CN103881038A - Preparation method and application of triblock copolymer containing spiropyrane group - Google Patents
Preparation method and application of triblock copolymer containing spiropyrane group Download PDFInfo
- Publication number
- CN103881038A CN103881038A CN201410039064.2A CN201410039064A CN103881038A CN 103881038 A CN103881038 A CN 103881038A CN 201410039064 A CN201410039064 A CN 201410039064A CN 103881038 A CN103881038 A CN 103881038A
- Authority
- CN
- China
- Prior art keywords
- spma
- bma
- solution
- neck bottles
- polyacrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method and application of a triblock copolymer containing a spiropyrane group. The method comprises the following steps: 1) preparing a solid sample Br-P(BMA-co-SPMA)-Br; 2) obtaining a triblock copolymer containing a spiropyrane group, namely, PDMAEMA-b-P(BMA-co-SPMA)-b-PDMAEMA; 3) dissolving 10mg polymer PDMAEMA-b-P-(BMA-co-SPMA)-b-PDMAEMA to DMF (Dimethyl Formamide) to obtain a stable micelle dispersion solution; then dropwise coating a micelle-containing polyacrylic acid solution onto a quartz plate to obtain a micelle-containing polyacrylic acid film sample. The triblock copolymer containing the spiropyrane group nearly does not pollute the environment and is an environment-friendly anti-counterfeiting coating material.
Description
Technical field
The present invention relates to a kind of block polymer, especially relate to a kind of Preparation method and use of the triblock copolymer containing spiropyran groups.
Background technology
By the isomerization of photoinduction control photosensitive group, realize the switching over of fluorescence, this fluorescence regulates material to have important application value in fields such as false proof, information storage, photoswitch and bio-medical materials.Spiro-pyrans is a kind of important photosensitive group, is widely used in preparing the adjustable intelligent material of fluorescence.Spiro-pyrans is introduced in hydrophobic cavity, and the fluorescence of the merocyanine type isomer of spiro-pyrans significantly strengthens, by the isomerization reaction of photoinduction control spiropyran groups, with regard to the variation of controllable adjustment color and the switching over of fluorescence.There is zwitter-ion and neutral quinoid structure in the merocyanine type body structure of spiro-pyrans in addition in nonpolar environment, along with the variation of temperature, merocyanine type body transforms between multiple isomer, color also changes along with temperature, and these features can be applicable to the anti-fake material field of Multiple recognition feature.[concrete visible Zhu M Q, Zhu L, Han J J, Wu W, Hurst J K, Li A D Q.J.Am.Chem.Soc., 2006, 128 (13): 4303-4309.Zhu L Y, Wu W W, Zhu Mi Q, Han J J, Hurst J K, Li A D Q.J.Am.Chem.Soc., 2007, 129 (12): 3524-3526.Zhu M Q, Zhang G F, Li C, Aldred M P, Chang E, Drezek R A, Li A D Q.J.Am.Chem.Soc., 2011, 133 (2): 365-372.Shiraishi Y, Miyamoto R, Hirai T.Org.Lett., 2009, 11 (7): 1571-1574.]
Summary of the invention
In order to develop the anti-fake material with triple recognition features, the object of the present invention is to provide a kind of Preparation method and use of the triblock copolymer containing spiropyran groups, prepare a kind of water-soluble polymers micella emulsion, by photosensitive group spiro-pyrans being introduced to the hydrophobic inner core of micella, significantly improve the fluorescence intensity of micella, by irradiating and close the isomerization of UV-light control spiro-pyrans, the performances such as the photochromic and fluorescent switch of adjusting micella.Selection polyacrylic acid is filmogen, water-soluble micella is dispersed in the polyacrylic acid aqueous solution, improve the concentration of micella, the polyacrylic acid solution that contains micella is coated on quartz plate, after dry, form polyacrylic acid film, film, except having photochromic performance, can also send stronger pink colour fluorescence, by the isomerization of UV-light and visible ray control spiro-pyrans, can regulate the switching over of film fluorescence.
