CN108707252A - A kind of nano combined ionic liquid gel material and its preparation and the strain transducer based on the material - Google Patents
A kind of nano combined ionic liquid gel material and its preparation and the strain transducer based on the material Download PDFInfo
- Publication number
- CN108707252A CN108707252A CN201810548926.2A CN201810548926A CN108707252A CN 108707252 A CN108707252 A CN 108707252A CN 201810548926 A CN201810548926 A CN 201810548926A CN 108707252 A CN108707252 A CN 108707252A
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- China
- Prior art keywords
- ionic liquid
- liquid gel
- nano
- nano combined
- gel material
- Prior art date
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 120
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- -1 Wherein Polymers 0.000 claims description 43
- 238000005253 cladding Methods 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
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- 229920000615 alginic acid Polymers 0.000 claims description 8
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- 230000002441 reversible effect Effects 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical group O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 7
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 6
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- 150000002500 ions Chemical class 0.000 claims description 5
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
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- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
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- 239000011630 iodine Substances 0.000 claims description 3
- 150000003235 pyrrolidines Chemical class 0.000 claims description 3
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical class C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 claims description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 10
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000004044 response Effects 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
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- WICWEYHSADNZSA-UHFFFAOYSA-N 2-(3-methyl-2h-imidazol-1-yl)acetic acid Chemical compound CN1CN(CC(O)=O)C=C1 WICWEYHSADNZSA-UHFFFAOYSA-N 0.000 description 2
- GZDQGGOQFBLAOL-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl(=O)(=O)(=O)O.C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 GZDQGGOQFBLAOL-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 238000010494 dissociation reaction Methods 0.000 description 2
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- UFWKYSSJTOGTAN-UHFFFAOYSA-N fluoroform;tetrabutylazanium Chemical compound FC(F)F.CCCC[N+](CCCC)(CCCC)CCCC UFWKYSSJTOGTAN-UHFFFAOYSA-N 0.000 description 2
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 description 1
- XDZAFZVZTAGZHI-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;ethyl sulfate Chemical class CCOS([O-])(=O)=O.CC[NH+]1CN(C)C=C1 XDZAFZVZTAGZHI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000028399 Critical Illness Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 230000008846 dynamic interplay Effects 0.000 description 1
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- 230000035876 healing Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
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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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- G—PHYSICS
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- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract
The invention discloses a kind of high preparation methods for stretching selfreparing multifunctional nano compound ion liquid gel rubber material, ferriferrous oxide nano-particle is coated and is added in ionic liquid solution, sequentially add high polymer monomer, initiator, it stirs evenly to form mixed solution, pours into ultraviolet irradiation or heating in glass mold and obtain nano combined ionic liquid gel material.The ionic liquid gel material has both high tensile property and self-healing properties, while also having self-sticking, electric conductivity, magnetic responsiveness, anti-flammability and wide operating temperature section.The present invention provides a kind of resistance strains based on the multifunctional nano compound ion liquid gel rubber material simultaneously, the sensor can both detect very big strain, small strain can also be detected, and there is higher sensitivity, solve the problems, such as that traditional strain transducer cannot carry out very big strain detecting.
Description
Technical field
The invention belongs to high molecular material and flexible electronic technical field, more particularly to a kind of nano combined ionic liquid is solidifying
Glue material and its preparation and strain transducer based on the material.
Background technology
Ionic liquid gel is a kind of viscoplasticity macromolecule being swollen a large amount of ionic liquids in its Space network of polymer
Material.Due to it with thermal stability, chemical inertness, almost without saturated vapor pressure, good conductivity and wide electrochemical window
The advantages such as mouth, before ionic liquid gel has a wide range of applications in fields such as capacitor, energy cell, sensor and drivers
Scape.Ionic liquid gel inevitably will produce damage during long-time service, to cause error message even raw
Critically ill danger.Selfreparing ionic liquid gel is that one kind has the function of that polymer mesh structure damaged structure can be repaired and gel is special
The intellectual material of property.The performance for assigning ionic liquid gel selfreparing, significantly to promote safety in utilization and the service life of material
Provide a kind of economic and easily new method.
