN115010862 A CN 115010862A CN 202210780602 A CN202210780602 A CN 202210780602A CN 115010862 A CN115010862 A CN 115010862A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 71
- 239000001913 cellulose Substances 0.000 title claims abstract description 71
- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
- 239000000806 elastomer Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000005496 eutectics Effects 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 31
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 31
- 229960003178 choline chloride Drugs 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 235000010980 cellulose Nutrition 0.000 claims description 64
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 24
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 24
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 24
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 235000013877 carbamide Nutrition 0.000 claims description 9
- 229920002301 cellulose acetate Polymers 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- 229920001046 Nanocellulose Polymers 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229920006218 cellulose propionate Polymers 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- 229940045136 urea Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of a cellulose-based ionic conductive elastomer, which comprises the following steps: choline chloride, urea and cellulose react for 0.1-4 h at the temperature of 60-150 ℃ according to a certain proportion, and then a certain amount of methacrylic anhydride is added to react for 10-60 min at the temperature of 50-130 ℃ to prepare the eutectic solvent containing the modified cellulose macromonomer. The second step is that: and (2) reacting the eutectic solvent with the monomer A at 60-130 ℃ for 0.5-5 h according to a certain mass ratio, adding a certain mass of photoinitiator, continuing to react for 10-30 min, and then pouring the reaction solution into a mold for ultraviolet curing for 5-70 min to obtain the cellulose-based ionic conductive elastomer. The invention can simply and efficiently prepare the cellulose-based ion conductive elastomer with excellent performance, and the obtained elastomer can be used as an electrode material for a flexible self-powered sensor.
Description
Technical Field
The invention relates to a preparation method of a cellulose-based ionic conductive elastomer.
Background
In recent years, with the concern of people on the problems of environmental pollution, increasingly deficient petroleum resources and the like, the search for preparing functional chemicals, polymer materials and the like by using renewable resources instead of fossil petroleum resources becomes a hot point of research. The forest biomass resource is taken as a renewable resource with abundant reserves on the earth, has the advantages of wide source, low price, renewability and the like, and is an important candidate for petroleum substitution strategy in China.
Flexible conductive materials are conductive polymeric materials with deformability, elasticity, and toughness, and are generally able to withstand deformation to maintain electrical conductivity and other functional properties. Unlike metal and plastic conductive composites, conductive elastomer composites have excellent flexibility and stretchability, and are expected to be widely applied to various fields, such as artificial skin, sensors, energy storage, medical devices, and the like. Cellulose is a natural renewable biomass resource which exists in the largest amount in nature, has good mechanical properties, flexibility, hydrophilicity, chemical combination and stable stability, is widely applied to various fields, and can be effectively connected with a conductive polymer based on the characteristics of porosity and rich hydroxyl of the cellulose material.
The cellulose-based conductive material is prepared by compounding cellulose serving as a matrix with other compounds. Cellulose conductive materials with various structures and various varieties can be prepared through simple mechanical, chemical and biological treatment, so that the rapid development of flexible electronic devices is promoted. The development of the cellulose-based conductive material relieves the problem of environmental pollution caused by the traditional petroleum-based conductive material, and provides necessary foundation and solid guarantee for the development and wide application of green flexible electronic devices. Therefore, the cellulose-based ionic conductive elastomer can further expand the application range of cellulose and realize high-value utilization of the cellulose, and has great significance for further developing natural materials with abundant resources and environmental protection.
Disclosure of Invention
The invention aims to: one of the purposes of the invention is to provide a cellulose-based ion conductive elastomer which has excellent mechanical property, elastic property and conductivity, and can be used as an electrode material for a self-powered wearable sensor, so that the added value of cellulose is further improved, and the application range of the cellulose-based ion conductive elastomer is expanded; the invention also aims to provide a preparation method of the cellulose-based ionic conductive elastomer, which has the characteristics of convenience and high efficiency.
The technical scheme is as follows: the cellulose-based ionic conductive elastomer has the following structural general formula:
wherein R is a functional group characteristic of cellulose and is H, -CH 2 CH 3 、-COCH 3 、-CH 2 CH 2 OH、-CH 2 CH 2 CH 2 Any one of OH.