The technical solution used in the present invention is:
One, a preparation method who contains the triblock copolymer of spiropyran groups, the step of the method is as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate and 0.14g is joined in two dry neck bottles, get the initiator B MB of 0.20g, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml methyl-phenoxide, join in two neck bottles, initiator B MB, the molar ratio of CuBr and part PMDETA remains on 1:1:1, the molar ratio of monomers B MA and SPMA is between 1:1000～1000:1, initiator and BMA, the mol ratio of two kinds of monomer total amounts of SPMA is between 1000:1～1:1000, sealing, then bleed thaw cycles three times of liquid nitrogen freezing, two neck bottles are placed in after 90 DEG C of oil bath reaction 40min, open two neck bottles, and in liquid nitrogen cooling stopped reaction, add dilution with toluene product solution, after separating by neutral alumina chromatography column, collect and flow out solution, and precipitate in-5 DEG C of methyl alcohol of 10 times of volumes, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample Br-P (BMA-co-SPMA)-Br, for subsequent use after vacuum-drying 24h at 45 DEG C,
2) 0.55g polymer B r-P (BMA-co-SPMA)-Br is joined in two dry neck bottles, the applying argon gas of bleeding circulation three times, measure 2.4ml monomer DMAEMA and 1.8ml toluene with syringe, and join in the two neck bottles that fill Br-P (BMA-co-SPMA)-Br, sealing, after polymer dissolution, the freezing thaw cycles three times of bleeding in liquid nitrogen, initiator B r-P (BMA-co-SPMA)-Br, the molar ratio of CuCl and part PMDETA remains on 1:1:1, the mol ratio of macromole evocating agent P (BMA-co-SPMA)-Br and monomer DMAEMA is between 1000:1～1:1000, then open two neck bottles and pass into argon gas, now add 76 μ l part PMDETA and 37mg CuCl, sealing, the freezing thaw cycles three times of bleeding in liquid nitrogen, two neck bottles are placed in to 70 DEG C of oil baths and react 20h, after reaction finishes, open two neck bottles, cooling stopped reaction in liquid nitrogen, add dilution with toluene product solution, separate and remove catalyzer by alkali alumina post, collect and flow out solution, in-5 DEG C of methyl alcohol of 10 times of volumes, precipitate, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample, obtain poly-(n-BMA-co-spiro-pyrans base ethyl-methyl acrylate)-b-polymethyl acrylic acid dimethylamino ethyl ester (its English is abbreviated as PDMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA) of triblock copolymer polymethyl acrylic acid dimethylamino ethyl ester-b-containing spiropyran groups, for subsequent use after vacuum-drying 24h at 45 DEG C,
3) 10mg polymer P DMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA is dissolved in the DMF of 1ml, ultrasonic 15min dissolves it completely, then 9ml deionized water is slowly added drop-wise in the DMF solution of polymkeric substance, stir simultaneously, after deionized water adds, continue to stir 12h, then, by the dialysis tubing of the maximum molecular weight cut-off 3500 obtaining, in deionized water, dialyse 2 days, change during this time fresh deionized water, after 2 days, obtain stable micella dispersion soln;
Concrete reaction formula and micelle formation schematic diagram are as shown in Figure 1.
Two, a kind of purposes of the triblock copolymer containing spiropyran groups
By after micellar solution lyophilize, obtain white powder sample, join in deionized water, stir simultaneously, be made into micella water dispersion soln, by the polyacrylic acid aqueous solution of mass percent concentration 25%, polyacrylic acid weight-average molecular weight 2.4 × 10
5slowly be added drop-wise in micellar solution, constantly stir micellar solution and polyacrylic acid solution are mixed simultaneously, dropwise rear continuation and stir 30min, then the polyacrylic acid dispersion soln that contains micella is dripped and is coated on quartz plate, after the complete volatile dry of solvent, obtain the polyacrylic acid film sample that contains micella.
The beneficial effect that the present invention has is:
1) polymeric film have simultaneously photochromic, fluorescence is adjustable and the performance of thermochromism, is a kind of anti-fake material with triple recognition features.
2) control the isomerization of spiro-pyrans a kind of component, just can regulate and control three kinds of stimuli responsive features such as photochromic, fluorescence intensity and thermochromism of micella simultaneously.
3) regulate micella colour-change and fluorescent switch by irradiating or closing UV-light, easy to operate, can repeatedly use, stability is higher, and the speed of response is very fast.
4) the synthetic polymkeric substance of the present invention obtains micella through self-assembly, to the less pollution of environment, is a kind of coated material of environmental protection.
Brief description of the drawings
Fig. 1 is reaction formula of the present invention and micelle formation schematic diagram.
Fig. 2 is the hydrogen-nuclear magnetic spectrogram of polymer B r-P (BMA-co-SPMA)-Br in chloroformic solution of deuteration that the present invention makes.
Fig. 3 is the hydrogen-nuclear magnetic spectrogram of block polymer PDMAEMA-b-P (BMA-co-SPMA)-b-PDMA EMA in chloroformic solution of deuteration that the present invention makes.
Fig. 4 is the transmission electron microscope photo of block polymer PDMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA self-assembled micelle of making of the present invention.
