CN106750424B - Flexible air-sensitive film and its preparation method and application - Google Patents
Flexible air-sensitive film and its preparation method and application Download PDFInfo
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- CN106750424B CN106750424B CN201611025794.2A CN201611025794A CN106750424B CN 106750424 B CN106750424 B CN 106750424B CN 201611025794 A CN201611025794 A CN 201611025794A CN 106750424 B CN106750424 B CN 106750424B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 38
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000001052 transient effect Effects 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 22
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 22
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 25
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 14
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000002687 intercalation Effects 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920006267 polyester film Polymers 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 9
- 125000001118 alkylidene group Chemical group 0.000 abstract description 6
- 230000000007 visual effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002463 transducing effect Effects 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 106
- 239000010408 film Substances 0.000 description 99
- 239000007789 gas Substances 0.000 description 24
- 229910052961 molybdenite Inorganic materials 0.000 description 21
- 150000001721 carbon Chemical group 0.000 description 20
- 241000446313 Lamella Species 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 230000004044 response Effects 0.000 description 10
- 230000008859 change Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910006247 ZrS2 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- -1 methylene, propylidene Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08F138/00—Homopolymers of compounds having one or more carbon-to-carbon triple bonds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The present invention provides a kind of flexible air-sensitive film, the flexibility air-sensitive film is combined by transient metal sulfide two-dimensional material and polybutadiene alkynes, and the polybutadiene alkynes is formed by diacetylene class monomer through ultraviolet polymerization；Wherein, shown in the general structure such as formula (I) of the diacetylene class monomer:In formula (I), R1For aryl, carbon atom number be 5-20 alkyl or carbon atom number be 1-10 naphthenic base, R2The alkylidene or bivalent substituted or unsubstituted aryl for being 3-20 for singly-bound, carbon atom number.The flexibility air-sensitive film has cooperateed with the advantage of both transient metal sulfide two-dimensional material and polybutadiene alkynes, and the Coordination Adsorption behavior of organic steam can be converted to visual transducing signal, realizes and senses to the specific efficient of organic steam.The present invention also provides the preparation method of the flexibility air-sensitive film and its applications in organic steam detection.
Description
Technical field
The present invention relates to organic steam sensing and device arts more particularly to a kind of flexible air-sensitive film and its preparations
Methods and applications.
Background technique
The raising of fast development and industrialization, the level of urbanization recently as social economy, atmosphere polluting problem
It is increasingly serious.Function admirable, portable, fast and stable gaseous contamination detection technique have effective control and control atmosphere pollution
It is significant.The source volatile organic compounds (Volatile Organic Compounds, VOCs, organic steam) is wide,
Harm is big, migration is fast, it has also become the key points and difficulties of air monitoring.For example, DMF (dimethylformamide) can be used as it is organic
Solvent and raw material are for a series of products for living with industrial consumption such as insecticide, hormone, dyestuff, synthetic fibers.It is
Colourless, light ammonia odor may also damage eye, skin and the irritating effect of respiratory tract to fetus；Its steam and air hold
Easily, open fire, high fever explosibility are met.Therefore, very necessary to the detection of the VOCs such as DMF.
The current detection in relation to VOCs mainly uses the large-scale expensive equipments such as gas-chromatography, gas chromatography mass spectrometry to carry out, inconvenient
In progress field assay and it is difficult to large-scale application.It yet there are no the portable gas biography that can carry out the VOCs such as DMF detection
Sensor.
Lipoid containing diacetylene structure can gather under ultraviolet light after formation high-sequential is closely spaced
Close the polybutadiene alkynes structure for forming blue.Polybutadiene alkynes (PDA) class conjugated highpolymer has unique electronics and optical property,
Under by the stimulation of the external environments such as organic solvent, temperature, pressure, electricity or pH, color can occur to change accordingly, make it
Unique advantage is shown in photoelectricity and sensor field.Since PDA in 1993 is used for virus sensing for the first time, numerous researchs
Worker utilizes the specific response property of polybutadiene alkynes molecule, as signal mark molecule, by the combination of itself and object
Behavior quantitative expression is visual optical signalling.At present the optical sensor based on PDA class conjugated highpolymer mainly with
The form of PDA vesica, the bluk recombination of PDA lipid or PDA nano-complex is sensed, and functional modification process is more complex, and
And it is not portable, it is mainly used for liquid-phase system sensing, it is weaker to the adsorption capacity of gas molecule, it is not suitable for gas phase sensing.