There are shifting contradictions for the mechanical property and self-healing properties of ionic liquid gel.In order to improve ionic liquid
The self-healing properties of gel are often to sacrifice its mechanical property as cost.In the ionic liquid gel reported at present, has and review one's lessons by oneself
The ionic liquid gel of renaturation energy has that mechanical property is excessively poor, bears larger stress；But it can bear centainly to answer
Power and the ionic liquid gel deformed upon and the function of often not having selfreparing.These defects significantly limit ionic liquid
Application of the body gel in new scientific and trechnolocial undertaking especially has the flexible electronic field of deformation demand.Currently, there has been no researchs to report
Road has both the preparation method of the multifunctional ion liquid gel rubber material of high tensile property and self-healing properties and is based on the material simultaneously
The strain transducer of material.With the appearance and fast development of flexible electronic product, the strain transducer of flexible extensible is got over
Carry out bigger demand.Therefore there is the ionic liquid of excellent mechanical property and self-healing properties simultaneously by chemical design
Gel rubber material has important engineering significance, also exactly flexible electronic field problem in the urgent need to address.
Invention content
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of high stretching selfreparing is multi-functional
Nano combined ionic liquid gel material and its preparation and the strain transducer based on the material, the technical principle of the preparation method
It is：Carboxyl in Fe (III) ion and polymer being dispersed in the ferriferrous oxide nano-particle in ionic liquid is formed
Dynamic reversible metal coordinate bond, reversible dissociation/combination of this dynamic key is so that there is ionic liquid gel independence (to be not necessarily to
External condition stimulate) repetition self-healing properties, disconnected during stretching, release after again can re-form reversible gold
Belong to coordinate bond, assigns the excellent mechanical property of the compound ion liquid gel and self-healing properties.
Dynamic reversible metal coordinate bond in material makes ionic liquid gel not only have excellent tensile property, elongation
Rate can reach 14 times, and with quick efficient self-repairability, at room temperature, 100% can repair its electric conductivity within 0.5 second
Can, the tensile stress selfreparing of 90.0%-97.6% and the tensile elongation selfreparing of 92.0%-98.4% are completed in 4 hours.
In addition, temperature can also influence the self-healing performance of ionic liquid nano-composite gel.The glass of ionic liquid nano-composite gel
It is very low to change transition temperatureTherefore, which (such as -25 DEG C) can realize selfreparing at a lower temperature, when
When temperature increases (such as 60 DEG C), self-healing properties improve.Meanwhile the ionic liquid nano-composite gel is assembled into resistance-type
Sensor realizes its application in flexible electronic field as strain transducer.The material overcomes the drawing of high molecular material
Stretch the contradiction between performance and self-healing properties, for the Multifucntional selfreparing flexible conducting material haveing excellent performance synthesis with
And the preparation of large deformation flexible pulling force sensor provides new approaches.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of nano combined ionic liquid gel material, including ferriferrous oxide nano-particle and polymer, wherein polymerization
Object can form dynamic reversible coordinate bond with Fe (III) ion on ferriferrous oxide nano-particle surface.
The polymer is 0.1wt%~10wt% of ferriferrous oxide nano-particle content.
The present invention also provides the preparation method of the nano combined ionic liquid gel material and answering based on the material
Become sensor, specifically comprises the following steps
Step 1, the cladding of ferriferrous oxide nano-particle.In inert gas (such as nitrogen) protects atmosphere, heating is gentle
Under slow stirring, polymer is added in the aqueous suspension of ferriferrous oxide nano-particle, it is poly- that continuation heating stirring obtains cladding
The ferriferrous oxide nano-particle aqueous suspension for closing object collects nano-particle with magnet, and drying is weighed；
Step 2, the preparation of reaction mixture.The four of the coated polymer that high polymer monomer, initiator and step 1 are obtained
Fe 3 O nano-particle is added in ionic liquid, is uniformly mixed and is obtained mixed liquor；
Step 3, the preparation of nano combined ionic liquid gel.Mixed liquor is poured into glass board mould, ultraviolet irradiation exists
(6~20 hours) are irradiated under ultraviolet lamp or receiving doped with ferriferrous oxide nano-particle is prepared in heating (1~10 hour)
Rice compound ion liquid gel rubber material.
Wherein, the polymer is alginate, polyvinyl alcohol (PVA), polyacrylamide (PAM), polymethyl
Sour (PMAA), poly hydroxy ethyl acrylate (PHEMA), polyvinyl acetate (PVAc), polyacrylonitrile (PAN), polystyrene
(PS) or polyvinylpyrrolidone (PVP).