Fig. 5 is that the polyacrylic acid film that comprises polymer micelle that the present invention makes is subject to the photo before and after UV-irradiation.UV-light sees through the overcover irradiate surface of hollow out, and the position being irradiated to is from the colourless blueness that becomes, and under ultraviolet lamp, strong pink colour fluorescence is sent at variable color position.
Fig. 6 is the photo of polyacrylic acid film under differing temps and the mechanism of thermochromism thereof that comprise polymer micelle that the present invention makes.35 DEG C time, film is aobvious red, 45 o'clock DEG C of aobvious pink colours of film, the aobvious lightpink of film 55 DEG C time.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, person skilled in art can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
1. block polymer is synthetic
The CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate (SPMA) and 0.14g is joined in two dry neck bottles, measure the initiator B MB of 0.20g with syringe, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml methyl-phenoxide, join in the two neck bottles that fill CuBr, sealing, then bleed thaw cycles three times of liquid nitrogen freezing, two neck bottles are placed in after 90 DEG C of oil bath reaction 40min, open two neck bottles, and in liquid nitrogen cooling stopped reaction, add a small amount of dilution with toluene product solution, after separating by neutral alumina chromatography column, collect and flow out solution, and precipitate in the methyl alcohol (5 DEG C) of 10 times of volumes, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample Br-P (BMA-co-SPMA)-Br, for subsequent use after vacuum-drying 24h at 45 DEG C, structure as shown in Figure 2.
0.55g polymer B r-P (BMA-co-SPMA)-Br is joined in two dry neck bottles, the applying argon gas of bleeding circulation three times, measure 2.4ml monomer DMAEMA and 1.8ml toluene with syringe, and join in the two neck bottles that fill Br-P (BMA-co-SPMA)-Br, sealing, after polymer dissolution, the freezing thaw cycles three times of bleeding in liquid nitrogen.Then open two neck bottles and pass into argon gas, now adding fast 76 μ l part PMDETA and 37mg CuCl, sealing, in liquid nitrogen, the freezing thaw cycles three times of bleeding, is placed in 70 DEG C of oil baths by two neck bottles and reacts 20h.After reaction finishes, open two neck bottles, cooling stopped reaction in liquid nitrogen, add a small amount of dilution with toluene product solution, separate and remove catalyzer by alkali alumina post, collect and flow out solution, precipitation in the methyl alcohol (5 DEG C) of 10 times of volumes, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, and suction filtration is collected solid sample, obtains di-block copolymer PDMAEMA-b-P (the BMA-co-SPMA)-b-PDMAEMA containing spiropyran groups, for subsequent use after vacuum-drying 24h at 45 DEG C, structure as shown in Figure 3.
2. the preparation of block polymer micelle
10mg polymer P DMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA is dissolved in the DMF of 1ml, ultrasonic 15min dissolves it completely, then 9ml deionized water is slowly added drop-wise in the DMF solution of polymkeric substance, vigorous stirring simultaneously, after adding, continues deionized water to stir 12h, then the mixing solutions obtaining is transferred to (maximum molecular weight cut-off 3500) in dialysis tubing, in deionized water, dialyse 2 days, change at set intervals during this time fresh deionized water, after 2 days, obtain stable micella dispersion soln.
As shown in Figure 4, be the transmission electron microscope photo of block polymer PDMAEMA-b-P (BMA-co-SPMA)-b-PDMAEMA self-assembled micelle of making of the present invention.
3. contain the preparation of the polyacrylic acid film of polymer micelle
By after micellar solution lyophilize, obtain white powder sample, the powdered sample that takes 16.7mg joins in 8.5ml deionized water, and vigorous stirring, is made into certain density micella water dispersion soln simultaneously.By the polyacrylic acid aqueous solution (the polyacrylic acid weight-average molecular weight 2.4 × 10 of 0.10g mass percent concentration 25%
5), be slowly added drop-wise in the micellar solution of 0.5ml, constantly stir micellar solution and polyacrylic acid solution are mixed simultaneously, dropwise rear continuation and stir 30min.Then the polyacrylic acid dispersion soln that contains micella is dripped and is coated on quartz plate, after the complete volatile dry of solvent, obtain the polyacrylic acid film sample that contains micella.
Fig. 5 is that the polyacrylic acid film that comprises polymer micelle that the present invention makes is subject to the photo before and after UV-irradiation.UV-light sees through the overcover irradiate surface of hollow out, and the position being irradiated to is from the colourless blueness that becomes, and under ultraviolet lamp, strong pink colour fluorescence is sent at variable color position.