Therefore, it is necessary to provide a kind of Portable gas dependent sensor and preparation method thereof for being suitable for VOCs (such as DMF).
Summary of the invention
In view of this, the flexibility air-sensitive film is by Transition Metal Sulfur the present invention provides a kind of flexible air-sensitive film
Compound two-dimensional material is combined with polybutadiene alkynes, and the polybutadiene alkynes is formed by diacetylene class monomer through ultraviolet polymerization, described
Flexible air-sensitive film has cooperateed with the advantage of both transient metal sulfide two-dimensional material and polybutadiene alkynes, can be by organic steam
The Coordination Adsorption behavior of (such as to DMF) is converted to visual transducing signal, realizes and passes to the specific efficient of organic steam
Sense.The present invention also provides the preparation method of the flexibility air-sensitive film and its applications in organic steam detection.
First aspect present invention provides a kind of flexible air-sensitive film, and the flexibility air-sensitive film is by transient metal sulfide
Two-dimensional material is combined with polybutadiene alkynes, and the polybutadiene alkynes is formed by diacetylene class monomer through ultraviolet polymerization；Wherein, described
Shown in the general structure such as formula (I) of diacetylene class monomer:
In formula (I), R1For aryl, carbon atom number be 5-20 alkyl or carbon atom number be 3-10 naphthenic base, R2For singly-bound, carbon
Atomicity is the alkylidene of 3-20, or is bivalent substituted or unsubstituted aryl.
Preferably, the transient metal sulfide two-dimensional material intercalation be distributed in the diacetylene class monomer polymerization at it is poly-
In diacetylene film, the flexible air-sensitive film of porous structure is formed.In the application, the polybutadiene alkyne film is wrapped in institute
Transient metal sulfide two-dimensional material surface is stated, the transient metal sulfide two-dimensional material is distributed in PDA polymer film, shape
At random intercalation configuration, the random intercalation of the transient metal sulfide two-dimensional material forms more in the flexibility air-sensitive film
Pore structure.
Preferably, the aperture of the porous structure of the flexible air-sensitive film is 0.1-100 μm.
It is further preferred that the aperture is 0.2-50 μm.More preferably 1-20 μm.
Preferably, the transient metal sulfide two-dimensional material and the molar ratio of diacetylene class monomer are (0.01-0.5):
1.Further preferably (0.02-0.46): 1.
Preferably, the mass ratio of the transient metal sulfide two-dimensional material and diacetylene class monomer is (0.01-0.2):
1。
In the application, the transient metal sulfide two-dimensional material is the transient metal sulfide after removing, is two-dimensional slice
Layer structure, thickness degree is in 1-100nm.It can be the nanometer material of the complete crystal plane structure of the controllable two dimension of single layer, bilayer and multilayer
Material.
Still optionally further, the transient metal sulfide two-dimensional material includes molybdenum disulfide MoS2, tungsten disulfide WS2, two
Vulcanize zirconium ZrS2, titanium disulfide TiS2With vanadium disulfide VS2One of or it is a variety of.
It is highly preferred that the transient metal sulfide two-dimensional material is molybdenum disulfide MoS2, tungsten disulfide WS2Or curing
Vanadium VS2。
In the application, the alkyl is saturated hydrocarbyl, refers to that the hydrogen atom combined on carbon atom in alkane molecule has 1
Alkyl, such as methyl, ethyl, isopropyl made of after being removed etc.；The alkylidene, refers in alkane molecule and ties on carbon atom
The hydrogen atom of conjunction have 2 be removed after made of alkyl, such as methylene, propylidene etc..
The divalent aryl refers to institute's shape after removing 2 hydrogen atoms on the aromatic core carbon or other carbon atoms of any aromatic hydrocarbon molecule
At group general name.Such as: phenylene2- naphthyleneThe hydrogen atom combined on the C atom in the divalent aryl can also by hetero atom,
Containing replaced heteroatomic group, such as All
Belong to such.
In the application, R2It can be the alkylidene that carbon atom number is 3-20, i.e. R2It can be-(CH2)n(n be 3-20 just
Integer) linear chain or branched chain alkylidene.It is preferred that the straight-chain alkyl-sub for being 3-20 at carbon atom number.
It is further preferred that the R2The straight-chain alkyl-sub for being 10-16 for carbon atom number.