The high polymer monomer is alginate (alginate, Alg), acrylamide (acrylamide, AAm), first
Base acrylic acid (methacrylic acid, MAA), 2- Methacrylamides (2-methylacrylamide, MAA), acrylic acid
(acrylic acid, AA), butyl acrylate (n-butyl acrylate, BA), ethyl acrylate (Ethyl Acrylate,
AA), N-isopropylacrylamide (N-isopropylacrylamide, NIPAm), hydroxyethyl methacrylate (hydroxyethyl
Methacrylate, HEMA), acrylonitrile (acrylonitrile, AN), styrene (styrene, ST) or N- vinyl pyrroles
Alkanone (N-Vinyl-2-pyrrolidone, NVP).
The ionic liquid is glyoxaline ion liquid, pyridine type ionic liquid, quaternary phosphonium salt ionic liquid, quaternary ammonium salt
Ionic liquid, pyrrolidines ionic liquid, piperidines ionic liquid, the ionic liquid with benzyl, sulfonic acid base class ionic liquid, hydroxyl
Base class ionic liquid, carboxyl class ionic liquid, alkenyl class ionic liquid halogen ionic liquid, tetrafluoroborate class ionic liquid
Body, hexafluoro-phosphate radical class ionic liquid or amino acid ion liquid.Such as 1- methyl imidazolium tetrafluoroborates, 1- ethyls -3-
Methylimidazole ethyl-sulfate salt, 1- ethyl -2,3- methylimidazoles toluenesulfonate, N- ethylpyridines bromide, N- ethyls -
3- picolines hexafluorophosphate, ethyl triphenyl phosphine perchlorate, tetrabutylammonium fluoroform sulphonate, N- ethyls, methyl pyrrole
Cough up alkane rhodanate, N- ethyls, methyl piperidine disulfate, 1- benzyl -3- methylimidazoles hexafluorophosphate, 1- sulfopropyls -3-
Methylimidazole inner salt, 1- hydroxyl butyl -2,3- methylimidazoles bromide, 1- carboxymethyl -3- methylimidazole bis-trifluoromethylsulfoandimides
Salt, 1- vinyl -3- methylimidazole dicyan amine salt or tetramethyl quaternary ammonium glycine ionic liquid etc..
The initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2- hydroxy-2-methyl -1- phenylacetones, benzene first
Acyl methyl formate or alkyl salt compounded of iodine.
In the step 1, the dosage of polymer is 0.1wt%~10wt% of ferriferrous oxide nano-particle, the step
In rapid 2, high polymer monomer dosage be nano combined ionic liquid gel material 1wt%~50wt%, the four of coated polymer
Fe 3 O nano-particle dosage is 0.1wt%~30wt% of nano combined ionic liquid gel material, and initiator amount is
The dosage of 0.01wt%~10wt% of high polymer monomer, ionic liquid are nano combined ionic liquid gel material
10wt%-90wt%.
In addition, the upper nano combined ionic liquid gel is cut into required shape as strain transducer.The present invention
The nano combined ionic liquid gel material can be used for resistance formula strain transducer, by nano combined ionic liquid gel
It is cut into required shape, and is connect with electrode material, as strain transducer.The principle of strain transducer provided by the invention is
Pressure resistance type strain transducer, i.e. the relative resistance variation of ionic liquid gel material are linear or index closes with strain variation
System.
In terms of nano combined ionic liquid gel material of the present invention is equally applicable in flexible electronic field.
The principle of the present invention：
The high selfreparing multifunctional nano compound ion liquid gel network that stretches of the present invention is matching based on dynamic reversible
Position key is constituted.Coordinate bond is on Fe (III) ions and polymeric chain on ferriferrous oxide nano-particle surface
The dynamic interaction of carboxylate radical, reversible dissociation/combination of this dynamic key is so that ionic liquid gel has without extraneous item
The repetition independence self-healing properties of part stimulation；In addition the incorporation of ferriferrous oxide nano-particle also gives gel magnetic response
Characteristic；And this multifunctional nano compound ion liquid gel also good characteristic with ionic liquid, such as wide temperature work
Make section, electric conductivity, anti-flammability and wide electrochemical window.Based on the strain transducer of this nano combined ionic liquid gel,
Belong to resistance strain, i.e., the relative resistance change of material is with the variation of strain is linear or exponential relationship.
Compared with prior art, the beneficial effects of the invention are as follows：
Compared with other ionic liquid gel materials, nano combined ionic liquid gel that the present invention prepares while having both
The characteristic of high stretch and selfreparing, elongation strain stimulate without external condition up to 1400%, selfreparing and efficiently (in rooms
Under temperature, 0.5 second can 100% repair its electric conductivity, in 4 hours complete 90.9% tensile stress selfreparing and
92.86% tensile elongation selfreparing), additionally there is magnetic responsiveness, can be driven under magnetic fields, conductivity magnitude
In 0.01~1S/m.When this nano combined ionic liquid gel material is applied to strain transducer, it can not only be bonded arbitrary
The testee of curved surface, and solve the problems, such as that traditional strain transducer strain length is shorter, extend strain transducer
Using measurement range, and it ensure that (gauge factor, GF=3~20 are calculated by GF=Δ R/R/ ε for high sensitivity
It arrives, Δ R represents increased resistance value when ε strains occur, R0Resistance value when representing without strain).
Description of the drawings
Fig. 1 is multi-functional Fe3O4The design preparation flow figure and mechanical property of@PAA/PAA ionic liquid gels and from
By processability schematic diagram.
Fig. 2 is high stretch (2a) and self-repairability (2b) displaying of the nano combined ionic liquid gel material of the present invention
Figure.
Fig. 3 is stretched (3a) to the nano combined sodium alginate ionic liquid gel sample of the present invention with electronic tensile machine
The result schematic diagram of (3b) is tested with self-healing properties, corresponds to embodiment 1.
Fig. 4 is the tack and conductivity of nano combined polymethylacrylic acid ionic liquid nano-composite gel.
Fig. 5 is the pressure sensing of nano combined polyacrylamide ionic liquid nano-composite gel.
Specific implementation mode
With reference to the embodiment embodiment that the present invention will be described in detail.
A kind of high stretching selfreparing multifunctional nano compound ion liquid gel rubber material of the present invention and answering based on the material
Become sensor.
Embodiment 1
With reference to 1a, 1b, 1c, 1d of figure 1, a kind of high stretching selfreparing multifunctional nano compound ion liquid gel of the present invention
The preparation process of material is as follows：
Step 1, the cladding of ferriferrous oxide nano-particle.In nitrogen protection atmosphere, at 80 DEG C, it is slowly stirred lower addition
The sodium alginate of 0.5wt% relative to ferriferrous oxide nano-particle quality continues stirring 60 minutes, obtains cladding alginic acid
The aqueous suspension of the ferriferrous oxide nano-particle of sodium collects nano-particle with magnet, and drying is weighed.
Step 2, the preparation of reaction mixture.Relative to gross mass be 20wt% polymeric hydantoin mosanom and
The ferriferrous oxide nano-particle of the above-mentioned cladding sodium alginate of 2.5wt% is added to the sub- liquid of 1- methyl imidazolium tetrafluoroborates
In, and the initiator ammonium persulfate for being 2.5wt% relative to the mass fraction of polymeric hydantoin mosanom is added, it is uniformly mixed and obtains
Mixed liquor.
Step 3, the preparation of nano combined ionic liquid gel.Mixed liquor is poured into the glass board mould for accompanying silica gel pad
In, it is placed in insulating box and heats 1 hour, the nano combined ionic liquid being prepared into doped with ferriferrous oxide nano-particle coagulates
Glue；It is with excellent mechanical property and free forming performance, as shown in the 1e and 1f of Fig. 1.
Extension test is carried out to the nano combined ionic liquid gel of the gained of dumbbell shaped with electronic tensile machine, such as the 2a of Fig. 2
It is shown.Nano combined ionic liquid gel can be stretched to 14 times of former length, and tensile break strength reaches 40kPa.Use knife blade
This nano combined ionic liquid gel is cut off, at room temperature after selfreparing 4h, repairing performance test is carried out with electronic tensile machine,
This nano combined ionic liquid gel can complete 90.9% tensile stress selfreparing and 92.86% tensile elongation is reviewed one's lessons by oneself
It is multiple.By sensor application on balloon, there is good response to the expansion of balloon.With the expansion of balloon, the resistance of sensor
It becomes larger, and then the expansion of balloon volume can be assessed, as shown in the 2b of Fig. 2.