Fig. 6 is the photo of polyacrylic acid film under differing temps and the mechanism of thermochromism thereof that comprise polymer micelle that the present invention makes.35 DEG C time, film is aobvious red, the aobvious pink colour of film 45 DEG C time, the aobvious lightpink of film 55 DEG C time.
Claims (2)
1. a preparation method who contains the triblock copolymer of spiropyran groups, is characterized in that, the step of the method is as follows:
1) CuBr of 0.26g monomer spiro-pyrans base ethyl-methyl acrylate and 0.14g is joined in two dry neck bottles, get the initiator B MB of 0.20g, 0.21ml part PMDETA, the monomers B MA of 3.0ml and 3.0ml methyl-phenoxide, join in two neck bottles, initiator B MB, the molar ratio of CuBr and part PMDETA remains on 1:1:1, the molar ratio of monomers B MA and SPMA is between 1:1000～1000:1, initiator and BMA, the mol ratio of two kinds of monomer total amounts of SPMA is between 1000:1～1:1000, sealing, then bleed thaw cycles three times of liquid nitrogen freezing, two neck bottles are placed in to 90
oafter C oil bath reaction 40min, open two neck bottles, and in liquid nitrogen cooling stopped reaction, add dilution with toluene product solution, after separating by neutral alumina chromatography column, collect and flow out solution, and at-5 of 10 times of volumes
oin C methyl alcohol, precipitate, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitating, this operation repeats twice, and suction filtration is collected solid sample Br-P (BMA-
co-SPMA)-Br, 45
ofor subsequent use after vacuum-drying 24h under C,
2) by 0.55g polymer B r-P (BMA-
co-SPMA)-Br joins in two dry neck bottles, and the applying argon gas of bleeding circulation three times, measures 2.4ml monomer DMAEMA and 1.8ml toluene with syringe, and joins and fill Br-P (BMA-
co-SPMA) in the two neck bottles of-Br, sealing, after polymer dissolution, the freezing thaw cycles three times of bleeding in liquid nitrogen, initiator B r-P (BMA-
co-SPMA) molar ratio of-Br, CuCl and part PMDETA remains on 1:1:1, macromole evocating agent P (BMA-
co-SPMA) mol ratio of-Br and monomer DMAEMA is between 1000:1～1:1000, then open two neck bottles and pass into argon gas, now adding 76 μ l part PMDETA and 37mg CuCl, sealing, in liquid nitrogen, the freezing thaw cycles three times of bleeding, is placed in 70 by two neck bottles
oin C oil bath, react 20h; After reaction finishes, open two neck bottles, cooling stopped reaction in liquid nitrogen, adds dilution with toluene product solution, is separated and is removed catalyzer by alkali alumina post, collects and flows out solution, at-5 of 10 times of volumes
oin C methyl alcohol, precipitate, suction filtration collecting precipitation sample, and be again dissolved in toluene, in methyl alcohol, precipitate, this operation repeats twice, suction filtration is collected solid sample, obtains poly-(n-BMA-co-spiro-pyrans base ethyl-methyl acrylate)-b-polymethyl acrylic acid dimethylamino ethyl ester of triblock copolymer polymethyl acrylic acid dimethylamino ethyl ester-b-containing spiropyran groups, 45
ofor subsequent use after vacuum-drying 24h under C;
3) by 10mg polymer P DMAEMA-
b-P (BMA-
co-SPMA)-
b-PDMAEMA is dissolved in the DMF of 1ml, ultrasonic 15min dissolves it completely, then 9ml deionized water is slowly added drop-wise in the DMF solution of polymkeric substance, stir simultaneously, after deionized water adds, continue to stir 12h, then, by the dialysis tubing of the maximum molecular weight cut-off 3500 obtaining, in deionized water, dialyse 2 days, change during this time fresh deionized water, after 2 days, obtain stable micella dispersion soln;
Concrete reaction formula and micelle formation schematic diagram are as shown in Figure 1.