The invention also provides a preparation method of the cellulose-based ionic conductive elastomer, which comprises the following steps:
(1) reacting choline chloride, urea and cellulose at a certain ratio at 60-150 ℃ for 0.1-4 h, adding a certain mass of methacrylic anhydride, and reacting at 50-130 ℃ for 10-60 min to prepare a eutectic solvent containing a modified cellulose macromonomer;
(2) and (2) reacting the eutectic solvent and the monomer A at the temperature of 60-130 ℃ for 0.5-5 h according to a certain mass ratio, adding a certain mass of photoinitiator, continuing to react for 10-30 min, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 5-70 min under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
In the step (1), the mol ratio of choline chloride to urea is 1: 1-5, and the mass ratio of choline chloride to urea to cellulose is 1: 0.01-0.04.
Wherein the cellulose is any one of nano-cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, microcrystalline cellulose, cellulose propionate, hydroxypropyl methyl cellulose, etc.
In the step (1), the mass of the methacrylic anhydride is 0.5-4 times of the mass of the cellulose.
In the step (2), the mass ratio of the low eutectic solvent to the monomer A is 1: 0.4-2, and the mass of the photoinitiator is 1-5 wt% of the mass of the monomer A.
Wherein, the monomer A is any one of acrylic acid, acrylamide, methacrylic acid, hydroxymethyl acrylamide, hydroxyethyl acrylate and hydroxyethyl methacrylate, and the photoinitiator is any one of benzoin dimethyl ether, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
Has the advantages that:
(1) the preparation method of the cellulose-based ionic conductive elastomer has the characteristics of simplicity, high efficiency and green raw materials, the modified cellulose can obviously improve the mechanical property and the elastic property of the ionic conductive elastomer, and the performance of the elastomer can be effectively regulated and controlled by changing the content of the cellulose.
(2) The cellulose-based ionic conductive elastomer has important application value in the fields of strain sensors, flexible wearable self-powered sensors and the like as a novel conductive polymer, has important significance in further improving high-value utilization of cellulose, and can further expand the application range of cellulose.
Drawings
Fig. 1 is a graph showing the conductivity of the cellulose-based ion-conductive elastomer of example 1.
FIG. 2 is an infrared spectrum of microcrystalline cellulose and modified microcrystalline cellulose macromonomer in example 1.
Fig. 3 is a unidirectional tensile stress-strain curve of the cellulose-based ionic conductive elastomer of example 1.
Fig. 4 is a graph showing the cyclic elongation and elastic recovery of the cellulose-based ionic conductive elastomer of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials and reagents in the following examples are all commercially available.
Example 1: preparation of cellulose-based ion-conductive elastomer from microcrystalline cellulose
The first step is as follows: adding choline chloride, urea and microcrystalline cellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 2, and the mass ratio of [ total mass of choline chloride and urea ]/[ microcrystalline cellulose ] < 1: 0.01, reacting for 2.5h at 120 ℃, adding methacrylic anhydride with the mass of 1.5 times that of microcrystalline cellulose, reacting for 20min at 110 ℃, and preparing a eutectic solvent containing the modified microcrystalline cellulose macromonomer;
the second step is that: the method comprises the steps of reacting a eutectic solvent and acrylic acid according to the mass ratio of the eutectic solvent to the acrylic acid of 1: 0.5 at 95 ℃ for 2 hours, adding a photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone accounting for 2 wt% of the mass of the acrylic acid, continuing to react for 10 minutes, pouring a reaction liquid into a polytetrafluoroethylene mold, and curing under an ultraviolet lamp for 15 minutes to obtain the cellulose-based ion conductive elastomer.
Fig. 1 is the conductivity of the cellulose-based ion-conductive elastomer of example 1: the cellulose-based ion-conducting elastomer is connected into a circuit with a bulb, and the bright bulb shows the excellent conductivity of the cellulose-based ion-conducting elastomer.
FIG. 2 is an IR spectrum of microcrystalline cellulose and modified microcrystalline cellulose macromer in example 1: the modified microcrystalline cellulose macromonomer in the figure is 1719cm -1 The peak position corresponds to the absorption peak of ester bond C ═ O, 1471cm -1 These results indicate that the modified microcrystalline cellulose macromonomer was successfully prepared.
Fig. 3 is a unidirectional tensile stress-strain curve of the cellulose-based ion-conductive elastomer of example 1: as can be seen from the figure, the conductive elastomer has good mechanical properties, the mechanical strength is 1.11MPa, and the elongation at break is 884.22%.
FIG. 4 is a graph of cyclic stretch and elastic recovery for cellulose-based ionic conductive elastomer of example 1: from the figure, it can be found that the elastic recovery coefficient of the elastomer is as high as 97.3%, which shows that the elastomer has excellent elastic performance.