Embodiment 2
A kind of high preparation process for stretching selfreparing multifunctional nano compound ion liquid gel rubber material of the present invention is as follows：
Step 1, the cladding of ferriferrous oxide nano-particle.In nitrogen protection atmosphere, at 80 DEG C, it is slowly stirred lower addition
The polyvinyl acetate of 1wt% relative to ferriferrous oxide nano-particle quality continues stirring 60 minutes, obtains cladding poly-vinegar
The aqueous suspension of the ferriferrous oxide nano-particle of vinyl acetate collects nano-particle with magnet, and drying is weighed.
Step 2, the preparation of reaction mixture.The high polymer monomer acetic acid second that the content relative to gross mass is 30wt%
The ferriferrous oxide nano-particle of the above-mentioned cladding polyvinyl acetate of enester and 1.5wt% is added to 1- ethyl -2,3- diformazans
In base imidazoles toluenesulfonate ionic liquid, and it is 5wt% to be added relative to the mass fraction of macromolecule vinylacetate
Initiator methyl benzoylformate, be uniformly mixed obtain mixed liquor.
Step 3, the preparation of nano combined ionic liquid gel.Mixed liquor is poured into the glass board mould for accompanying silica gel pad
In, ultraviolet lighting 7 hours is prepared into the nano combined ionic liquid gel doped with ferriferrous oxide nano-particle；
The 3a institutes of extension test such as Fig. 3 are carried out to the nano combined ionic liquid gel of the gained of dumbbell shaped with electronic tensile machine
Show, nano combined ionic liquid gel can be stretched to 11 times of former length, and tensile break strength reaches 71.3kPa.Use knife blade
This nano combined ionic liquid gel is cut off, at room temperature after selfreparing 4h, self-healing properties survey is carried out with electronic tensile machine
Examination, this nano combined ionic liquid gel can complete 70.46% tensile stress selfreparing and 75.4% tensile elongation certainly
It repairs.Applied on finger, also there is response very to digital flexion.Finger bends different angles, different resistance occurs and becomes
Change, and then good response is made to the bending degree of finger, as shown in the 3b of Fig. 3.
Embodiment 3
A kind of high preparation process for stretching selfreparing multifunctional nano compound ion liquid gel rubber material of the present invention is as follows：
Step 1, the cladding of ferriferrous oxide nano-particle.In nitrogen protection atmosphere, at 80 DEG C, it is slowly stirred lower addition
The polymethylacrylic acid of 5wt% relative to ferriferrous oxide nano-particle quality continues stirring 60 minutes, obtains coating poly- first
The aqueous suspension of the ferriferrous oxide nano-particle of base acrylic acid collects nano-particle with magnet, and drying is weighed.
Step 2, the preparation of reaction mixture.Relative to gross mass be 40wt% macromolecule methacrylic acid and
The ferriferrous oxide nano-particle of the above-mentioned cladding polymethylacrylic acid of 9wt% is added to 1- hydroxyl butyl -2,3- methylimidazoles
In the sub- liquid of bromide, and the initiator sodium peroxydisulfate for being 0.5wt% relative to the mass fraction of macromolecule methacrylic acid is added,
It is uniformly mixed and obtains mixed liquor.
Step 3, the preparation of nano combined ionic liquid gel.Mixed liquor is poured into the glass board mould for accompanying silica gel pad
In, it is placed in insulating box and heats 1 hour, the nano combined ionic liquid being prepared into doped with ferriferrous oxide nano-particle coagulates
Glue；
Extension test is carried out to the nano combined ionic liquid gel adhesion strength of the gained of dumbbell shaped with electronic tensile machine, such as
The 4a of Fig. 4,4b, shown in 4c.Nano combined ionic liquid gel is 207.4 ± 24.98N/m, nanometer to the adhesion strength of PDMS
Compound ion liquid gel is 347.3 ± 6.97N/m to the adhesion strength of Cu pieces.Increasing strain, the brightness of LED light is dimmed, this
Show the sensing capability in strain path of the sensor.This nano combined ionic liquid gel is cut off with knife blade
20 times, the conductivity of self-healing sample is restored to the 4e of conductivity such as Fig. 4 of raw sample in 0.5s, shown in 4f..