Work as R2When for singly-bound, it is equivalent to-COOH and is directly connected directly with the main structure of diacetylene, at this point, the fourth two
The general structure of acetylenic monomer is
In the application, R1It can be the linear or branched alkyl group that carbon atom number is 5-20.It is preferred that being 5-20 at carbon atom number
Straight chained alkyl.
It is further preferred that the R1The linear or branched alkyl group for being 8-16 for carbon atom number.
In an embodiment of the present invention, the diacetylene class monomer is 10,12-, bis- pentadecane diacetylenic acid (PCDA)；It is tied
Structure formula isAt this point, R1It is for carbon atom number
12 straight chained alkyl, R2For-(CH2)8Straight-chain alkyl-sub.
In an embodiment of the present invention, the diacetylene class monomer is 5,7-, 16 carbon diacetylenic acid；Its structural formula isAt this point, R1The straight chained alkyl for being 8 for carbon atom number, R2For-(CH2)3Straight-chain alkyl-sub.
In an embodiment of the present invention, the diacetylene class monomer is 10,12-, 17 diacetylenic acid；Its structural formula isAt this point, R1For carbon atom number
For 14 straight chained alkyl, R2For-(CH2)8Straight-chain alkyl-sub.
In an embodiment of the present invention, the diacetylene class monomer is 10,12-, 23 acetylenic acid；Its structural formula isAt this point, R1The straight chain alkane for being 10 for carbon atom number
Base, R2For-(CH2)8Straight-chain alkyl-sub.
In an embodiment of the present invention, the diacetylene class monomer is 10,12-, 29 diacetylenic acid；Its structural formula isAt this point, R1For carbon original
The straight chained alkyl that subnumber is 16, R2For-(CH2)8Straight-chain alkyl-sub.
In an embodiment of the present invention, the diacetylene class monomer is 2,4-, 15 diacetylenic acid；Its structural formula isAt this point, R1The straight chained alkyl for being 10 for carbon atom number, R2For singly-bound.
In an embodiment of the present invention, the diacetylene class monomer is 2,4-, 17 diacetylenic acid；Its structural formula isAt this point, R1The straight chained alkyl for being 12 for carbon atom number, R2For list
Key.
In an embodiment of the present invention, the diacetylene class monomer is 2,4-, 19 diacetylenic acid；Its structural formula isAt this point, R1The straight chained alkyl for being 14 for carbon atom number, R2
For singly-bound.
In an embodiment of the present invention, the diacetylene class monomer is 2,4-, 21 diacetylenic acid；Its structural formula isAt this point, R1The straight chain alkane for being 16 for carbon atom number
Base, R2For singly-bound.
First aspect present invention provide flexible air-sensitive film, be by after removing transient metal sulfide two-dimensional material with
Polybutadiene alkynes is combined, and the polybutadiene alkynes is formed by diacetylene class monomer through ultraviolet polymerization, the transient metal sulfide
Two-dimensional material intercalation the diacetylene class monomer polymerization at polybutadiene alkyne film in, the flexible air-sensitive for forming porous structure is thin
Film.The flexibility air-sensitive film has cooperateed with the advantage of both transient metal sulfide two-dimensional material and polybutadiene alkynes, wherein described
Transient metal sulfide two-dimensional material has good flexible and ductility, is the ideal material of flexible, the wearable device of building,
Also there is excellent assembling property, high-specific surface area, organic steam (especially DMF gas molecule) can be shown stronger
Coordination and adsorption capacity, effectively increase the transparency of flexible air-sensitive film and the response performance to organic gas；Diacetylene class
The polybutadiene alkynes structure that monomer is formed has the functional site combined to organic steam specificly-response, the flexibility air-sensitive film
The Coordination Adsorption behavior of organic steam (such as to DMF) can be converted to visual transducing signal, and (color is by blue to red change
Change), it realizes and the specific efficient of organic steam is sensed.The transient metal sulfide two-dimensional material of addition effectively increases flexibility
The transparency and gas response performance of air-sensitive film.
Second aspect of the present invention provides a kind of preparation method of flexible air-sensitive film, comprising the following steps:
(1) that diacetylene class monomer shown in formula (I) and transient metal sulfide two-dimensional material are added to first is organic molten
In agent, through ultrasonic disperse and after mixing evenly, precursor solution is obtained；Wherein, first organic solvent includes ethyl alcohol, methanol
Or acetone；
In formula (I), R1For aryl, carbon atom number be 5-20 alkyl or carbon atom number be 3-10 naphthenic base, R2For singly-bound, carbon
Atomicity is the alkylidene of 3-20 or the aryl of bivalent substituted；
(2) precursor solution is dropped to or is coated in the flexible substrates to hydrophilic treated, sufficiently after drying, then passed through
Ultraviolet polymerization forms flexible air-sensitive film described in first aspect present invention in the flexible substrates.