Example 2: preparation of cellulose-based ion-conductive elastomer from microcrystalline cellulose
The first step is as follows: adding choline chloride, urea and microcrystalline cellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 1, and the mass ratio of [ total mass of choline chloride and urea ]/[ microcrystalline cellulose ] < 1: 0.03, reacting for 2.5h at 150 ℃, adding methacrylic anhydride with the mass of 3 times of microcrystalline cellulose, reacting for 20min at 110 ℃, and preparing a eutectic solvent containing the modified microcrystalline cellulose macromonomer;
the second step is that: reacting a eutectic solvent and acrylamide according to the mass ratio of the eutectic solvent to the acrylamide of 1: 2 at 110 ℃ for 2h, adding a photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone accounting for 2 wt% of the mass of the acrylamide, continuing to react for 20min, pouring the reaction liquid into a polytetrafluoroethylene die, and curing for 70min under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
Example 3: preparation of cellulose-based ion-conductive elastomer from microcrystalline cellulose
The first step is as follows: adding choline chloride, urea and microcrystalline cellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 2, and the mass ratio of [ total mass of choline chloride and urea ]/[ microcrystalline cellulose ] < 1: 0.04, reacting for 2.5h at 90 ℃, adding methacrylic anhydride with the mass of 3 times of microcrystalline cellulose, reacting for 20min at 80 ℃, and preparing a eutectic solvent containing the modified microcrystalline cellulose macromonomer;
the second step is that: the method comprises the steps of reacting a eutectic solvent and methacrylic acid according to the mass ratio of the eutectic solvent to the methacrylic acid of 1: 1.5 at 95 ℃ for 4 hours, adding a photoinitiator benzoin dimethyl ether accounting for 5 wt% of the mass of the methacrylic acid, continuing to react for 10 minutes, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 60 minutes under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
Example 4: preparation of cellulose-based ion-conductive elastomer from hydroxypropyl methyl cellulose
The first step is as follows: adding choline chloride, urea and microcrystalline cellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 4, and the mass ratio of [ total mass of choline chloride and urea ]/[ hydroxypropyl methyl cellulose ] < 1: 0.01, reacting for 3 hours at 60 ℃, adding methacrylic anhydride with 2 times of mass of hydroxypropyl methyl cellulose, reacting for 30 minutes at 70 ℃, and preparing a eutectic solvent containing the modified hydroxypropyl methyl cellulose macromonomer;
the second step is that: the method comprises the steps of reacting a eutectic solvent and hydroxyethyl acrylate according to the mass ratio of the eutectic solvent to the hydroxyethyl acrylate of 1: 1 at 95 ℃ for 2 hours, adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone accounting for 2 wt% of the mass of the hydroxyethyl acrylate, continuing to react for 20 minutes, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 30 minutes under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
Example 5: preparation of cellulose-based ion-conductive elastomer by using nanocellulose
The first step is as follows: adding choline chloride, urea and nanocellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 5, and the mass ratio of [ total mass of choline chloride and urea ]/[ nanocellulose ] < 1: 0.04, reacting at 70 ℃ for 4 hours, adding methacrylic anhydride with the mass of 1.5 times that of the nanocellulose, reacting at 110 ℃ for 10 minutes, and preparing a eutectic solvent containing the modified nanocellulose macromonomer;
the second step is that: reacting the eutectic solvent and acrylic acid according to the mass ratio of the eutectic solvent to the acrylic acid of 1: 1 at 120 ℃ for 4 hours, adding a photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone accounting for 1 wt% of the mass of the acrylic acid, continuing to react for 10 minutes, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 30 minutes under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
Example 6: preparation of cellulose-based ion-conductive elastomer by using hydroxyethyl group
The first step is as follows: adding choline chloride, urea and hydroxyethyl cellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 2, and the mass ratio of [ total mass of choline chloride and urea ]/[ hydroxyethyl cellulose ] < 1: 0.03, reacting at 120 ℃ for 4 hours, adding methacrylic anhydride with the mass of 0.5 time of that of the hydroxyethyl cellulose, reacting at 60 ℃ for 40 minutes, and preparing a eutectic solvent containing the modified hydroxyethyl cellulose macromonomer;
the second step is that: reacting a eutectic solvent and acrylic acid according to the mass ratio of the eutectic solvent to the acrylic acid of 1: 0.5 at 95 ℃ for 2h, adding a photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone accounting for 2 wt% of the mass of the acrylic acid, continuing to react for 10min, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 15min under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
Example 7: preparation of cellulose-based ion-conductive elastomer by using carboxymethyl cellulose
The first step is as follows: adding choline chloride, urea and carboxymethyl cellulose into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ] < 1: 2, and the mass ratio of [ total mass of choline chloride and urea ]/[ carboxymethyl cellulose ] < 1: 0.03, reacting at 120 ℃ for 2.5h, adding methacrylic anhydride with 2 times of the mass of carboxymethyl cellulose, reacting at 100 ℃ for 30min, and preparing a eutectic solvent containing the modified carboxymethyl cellulose macromonomer;
the second step is that: and (2) reacting the eutectic solvent and hydroxymethyl acrylamide according to the mass ratio of the eutectic solvent to the hydroxymethyl acrylamide of 1: 2 at 95 ℃ for 2 hours, adding a photoinitiator 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone accounting for 4 wt% of the mass of the hydroxymethyl acrylamide, continuing to react for 30 minutes, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing under an ultraviolet lamp for 15 minutes to obtain the cellulose-based ion conductive elastomer.