2. the purposes of a kind of triblock copolymer containing spiropyran groups according to claim 1, it is characterized in that: by after micellar solution lyophilize, obtain white powder sample, join in deionized water, stir simultaneously, be made into micella water dispersion soln, by the polyacrylic acid aqueous solution of mass percent concentration 25%, polyacrylic acid weight-average molecular weight 2.4 × 10
5slowly be added drop-wise in micellar solution, constantly stir micellar solution and polyacrylic acid solution are mixed simultaneously, dropwise rear continuation and stir 30min, then the polyacrylic acid dispersion soln that contains micella is dripped and is coated on quartz plate, after the complete volatile dry of solvent, obtain the polyacrylic acid film sample that contains micella.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410039064.2A CN103881038B (en) | 2014-01-27 | 2014-01-27 | Containing the Preparation method and use of the triblock copolymer of spiropyran groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410039064.2A CN103881038B (en) | 2014-01-27 | 2014-01-27 | Containing the Preparation method and use of the triblock copolymer of spiropyran groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881038A true CN103881038A (en) | 2014-06-25 |
| CN103881038B CN103881038B (en) | 2016-04-20 |
Family
ID=50950196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410039064.2A Active CN103881038B (en) | 2014-01-27 | 2014-01-27 | Containing the Preparation method and use of the triblock copolymer of spiropyran groups |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881038B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661894A (en) * | 2020-12-23 | 2021-04-16 | 江南大学 | Preparation method of water-based self-adhesive anti-counterfeiting emulsion |
| CN113897247A (en) * | 2021-10-13 | 2022-01-07 | 曲阜师范大学 | Preparation of biodiesel by photo-magnetic dual-response emulsion method |
-
2014
- 2014-01-27 CN CN201410039064.2A patent/CN103881038B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| DEMETRA S.ACHILLEOS ET AL: "Multiresponsive spiropyran-based copolymers synthesized by atom transfer radical polymerization", 《MACROMOLECULES》 * |
| 张磊等: "含螺吡喃嵌段聚合物的合成及其光敏性能研究", 《2013年全国高分子学术论文报告会论文摘要集——主题F：功能高分子》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661894A (en) * | 2020-12-23 | 2021-04-16 | 江南大学 | Preparation method of water-based self-adhesive anti-counterfeiting emulsion |
| CN113897247A (en) * | 2021-10-13 | 2022-01-07 | 曲阜师范大学 | Preparation of biodiesel by photo-magnetic dual-response emulsion method |
| CN113897247B (en) * | 2021-10-13 | 2023-11-21 | 曲阜师范大学 | Preparation of biodiesel by photo-magnetic dual-response emulsion method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881038B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2519377C9 (en) | Functionalised thin-film polyamide membranes | |
| CN102585121B (en) | Block polymer capable of being used as white board pen ink dispersing agent and white board pen ink | |
| CN111116813A (en) | Preparation method of fluorescent microspheres based on crosslinked polymer | |
| CN102046679A (en) | Improved method for making sulfonated block copolymers, method for making membranes from such block copolymers and membrane structures | |
| CN102099390B (en) | Method for preparing a polymer particle dispersion in an aqueous medium | |
| US20030086978A1 (en) | Photochromic nanocapsule and preparation method thereof | |
| CN103910838B (en) | Contain the Preparation method and use of the di-block copolymer of spiropyran groups | |
| CN111587402B (en) | Resist composition and resist film | |
| CN104327294A (en) | pH responsive polyion liquid composite membrane and preparation method thereof | |
| CN106905551B (en) | A kind of counter opal structure temperature-sensitive material and preparation method thereof | |
| CN103881038A (en) | Preparation method and application of triblock copolymer containing spiropyrane group | |
| CN105237669A (en) | Preparation of 248 nm deep ultraviolet photoresist film forming resin based on RAFT polymerization method | |
| CN1704152A (en) | Preparation of hydrophilic polyvinylidene fluoride microporous membrane | |
| CN101880343B (en) | Fluorescent polymer environment-friendly material with Beta-dione aggregative luminous structure | |
| CN104628974A (en) | Amphiphilic copolymer capable of endowing pH response of membrane material and preparation method thereof | |
| CN105482019B (en) | A kind of formaldehydeless fluorescent pigment latex of high temperature resistant and preparation method thereof | |
| CN101456937A (en) | Polymethano-poly(methyl)acrylic ester two-block copolymer and preparation method thereof | |
| KR100781599B1 (en) | Sensor using polydiacetylene-embedded polymer film and process for preparing the same | |
| US20140099580A1 (en) | Spatial and temporal control of brush formation on surfaces | |
| CN102190766B (en) | Polyvinyl environmentally responsive diblock and triblock copolymers and preparation methods thereof | |
| Zhang et al. | Fabrication of Electrospinning Fibers from Spiropyran‐Based Polymeric Nanowires and their Photochromic Properties | |
| CN106835319A (en) | A kind of preparation method of photochromic block copolymer | |
| CN111662406B (en) | Intelligent response type branched copolymer containing metastable state photoacid and preparation method thereof | |
| JP2014221868A (en) | Method for producing block copolymer and photonic material using the same | |
| CN115723457A (en) | Reversible humidity response fluorescent color-changing system, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |