CN103254453A - Method for preparing photochromic thin film by using organogel dispersed in polymers - Google Patents
Method for preparing photochromic thin film by using organogel dispersed in polymers Download PDFInfo
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Abstract
The invention discloses a method for preparing a photochromic thin film by using organogel dispersed in polymers. The method comprises the following steps: first, uniformly mixing a polypropylene glycol liquor with low molecular weight of a photochromic compound and small molecular gel in a low boiling point solvent, and dispersing the uniform liquor to deionized water containing a surfactant under a high-speed shearing action to obtain a compound emulsion; then, continuously dispersing the compound emulsion under a high-speed shearing action in a PVA (Polyvinyl Acetate) aqueous liquor to obtain a novel compound emulsion; and finally, knifing the compound emulsion, freezing and storing and drying at room temperature to obtain the thin film. The polymer PVA provides the strength of the material, and the organogel formed from the polypropylene glycol liquor of the photochromic compound is uniformly dispersed in a PVA matrix. The organogel isolates the photochromic compound from the polymer matrix to provide a sufficient isomeric space for the photochromic compound, so that the isomeric speed of the molecules of the photochromic compound is high, and the photochromic material prepared from organogel dispersed in polymers is quick in response.
Description
Technical field
The invention belongs to the photochromic material field, be specifically related to a kind of preparation method of polymer dispersed organogel photochromic film.
Background technology
Spiro-pyrans has wide practical use in photochromic material Yu Luo oxazine molecule is the photochromic compounds of a quasi-representative.Consider that from the practicability angle organic photochromic material must present solid-state, could satisfy the application in fields such as information storage and light-sensitive sunglasses.In addition, material also need have good processing and mechanical property.With organic photochromic molecule and the compound preparation photochromic film of polymkeric substance, be considered to the most rising and method actual application value.Yet, no matter be to utilize the physics method directly photochromic compound to be distributed in the polymkeric substance, still utilize grafting copolymerization process to be introduced on the macromolecular chain, the isomerization process of the photochromic compound that all can slow down.It is most important how to improve the isomery speed of photochromic compound in polymkeric substance.Organogel is that a class is by the Low Molecular-Weight Gel agent three-dimensional physical network arrangement that self-assembly forms in organic solvent.Spiro-pyrans Huo Luo oxazine molecular melting in organic solvent, and then is introduced in the organogel, and the isomerization speed of spiro-pyrans Huo Luo oxazine is near its isomery speed in corresponding solution.
Usually the organogel preparation method is: heating is dissolved in the organic solvent Low Molecular-Weight Gel agent fully, and naturally cooling becomes gel then.But the process of heating for dissolving gelifying agent will be destroyed the photochromic characteristic of spiro-pyrans Huo spirooxazine compounds.Therefore, normal temperature or dissolution in low temperature gelifying agent prepare organogel, most important with the method for maintenance spiro-pyrans Huo Luo oxazine photochromic characteristic.On the other hand, the organogel existence is squeezed and produces the solvent leakage problems, has limited its practical application.
Summary of the invention
The present invention is directed to heating for dissolving and prepare the photochromic characteristic of organogel destructible photochromic compound, and organogel produces the shortcoming of solvent seepage, a kind of preparation method of polymer dispersed organogel photochromic film is provided, this method adopts low boiling point organic solvent to solve the problem that gel factor room temperature is dissolved as cosolvent, adopts emulsification/solvent evaporation method that organogel is dispersed in the polymeric matrix simultaneously.
The preparation method of a kind of polymer dispersed organogel photochromic film provided by the invention in turn includes the following steps:
(1) photochromic compound is dissolved under the lucifuge condition in the low-molecular-weight polypropylene glycol (PPG), obtains the PPG solution of photochromic compound;
(2) solution and the Low Molecular-Weight Gel agent with step (1) gained joins in the low boiling point organic solvent, mixes under the lucifuge condition, obtains including the homogeneous solution of photochromic compound, polypropylene glycol and gelifying agent;
(3) homogeneous solution with step (2) joins in the deionized water that contains tensio-active agent, and high speed shear is disperseed under the condition of ice bath, obtains including the composite emulsion of photochromic compound, polypropylene glycol and gelifying agent;
(4) composite emulsion with step (3) gained is added in polyvinyl alcohol (PVA) aqueous solution, and the back high speed shear that stirs under the condition of ice bath is disperseed, and obtains including the composite emulsion of photochromic compound, polypropylene glycol, gelifying agent and PVA;
(5) the resultant composite emulsion of step (4) is placed on the clean sheet glass, knifing, after the freezing preservation, the lucifuge drying obtains polymer dispersed organogel photochromic film.
Superiority of the present invention is: polymer P VA provides material with intensity, the organogel that the polypropylene glycol solution of photochromic compound forms is dispersed in the PVA matrix, organogel is opened photochromic compound and polymeric matrix are isolated, offer the isomery space of photochromic compound abundance, therefore the isomery speed of photochromic compound molecule is fast, and the polymer dispersed organogel photochromic material response that obtains fast.
Description of drawings
Fig. 1 a is the prepared 1%DBS organogel of embodiment 1 UV-Vis absorption spectrum before and after ultraviolet excitation.
Fig. 1 b is the prepared 1%DBS organogel of embodiment 1 extinction curve and with one-level exponential attenuation equation model curve in time after ultraviolet excitation this absorbing wavelength place absorbance A to the saturated absorbancy of maximum absorption wave strong point is stopping to excite.
Fig. 2 a is UV-Vis absorption spectrum before and after the embodiment 1 prepared film ultraviolet excitation.
Fig. 2 b is embodiment 1 prepared film extinction curve and with one-level exponential attenuation equation model curve in time after ultraviolet excitation this absorbing wavelength place absorbance A to the saturated absorbancy of maximum absorption wave strong point is stopping to excite.
Fig. 3 is the prepared sem photograph (SEM) of polymer dispersed organogel photochromic film after solvent (normal hexane) soaks out organic solution of embodiment 1.
Embodiment
The inventive method adopts photochromic compound (as the spiro-pyrans of discoloration excellence with the Luo oxazine) as color-changing unit, select for use water-soluble polymers PVA as matrix, adopt low boiling point organic solvent to solve the problem of gel factor room temperature dissolving as cosolvent on the one hand, adopt emulsification/solvent evaporation method to disperse the organogel that forms on the other hand, thereby prepare a kind of polymer dispersed organogel photochromic film.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described further.Need to prove at this, understand the present invention for the explanation of these embodiments for helping, but do not constitute limitation of the invention.In addition, below in each embodiment of described the present invention involved technical characterictic just can not make up mutually as long as constitute conflict each other.
The concrete preparation process of the polymer dispersed organogel photochromic film that example of the present invention provides is as follows:
1. photochromic compound room temperature magnetic agitation lucifuge is dissolved in the low-molecular-weight polypropylene glycol, obtains the polypropylene glycol solution of photochromic compound, the concentration of photochromic compound in polypropylene glycol is 0.1-5wt%;
2. with step 1. polypropylene glycol solution and the Low Molecular-Weight Gel agent of gained photochromic compound join in the low boiling point organic solvent, room temperature lucifuge magnetic agitation obtains homogeneous solution.Described low boiling point organic solvent is 5 with the polypropylene glycol liquor capacity ratio of photochromic compound: 1-25: 1, and the mass ratio of the polypropylene glycol solution of Low Molecular-Weight Gel agent and photochromic compound is 1: 20-1: 200.
In order to compare, can get the part homogeneous solution, splash into to circular silica glass groove, treat that low boiling point organic solvent volatilization makes organogel fully;
3. the homogeneous solution that 2. step is obtained is added in the deionized water that contains tensio-active agent, surfactant concentrations is 0.15-5wt% in the water, the volume ratio of water phase surfactant mixture and homogeneous solution is 1: 1-15: 1, the ice bath high speed is sheared and is uniformly dispersed, and obtains including the composite emulsion of photochromic compound, polypropylene glycol and gelifying agent;
4. the composite emulsion that 3. step is obtained including photochromic compound, polypropylene glycol and gelifying agent is added in polyvinyl alcohol (PVA) aqueous solution, the PVA aqueous solution is 1 with the volume ratio that includes the composite emulsion of photochromic compound, polypropylene glycol and gelifying agent: 1-10: 1, the massfraction of PVA is 8-15wt% in the aqueous solution, the even back high speed shear of magnetic agitation in the ice bath obtains including the composite emulsion of photochromic compound, polypropylene glycol, gelifying agent and PVA;
5. get the composite emulsion that includes photochromic compound, polypropylene glycol, gelifying agent and PVA, drop on the sheet glass of ultrasonic clean dry, use the spreader knifing, the specification of spreader is chosen 100-500 μ m, institute's knifing is after refrigerator and cooled is hidden 12-24h, the room temperature 24-48h that keeps in Dark Place namely makes polymer dispersed organogel photochromic film of the present invention.
Among the above-mentioned preparation method:
Described photochromic compound can be spiro-pyrans compounds or spirooxazine compounds, preferred a kind of in the following substances: 8-nitro-1 ', 3 ', 3 '-trimethylammonium spiral shell indoline chromene (being called for short SP1), 1 ',-(3-methyl butyl)-3 ', 3 '-dimethyl-6-nitro-chromene) (being called for short SP2), 1,3,3-tri-methyl indole quinoline-Nai Bing oxazines (being called for short SO1), 1,3-dihydroxyl-1,3,3-trimethylammonium-spiral shell indoline-2,3 '-Nai Bing oxazine (being called for short SO2);
Described polypropylene glycol (PPG) is a kind of among PPG400, PPG1000, PPG2000, PPG3000, the PPG4000 (their relative molecular mass is respectively 400,1000,2000,3000,4000) preferably;
Described low boiling point organic solvent is a kind of in methylene dichloride, chloroform, acetone, the tetrahydrofuran (THF) preferably;
Described Low Molecular-Weight Gel agent can be preferred 1,3:2,4-O-two benzals-D-sorbyl alcohol (DBS), 1,3:2,4-O-two (4-methyl benzal)-D-sorbyl alcohol (MDBS), 1,3:2, a kind of in 4-O-two (3,4-dimethyl benzal)-D-sorbyl alcohol (DMDBS);
Described tensio-active agent is quaternary amine coupling type Gimini tensio-active agent (12-6-12), nitrogen heterocyclic coupling type Gimini tensio-active agent (12-6-12PB), polyvinyl alcohol (PVA preferably, average weight-molecular mass is 13000～23000, and alcoholysis degree is 87～89%) in a kind of;
Described PVA is that mean polymerisation degree is 2600, and alcoholysis degree is 97～98.8% polyvinyl alcohol.
Embodiment 1:
0.02g spiro-pyrans SP1 room temperature lucifuge is dissolved among the 1g PPG1000, and the organic solution that makes is added to the 10ml methylene dichloride, add 0.01g DBS simultaneously, room temperature lucifuge magnetic agitation.After treating that DBS dissolves fully, get above-mentioned solution 2ml on the one hand, splash into to circular silica glass groove, treat that methylene dichloride volatilization makes organogel fully, get 2ml on the other hand, being added to the 4ml massfraction is the PVA aqueous solution of 4wt%, in the ice bath with 3000rpm high speed shear 1min.After shearing finishes, immediately emulsion is added to the PVA aqueous solution that the 5ml massfraction is 10wt%, in the ice bath behind the magnetic agitation 2min, immediately with 4500rpm high speed shear 2min.After shearing finishes, film with 400 μ m specification spreaders, institute films and puts into cold compartment of refrigerator, takes out behind the 12h, and 24h is preserved in the room temperature dark place, obtains polymer dispersed organogel photochromic film.
The material of the present invention of example 1 preparation, PVA disperse the PPG1000 solution of the spiro-pyrans in the organogel photochromic film comparison example 1, DBS/PPG1000 organogel to see the following form with the kinetic constant of secretly fading of the SP1/PMMA film of direct solution casting method (chloroform dissolving polymethylmethacrylate (PMMA) and spiro-pyrans SP1, the SP1 doping is 2wt%) preparation:
The a--kinetic constant measuring method that secretly fades: ultraviolet excitation removes excitation light source immediately to the saturated absorbancy of sample maximum absorption wave strong point, and measures this absorbancy extinction curve in time, and curve carries out match with one-level exponential attenuation kinetic equation.