Embodiment 4
A kind of high preparation process for stretching selfreparing multifunctional nano compound ion liquid gel rubber material of the present invention is as follows：
Step 1, the cladding of ferriferrous oxide nano-particle.In nitrogen protection atmosphere, at 80 DEG C, it is slowly stirred lower addition
The polyacrylamide of 4wt% relative to ferriferrous oxide nano-particle quality continues stirring 60 minutes, obtains cladding polypropylene
The aqueous suspension of the ferriferrous oxide nano-particle of amide collects nano-particle with magnet, and drying is weighed.
Step 2, the preparation of reaction mixture.Relative to gross mass be 35wt% high polymer polyacrylamide and
The ferriferrous oxide nano-particle of the above-mentioned cladding polyacrylamide of 19wt% is added to 1- vinyl -3- methylimidazole cdicynanmides
In salt liquid, and the initiator alkyl salt compounded of iodine for being 7wt% relative to the mass fraction of macromolecule acrylamide, mixing is added
Uniformly obtain mixed liquor.
Step 3, the preparation of nano combined ionic liquid gel.Mixed liquor is poured into the glass board mould for accompanying silica gel pad
In, ultraviolet lighting 13 hours is prepared into the nano combined ionic liquid gel doped with ferriferrous oxide nano-particle；
It is self-assembled into stress strain gauge with the nano combined ionic liquid gel of gained, strain is cured less than 800% gel
It is respectively 3.82 and 3.96 to close front and back GF；Strain is located at 800%-1000%, and the front and back GF of gel healing is respectively 19.6 Hes
20.2 as shown in the 5a of Fig. 5.Compared to other, ionic liquid gel be self-assembled into stress strain gauge have very high sensitivity and
The 5b of prodigious deformation such as Fig. 5, shown in 5c.By sensor application on balloon, there is good response to the expansion of balloon, applies
In the 5d on finger, also having such as Fig. 5 of response very to digital flexion, shown in 5e.
In more embodiments, the polymer of coated ferriferrous oxide can also be polyvinyl alcohol, polyacrylic acid, poly- methyl
Hydroxy-ethyl acrylate, polyacrylonitrile, polystyrene, polyvinylpyrrolidone etc..High polymer monomer be not limited to alginate,
Vinylacetate, methacrylic acid, acrylamide can also be other kin carboxylic-acid substances, such as acrylic acid, third
Olefin(e) acid butyl ester, ethyl acrylate, acrylonitrile, styrene, vinyl pyrrolidone, hydroxyethyl methacrylate etc..Ionic liquid
Solvent can also be its alloytype ionic liquid, for example, 1- ethyl-3-methylimidazole ethyl-sulfates salt, N- ethylpyridines bromide, N-
Ethyl -3- picolines hexafluorophosphate, ethyl triphenyl phosphine perchlorate, tetrabutylammonium fluoroform sulphonate, N- ethyls, first
Base pyrrolidines rhodanate, N- ethyls, methyl piperidine disulfate, 1- benzyl -3- methylimidazoles hexafluorophosphate, 1- sulphurs third
Base -3- methylimidazoles inner salt, 1- carboxymethyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt, methyl quaternary ammonium glycine ionic liquid
Body etc..
The present invention be for the first time prepare while having both high stretch and self-repairability ionic liquid gel material and
This multifunctional ion liquid gel rubber material also has magnetic responsiveness, electric conductivity and anti-flammability and wide temperature operation interval.It should be from
Sub- liquid gel material has broad application prospects in flexible electronic field.
It is as follows the present invention also provides the strain transducer based on such material：
The nano combined ionic liquid gel is cut into strip as pressure resistance type strain transducer, material is occurring
During strain, respective change can occur for relative resistance, and the mechanical deformation of sensed object is used for this.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of nano combined ionic liquid gel material, which is characterized in that including ferriferrous oxide nano-particle and polymer,
Wherein, polymer can form dynamic reversible coordinate bond with Fe (III) ion on ferriferrous oxide nano-particle surface.
2. nano combined ionic liquid gel material according to claim 1, which is characterized in that the polymer is four oxidations
0.1wt%~10wt% of three-iron nanoparticle content.