Preferably, in the precursor solution, the transient metal sulfide two-dimensional material is rubbed with diacetylene class monomer
You are than being (0.01-0.5): 1.
It is further preferred that concentration of the transient metal sulfide two-dimensional material in the precursor solution is
0.05-5mg/mL。
It is alternatively possible to which diacetylene class monomer shown in the formula (I) to be first dispersed in the first solvent, obtain fourth two
Acetylenic monomer solution；The transient metal sulfide two-dimensional material after removing is added into the diacetylene class monomer solution again；?
Diacetylene class monomer shown in formula (I) can be dispersed in first with the transient metal sulfide two-dimensional material after removing respectively has
In solvent, corresponding solution is obtained, then diacetylene class monomer solution and transient metal sulfide two-dimensional material solution are pressed one
Certainty ratio is mixed.Carry out ultrasonic disperse and stirring operation again later.
Wherein, the precursor solution is dropped to or is coated in the flexible substrates to hydrophilic treated, sufficiently after drying, shape
At flexible air-sensitive film presoma；After the flexibility air-sensitive film presoma carries out in-situ polymerization under ultraviolet light, described soft
Property substrate on form the flexible air-sensitive film.
The flexible substrates are transparent, and have certain flexibility, so that following process is at wearable device.
Preferably, the flexible and transparent substrate includes polyester (PET) film, polyimides (PI) film or polyvinyl alcohol
(PVA) film, but not limited to this.
It is further preferred that the transient metal sulfide two-dimensional material is made with the following method:
Transient metal sulfide material to be stripped is added in the second organic solvent, the ultrasound 12- under 500-1800w
72 hours；After ultrasound, with 1500-6000rpm low-speed centrifugal 5-30min, collect supernatant, and to the supernatant with
The speed high speed centrifugation 30-120min of 9000-15000rpm, collects body precipitating, and filtering is dried in vacuo in 60-100 DEG C, obtains
Solids, the solids are the transient metal sulfide two-dimensional material after removing.
Wherein, second organic solvent (polar) includes N-Methyl pyrrolidone (NMP), dimethyl sulfoxide
(DMSO), dimethylformamide (DMF), 1,3- dimethyl -2- imidazolidinone (DMI) or tetrahydrofuran (THF).
It is further preferred that concentration of the transient metal sulfide material to be stripped in second organic solvent
For 0.5-5mg/mL.
Optionally, the power of ultrasonic treatment described in step (1) is 1000-1800W, ultrasonic time 10-30min.Institute
Stirring is stated to be vigorously stirred, the revolving speed of the stirring is 500-1000rpm/min.
Preferably, the hydrophilic treated of the flexible substrates is handled using oxygen plasma.
Further, using O2When plasma (plasma) carries out hydrophilic treated, O2The power of plasma instrument is 100-
500W, time are 1-5min (more preferably 2min).
In the application, by the precursor solution it is sufficiently dry after ultraviolet polymerization again, rather than it is precursor solution is direct
Ultraviolet polymerization can will affect the flexible air-sensitive film discoloration obtained after polymerization in this way to avoid the solvent of remaining.
Preferably, the drying is carried out at 40-80 DEG C.More preferably carry out under vacuum conditions.
Preferably, the time of the ultraviolet polymerization is 2-30min.
It is further preferred that the time of the ultraviolet polymerization is 5-20min or 8-18min.
The preparation method for the flexible air-sensitive film that second aspect of the present invention provides, preparation method is simple to operation, obtained
Flexible air-sensitive film, it is flexible that preferably the flexible air-sensitive film is placed in the atmosphere containing organic steam (such as DMF), it is logical
It crosses the color change for visually observing film or quantitatively calculates the flexible air-sensitive film and change in the optical property of visible region, it can
The content of qualitative or quantitative assessment organic steam.Portable visualization, wearable biography can be made in the flexibility air-sensitive film
Inductor component realizes real-time, the quick detection to organic steam, to fill up in the prior art to the sky of organic steam sensing
It is white.