Example 8: preparation of cellulose-based ion-conductive elastomer from cellulose acetate
The first step is as follows: adding choline chloride, urea and cellulose acetate into a round-bottom flask according to the molar ratio of [ choline chloride ]/[ urea ]/[ cellulose acetate ]/[ total mass of choline chloride and urea ]/[ cellulose acetate ]/[ 1: 0.03 ], reacting at 120 ℃ for 4 hours, adding methacrylic anhydride with the mass of 1.5 times that of the cellulose acetate, reacting at 110 ℃ for 20 minutes, and preparing a eutectic solvent containing a modified cellulose acetate macromonomer;
the second step is that: and (2) reacting the eutectic solvent and hydroxyethyl methacrylate at a mass ratio of [ eutectic solvent ]/[ hydroxyethyl methacrylate ] (1: 1) at 95 ℃ for 0.5h, adding a photoinitiator 2 wt% of the mass of the hydroxyethyl methacrylate, namely 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, continuing to react for 10min, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 30min under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer.
Tests show that the cellulose-based ion conductive elastomer prepared in the embodiments 1-8 has good mechanical property, conductivity and elastic property, and has important application value in the fields of strain sensors, flexible wearable self-powered sensors and the like.
Claims (2)
1. A cellulose-based ionic conduction elastomer is characterized by the following structural general formula:
wherein R is a functional group characteristic of cellulose and is H, -CH 2 CH 3 、-COCH 3 、-CH 2 CH 2 OH、-CH 2 CH 2 CH 2 Any one of OH.
2. A preparation method of a cellulose-based ionic conductive elastomer is characterized by comprising the following steps:
(1) reacting choline chloride, urea and cellulose at a certain ratio at 60-150 ℃ for 0.1-4 h, adding methacrylic anhydride with a certain mass to react at 50-130 ℃ for 10-60 min to prepare a eutectic solvent containing a modified cellulose macromonomer, wherein the molar ratio of the choline chloride to the urea is 1: 1-5, the mass ratio of the total mass of the choline chloride and the urea to the cellulose is 1: 0.01-0.04, the methacrylic anhydride with a certain mass is 0.5-4 times of the mass of the cellulose, and the cellulose is any one of nano cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, microcrystalline cellulose, cellulose propionate and hydroxypropyl methyl cellulose;
(2) reacting a eutectic solvent and a monomer A for 0.5-5 h at 60-130 ℃ according to a certain mass ratio, adding a certain mass of photoinitiator, continuing to react for 10-30 min, pouring the reaction liquid into a polytetrafluoroethylene mold, and curing for 5-70 min under an ultraviolet lamp to obtain the cellulose-based ion conductive elastomer, wherein the monomer A is any one of acrylic acid, acrylamide, methacrylic acid, hydroxymethyl acrylamide, hydroxyethyl acrylate and hydroxyethyl methacrylate, the eutectic solvent and the monomer A are (the eutectic solvent) and (the monomer A) are 1: 0.4-2 according to a certain mass ratio, and the photoinitiator is benzoin dimethyl ether, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl phenylpropanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, Any one of 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, wherein the photoinitiator with a certain mass accounts for 1-5 wt% of the monomer A.
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