3. the preparation method of nano combined ionic liquid gel material described in claim 1, which is characterized in that including walking as follows
Suddenly：
Step 1, the cladding of ferriferrous oxide nano-particle
It in inert gas shielding atmosphere, heats and is slowly stirred down, in the aqueous suspension of ferriferrous oxide nano-particle
Polymer is added, continues heating stirring and obtains the ferriferrous oxide nano-particle aqueous suspension of coated polymer, received with magnet
Collect nano-particle, drying is weighed；
Step 2, the preparation of reaction mixture
The ferriferrous oxide nano-particle for the coated polymer that high polymer monomer, initiator and step 1 obtain is added to ion
In liquid, it is uniformly mixed and obtains mixed liquor；
Step 3, the preparation of nano combined ionic liquid gel
Mixed liquor is poured into glass board mould, ultraviolet irradiation or heating are prepared doped with ferriferrous oxide nano-particle
Nano combined ionic liquid gel material.
4. the preparation method of nano combined ionic liquid gel material according to claim 3, which is characterized in that the polymerization
Object is alginate, polyacrylamide (PAM), polyvinyl alcohol (PVA), polymethylacrylic acid (PMAA), polymethylacrylic acid hydroxyl
Ethyl ester (PHEMA), polyvinyl acetate (PVAc), polyacrylonitrile (PAN), polystyrene (PS) or polyvinylpyrrolidone
(PVP)。
5. the preparation method of nano combined ionic liquid gel material according to claim 3, which is characterized in that the high score
Sub- monomer is alginate (alginate, Alg), acrylamide (acrylamide, AAm), methacrylic acid
(methacrylic acid, MAA), 2- Methacrylamides (2-methylacrylamide, MAA), acrylic acid (acrylic
Acid, AA), butyl acrylate (n-butyl acrylate, BA), ethyl acrylate (Ethyl Acrylate, AA), isopropyl
Acrylamide (N-isopropylacrylamide, NIPAm), hydroxyethyl methacrylate (hydroxyethyl
Methacrylate, HEMA), acrylonitrile (acrylonitrile, AN), styrene (styrene, ST) or N- vinyl pyrroles
Alkanone (N-Vinyl-2-pyrrolidone, NVP).
6. the preparation method of nano combined ionic liquid gel material according to claim 3, which is characterized in that the ion
Liquid is glyoxaline ion liquid, pyridine type ionic liquid, quaternary phosphonium salt ionic liquid, ion liquid of quaternaries, pyrrolidines
Class ionic liquid, piperidines ionic liquid, the ionic liquid with benzyl, sulfonic acid base class ionic liquid, hydroxy kind ionic liquid, carboxylic
Base class ionic liquid, alkenyl class ionic liquid, halogen ionic liquid, tetrafluoroborate class ionic liquid, hexafluoro-phosphate radical class
Ionic liquid or amino acid ion liquid；The initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2- hydroxyl -2- first
Base -1- phenylacetones, methyl benzoylformate or alkyl salt compounded of iodine.
7. special according to the preparation method of nano combined ionic liquid gel material described in claim 3~6 any claim
Sign is, in the step 1, the dosage of polymer is 0.1wt%~10wt% of ferriferrous oxide nano-particle, the step
In 2, high polymer monomer dosage is 1wt%~50wt% of nano combined ionic liquid gel material, four oxygen of coated polymer
Change 0.1wt%~30wt% that three Fe nanometer particles dosages are nano combined ionic liquid gel material, initiator amount is height
0.01wt%~10wt% of molecule monomer, the dosage of ionic liquid are the 10wt%- of nano combined ionic liquid gel material
90wt%.
8. the strain transducer based on nano combined ionic liquid gel material described in claim 1.
9. the strain transducer of nano combined ionic liquid gel material according to claim 8, which is characterized in that by nanometer
Compound ion liquid gel is cut into required shape, and is adhesively joined with electrode material.
10. application of the nano combined ionic liquid gel material in terms of flexible electronic field described in claim 1.
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| CN112629399A (en) * | 2020-11-24 | 2021-04-09 | 南京航空航天大学 | Flexible sensing element of polyvinyl chloride ionic gel and preparation method thereof |
| CN112629399B (en) * | 2020-11-24 | 2022-04-22 | 南京航空航天大学 | Flexible sensing element of polyvinyl chloride ionic gel and preparation method thereof |
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