Third aspect present invention provides a kind of gas sensor, and the gas sensor includes flexible sensing element, institute
Stating flexible sensing element includes the flexible air-sensitive film in flexible substrates and flexible substrates, is had on the flexibility air-sensitive film
The surface region contacted can be formed with gas to be sensed by having.That is, the flexibility air-sensitive film is non-contact with the flexible substrates
One side (upper surface) partly or entirely exposure (exposed to ambient enviroment), to allow flexible sensing element and gas phase to be sensed
Contact.
Preferably, the gas sensor is wearable.The wearable device is worn to (such as right containing organic steam
DMF in environment), the flexible air-sensitive film can be assessed using visual method in the color change of visibility region, is realized to this
The quick detection or early warning of organic steam in environment.
In an embodiment of the present invention, the flexible sensing element directly can be provided directly as ring structure (will
The flexible air-sensitive film formed on a flexible substrate passes through gluing cyclization).
In another embodiment of the present invention, the gas sensor further includes gas sensor ontology, the sensing
(e.g. chimeric) is arranged among the gas sensor ontology in element.The ontology may be constructed such that annular, arc, piece
Shape, spherical shape and other structures.In addition, can also be integrated with other intelligent devices etc. in the gas sensor.
Fourth aspect present invention additionally provides as described in the first aspect of the invention or such as second aspect of the present invention preparation
Flexibility air-sensitive film made from method or gas sensor as described in the third aspect of the present invention are in gas sensor detection
Using.Application preferably in the detection of DMF steam.
The beneficial effect comprise that
1, the flexible air-sensitive film is formed by transient metal sulfide two-dimensional material and diacetylene class monomer ultraviolet polymerization,
The flexibility air-sensitive film has high transparency, high flexibility, shows visual response characteristic, the transition of addition to organic steam
Metal sulfide two-dimensional material can also effectively improve the transparency and gas response performance of flexible air-sensitive film；
2, the flexible air-sensitive film is flexible, good to the responsiveness of organic steam, organic suitable for gaseous contamination
Real-time, the quick early warning of steam, the flexibility air-sensitive film are easy to integrated with existing electronic equipment, are expected to develop wearable, more function
Energy property device is avoided using high-cost large-scale detection device；
3, in the preparation method of the flexible air-sensitive film, cost of material is low, and preparation process is simple, condition is easily-controllable, is easy to
Realize industrialization.
Detailed description of the invention
Fig. 1 is the electromicroscopic photograph of the flexible air-sensitive film obtained in embodiment 1；Wherein, (A) is stereoscan photograph
(SEM), (B), (C) are transmission electron microscope photo (TEM)；
Ultra-violet absorption spectrum of the Fig. 2 for the flexible air-sensitive film obtained in embodiment 1-4 before and after being sensed to DMF
Variation diagram；
Fig. 3 is flexibility, the stability (A) of the obtained flexible air-sensitive film in embodiment 1, and to gas with various
Selectivity test result (B)；
Ultraviolet suction of the Fig. 4 for the flexible air-sensitive film obtained in embodiment 1 to a series of DMF sensing front and back of concentration
Receive the variation diagram (A) of spectrum and the linearity curve (B) of fitting；
Fig. 5 is the schematic diagram of wearable device constructed by the flexible air-sensitive film of the embodiment of the present invention.
Specific embodiment
With reference to the accompanying drawings and embodiments, technical scheme in the embodiment of the invention is clearly and completely described, shows
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Apply example, those of ordinary skill in the art's every other embodiment obtained without making creative work, all
Belong to the scope of protection of the invention.It should be pointed out that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
It is of the invention in limiting.
Embodiment 1
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
(1) 1g MoS is weighed2Solid, which is added in 500mL NMP, carries out ultrasound 72h, wherein the power of ultrasound is 500W, surpasses
After sound, 30min is centrifuged with the revolving speed of 5000rpm, collects supernatant after centrifugation；By gained supernatant again with 13000rpm from
Heart 1h collects precipitating, dry to get the lamella MoS for arriving removing after cleaning repeatedly2Two-dimensional material；
(2) the above-mentioned lamella MoS of 1mg is taken21mL ethyl alcohol is added in two-dimensional material, and ultrasonic disperse is uniform, obtains MoS2Dispersion
Liquid；Claim 10,12-, the bis- pentadecane diacetylenic acid (PCDA) of 10mg to be dissolved in 1mL ethanol solution, after filtering, obtains PCDA monomer solution；
(3) by the above-mentioned MoS of 10 μ L2Dispersion liquid is mixed with the PCDA solution of 100 μ L, with the power ultrasound 10min of 1200W
After be vigorously agitated again 30min, obtain MoS2/ PCDA precursor solution；
(4) PET film is taken, O is carried out under 200w power2After plasma plasma handles 2min, hydrophilic treated is obtained
PET film afterwards；By MoS2/ PCDA precursor solution is spun on hydrophilic PET film, dry in 60 DEG C of drying convection ovens
It is dry for 24 hours；This film is ordered to get to the flexible air-sensitive film of blue homogeneous transparent using 252nm ultraviolet lighting 10min later
Entitled PDA/MoS2-1。
Fig. 1 is the electromicroscopic photograph of the flexible air-sensitive film obtained in embodiment 1.From figure 1 it appears that can obtain
PDA and MoS2Composite construction, PDA polymer film is wrapped in MoS2Sheet surfaces, MoS2Lamella is distributed in PDA polymer film,
Form random intercalation configuration, MoS2The random intercalation of lamella the flexibility air-sensitive film formed porous structure, be conducive to for
The sensing of gas molecule provides action site.The aperture of the porous structure of the flexibility air-sensitive film is 0.5-20 μm.
Embodiment 2
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
(1) method same as Example 1 is used, the lamella MoS of removing is obtained2Two-dimensional material；
(2) the above-mentioned lamella MoS of 1mg is taken21mL ethyl alcohol is added in two-dimensional material, and ultrasonic disperse is uniform, obtains MoS2Dispersion
Liquid；Claim the PCDA of 10mg to be dissolved in 1mL ethanol solution, be filtered to remove oligomer, obtains PCDA monomer solution；
(3) by the above-mentioned MoS of 20 μ L2Dispersion liquid is mixed with the PCDA solution of 100 μ L, with the power ultrasound 10min of 1200W
After be vigorously agitated again 30min, obtain MoS2/ PCDA precursor solution；
(4) PET film is taken, after plasma hydrophilic treated, by MoS2/ PCDA precursor solution is spun on hydrophilic PET
On film, drying is for 24 hours；The flexible air-sensitive film for arriving blue homogeneous transparent using 252nm ultraviolet lighting 10min later, by this
Film is named as PDA/MoS2-2。
Embodiment 3
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
(1) method same as Example 1 is used, the lamella MoS of removing is obtained2Two-dimensional material；
(2) the above-mentioned lamella MoS of 1mg is taken21mL ethyl alcohol is added in two-dimensional material, and ultrasonic disperse is uniform, obtains MoS2Dispersion
Liquid；Claim the PCDA of 10mg to be dissolved in 1mL ethanol solution, be filtered to remove oligomer, obtains PCDA monomer solution；
(3) by the above-mentioned MoS of 50 μ L2Dispersion liquid is mixed with the PCDA solution of 100 μ L, with the power ultrasound 10min of 1200W
After be vigorously agitated again 30min, obtain MoS2/ PCDA precursor solution；
(4) PET film is taken, after plasma hydrophilic treated, by MoS2/ PCDA precursor solution is spun on hydrophilic PET
On film, drying is for 24 hours；The flexible air-sensitive film for arriving blue homogeneous transparent using 252nm ultraviolet lighting 10min later, by this
Film is named as PDA/MoS2-3。
Embodiment 4
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
(1) method same as Example 1 is used, the lamella MoS of removing is obtained2Two-dimensional material；
(2) the above-mentioned lamella MoS of 1mg is taken21mL ethyl alcohol is added in two-dimensional material, and ultrasonic disperse is uniform, obtains MoS2Dispersion
Liquid；Claim the PCDA of 5mg to be dissolved in 1mL ethanol solution, be filtered to remove oligomer, obtains PCDA monomer solution；
(3) by the above-mentioned MoS of 100 μ L2Dispersion liquid is mixed with the PCDA solution of 100 μ L, with the power ultrasound of 1200W
It is vigorously agitated again 30min after 10min, obtains MoS2/ PCDA precursor solution；
(4) PET film is taken, after plasma hydrophilic treated, by MoS2/ PCDA precursor solution is spun on hydrophilic PET
On film, drying is for 24 hours；252nm ultraviolet lighting 10min is used later, on the substrate the flexible air-sensitive of shape blue homogeneous transparent
This film is named as PDA/MoS by film2-4。
Embodiment 5
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
By the lamella WS after removing2After the ethanol solution mixing of the ethanol solution, 16 carbon diacetylenic acid of 5,7- of two-dimensional material
Precursor solution is obtained, the precursor solution is spun to hydrophilic polyimides (PI) film substrate surface, after dry,
It is placed under the ultraviolet light of 254nm and polymerize 20min, form transparent flexible air-sensitive film on the substrate, wherein the forerunner
In liquid solution, lamella WS2Two-dimensional material and the molar ratio of 16 carbon diacetylenic acid of 5,7- are 0.08:1.
Embodiment 6
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
By the lamella VS after removing2The methanol solution mixing of the ethanol solution, 29 diacetylenic acid of 10,12- of two-dimensional material
After obtain precursor solution, the precursor solution is spun to hydrophilic PET base surface, after dry, is placed in 254nm's
Polyase 13 0min under ultraviolet light forms transparent flexible air-sensitive film on the substrate, wherein in the precursor solution, piece
Layer VS2Two-dimensional material and the molar ratio of 29 diacetylenic acid of 10,12- are 0.1:1.
Embodiment 7
A kind of preparation method of flexibility air-sensitive film, comprising the following steps:
By the lamella ZrS after removing2After the acetone soln mixing of the ethanol solution, 19 diacetylenic acid of 2,4- of two-dimensional material
To precursor solution, the precursor solution is spun to hydrophilic polyvinyl alcohol (PVA) film substrate surface, after dry,
It is placed under the ultraviolet light of 254nm and polymerize 45min, form transparent flexible air-sensitive film on the substrate, wherein the forerunner
In liquid solution, lamella ZrS2Two-dimensional material and the molar ratio of 29 diacetylenic acid of 10,12- are 0.3:1.
Effect example:
Under room temperature, by the simple PCDA ultraviolet polymerization of same size at PDA film and embodiment 1-4 in make
Standby PDA/MoS2Flexible air-sensitive film is respectively placed in the chamber of the steam containing DMF, respectively to flexibility made from each embodiment
Air-sensitive film is characterized through the UV absorption property before and after contact DMF, and it is flexible in each embodiment before and after the processing to compare DMF
The variation of air-sensitive film color.The characterization result of ultraviolet spectra is as shown in Figure 2.In (A)-(E) of Fig. 2, each dotted line is to connect with DMF
Curve after touch, solid line are the curve not contacted with DMF, wherein (A) be independent PCDA ultraviolet polymerization at PDA film, (B)-
It (E) is respectively the PDA/MoS prepared in embodiment 1-4 in2Flexible air-sensitive film, (F) are the fitting knot of each sample in (A)-(E)
Fruit.
Figure it is seen that after DMF is handled, the PDA/MoS of embodiment 1-42The UV absorption light of flexible air-sensitive film
Spectrum changes, and major absorbance peak is changed to 550nm by 640nm, and the response performance obviously than independent PDA film is brighter
It is aobvious.
By the change (CR) for calculating blue light, two peak intensity of feux rouges after DMF is handled, it can be estimated that the response of each film
Property.Wherein,B0、B1The respectively described flexible air-sensitive film handles forward and backward through DMF organic steam
Blue light percentage,ABlue、ARedIt is the absorbance near 640nm, 550nm respectively.It is logical
It crosses comparison sensing capabilities to obtain, the change of the blue light of flexibility air-sensitive film described in embodiment 1-4, two peak of feux rouges is obviously compared individually
PDA film is big, illustrates the diacetylene class monomer and lamella MoS2After two-dimensional material in-situ copolymerization, more to the response performance of DMF
Obviously, meanwhile, lamella MoS in embodiment 2 under identical condition2The additive amount of two-dimensional material is best: MoS2With PCDA monomer
Mass ratio is 5%.In addition, the concentration of DMF can also be evaluated by calculating CR.
(A) is the film bends the performance test results of the obtained flexible air-sensitive film in embodiment 1 in Fig. 3, in Fig. 3
It (B) is the selectivity test result to gas with various of the flexible air-sensitive film obtained in embodiment 1.(A) can be in Fig. 3
Find out, which tests the sensing capabilities of its DMF steam for being 0.1% to volume fraction after bending 500 times,
It was found that remaining to maintain 90% of initial value or more；(B) is as can be seen that the flexibility air-sensitive film shows DMF steam in Fig. 3
Good selectivity.Thus illustrate, the flexibility air-sensitive film is preferable to the selectivity of DMF, and flexibility senses stability to DMF
Preferably, it can be used for constructing high flexibility, construct wearable device.
Fig. 4 is the flexible air-sensitive film obtained in embodiment 1 to the response curve to various concentration DMF.It can from Fig. 4
To find out, which is 0.01% to 4% (volume fraction) to the detection linearly interval of DMF.
Application Example
Using the transparency and high flexibility of the flexible air-sensitive film of 1-4 of embodiment of the present invention preparation, building is worn
The schematic diagram for wearing equipment (bracelet) is as shown in Figure 5.In the spin coating stage, there is precursor solution to spin coating using template (exposure mask)
The film that (monomer of class containing diacetylene and transient metal sulfide two-dimensional material) is dried afterwards carries out patterned process, thus on film
DMF printed words are formed, the flexible air-sensitive film with DMF printed words are obtained after uv photopolymerization, and glue on a flexible substrate will be passed through
Ring is sticked into, bracelet wearable device is obtained.After DMF is handled, DMF printed words become red by blue, illustrate that the bracelet can be used for
The gas sensing of DMF organic steam can be configured to the wearable gas alarm device of DMF.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (12)
1. it is a kind of flexibility air-sensitive film, which is characterized in that it is described flexibility air-sensitive film by transient metal sulfide two-dimensional material with
Polybutadiene alkynes is combined, and the polybutadiene alkynes is formed by diacetylene class monomer through ultraviolet polymerization；Wherein, the diacetylene class list
Shown in the general structure of body such as formula (I):
In formula (I), R1The straight chained alkyl for being 5-20 for carbon atom number, R2The straight-chain alkyl-sub for being 3-20 for singly-bound or carbon atom number.
2. flexibility air-sensitive film as described in claim 1, which is characterized in that the transient metal sulfide two-dimensional material intercalation
Be distributed in the diacetylene class monomer polymerization at polybutadiene alkyne film in, form the flexible air-sensitive film of porous structure.
3. flexibility air-sensitive film as claimed in claim 2, which is characterized in that the aperture of the porous structure is 0.1-100 μm.
4. flexibility air-sensitive film as described in claim 1, which is characterized in that the transient metal sulfide two-dimensional material and fourth
The molar ratio of two acetylenic monomers is (0.01-0.5): 1.
5. flexibility air-sensitive film as described in claim 1, which is characterized in that the transient metal sulfide two-dimensional material includes
One of molybdenum disulfide, tungsten disulfide, curing zirconium, titanium disulfide and vanadium disulfide are a variety of.
6. flexibility air-sensitive film as described in claim 1, which is characterized in that the R2The straight chain for being 10-16 for carbon atom number is sub-
Alkyl；The R1The straight chained alkyl for being 8-16 for carbon atom number.
7. a kind of preparation method of flexibility air-sensitive film, which comprises the following steps:
(1) diacetylene class monomer shown in formula (I) and transient metal sulfide two-dimensional material are added in the first organic solvent,
Through ultrasonic disperse and after mixing evenly, precursor solution is obtained；Wherein, first organic solvent includes ethyl alcohol, methanol or third
Ketone；
In formula (I), R1The straight chained alkyl for being 5-20 for carbon atom number, R2The straight-chain alkyl-sub for being 3-20 for singly-bound or carbon atom number；
(2) precursor solution is dropped to or is coated in the flexible substrates to hydrophilic treated, sufficiently after drying, then through ultraviolet
Polymerization forms flexible air-sensitive film in the flexible substrates, and the flexibility air-sensitive film is by transient metal sulfide two dimension material
Material is combined with polybutadiene alkynes, and the polybutadiene alkynes is formed by diacetylene class monomer through ultraviolet polymerization.
8. preparation method as claimed in claim 7, which is characterized in that the flexible substrates include polyester film, polyimides
Film or polyvinyl alcohol film.
9. preparation method as claimed in claim 7, which is characterized in that the power of ultrasonic treatment described in step (1) is 1000-
1800W, ultrasonic time 10-30min.
10. a kind of gas sensor, the gas sensor includes flexible sensing element, and the flexible sensing element includes flexibility
Substrate, and the flexible air-sensitive film as claimed in any one of claims 1 to 6 being arranged in the flexible substrates, the flexibility
The surface region contacted can be formed with gas to be sensed by having on air-sensitive film.
11. gas sensor as claimed in claim 10, which is characterized in that the gas sensor is wearable.
12. flexible air made from the as claimed in any one of claims 1 to 6 or described in any item preparation methods of claim 7-9
Application of the gas sensor described in sensitive film or claim 10-11 in organic steam detection.
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