The fade rates of spiro-pyrans is suitable with its PPG1000 solution in the organogel, and the curve that fades meets one-level decay kinetic equation; The kinetic constant of secretly fading (tl) of the photochromic film of the present invention's preparation only is slightly larger than the tl of spiro-pyrans PPG1000 solution, and the two is in an order of magnitude, the system of directly disperseing spiro-pyrans well below polymer.
Embodiment 2:
0.01g Luo oxazine SO1 room temperature lucifuge is dissolved among the 1g PPG400, and the organic solution that makes is added to 15ml acetone, add 0.02g MDBS simultaneously, the room temperature lucifuge stirs.After treating that MDBS dissolves fully, get above-mentioned solution 2ml on the one hand, splash into to circular silica glass groove, treat that acetone volatilization makes organogel fully, get 1ml on the other hand, being added to the 3ml massfraction is the Gimini tensio-active agent 12-6-12 aqueous solution of 0.15wt%, in the ice bath with 3000rpm high speed shear lmin.After shearing finishes, immediately emulsion is added to the PVA aqueous solution that the 10ml massfraction is 8wt%, in the ice bath behind the magnetic agitation 2min, immediately with 6000rpm high speed shear 2min.After shearing finishes, film with 300 μ m specification spreaders, institute films and puts into cold compartment of refrigerator, takes out behind the 12h, and 24h is preserved in the room temperature dark place, obtains polymer dispersed organogel photochromic film.
Embodiment 3:
0.001g spiro-pyrans SP2 room temperature lucifuge is dissolved among the 1g PPG2000, and the organic solution that makes is added to the 5ml chloroform, add 0.005g DMDBS simultaneously, the room temperature lucifuge stirs.After treating that DMDBS dissolves fully, get above-mentioned solution 2ml on the one hand, splash into to circular silica glass groove, treat that chloroform volatilization makes organogel fully, get 1ml on the other hand, being added to the 4ml massfraction is the Gimini tensio-active agent 12-6-12PB aqueous solution of 0.5wt%, in the ice bath with 2800rpm high speed shear 1min.After shearing finishes, immediately emulsion is added to the PVA aqueous solution that the 18ml massfraction is 12wt%, in the ice bath behind the magnetic agitation 2min, immediately with 5000rpm high speed shear 2min.Film with 200 μ m specification spreaders, institute films and puts into cold compartment of refrigerator, takes out behind the 12h, and 24h is preserved in the room temperature dark place, obtains polymer dispersed organogel photochromic film.
Embodiment 4:
0.025g Luo oxazine SO2 room temperature lucifuge is dissolved among the 1g PPG3000, and the organic solution that makes is added to the 15ml methylene dichloride, add 0.01g MDBS simultaneously, the room temperature lucifuge stirs.After treating that MDBS dissolves fully, get above-mentioned solution 2ml on the one hand, splash into to circular silica glass groove, treat that methylene dichloride volatilization makes organogel fully, get 1ml on the other hand, being added to the 5ml massfraction is the PVA aqueous solution of 5wt%, in the ice bath with 3000rpm high speed shear 1min.After shearing finishes, immediately emulsion is added to the PVA aqueous solution that the 27ml massfraction is 15wt%, in the ice bath behind the magnetic agitation 2min, immediately with 6000rpm high speed shear 2min.After shearing finishes, film with 100 μ m specification spreaders, institute films and puts into cold compartment of refrigerator, takes out behind the 12h, and 24h is preserved in the room temperature dark place, obtains polymer dispersed organogel photochromic film.
Embodiment 5:
0.05g spiro-pyrans SP1 room temperature lucifuge is dissolved among the 1g PPG4000, and the organic solution that makes is added to the 25ml tetrahydrofuran (THF), add 0.05g DBS simultaneously, the room temperature lucifuge stirs.After treating that DBS dissolves fully, get above-mentioned solution 2ml on the one hand, splash into to circular silica glass groove, treat that tetrahydrofuran (THF) volatilization makes organogel fully, get 0.5ml on the other hand, being added to the 5ml massfraction is the Gimini tensio-active agent 12-6-12 aqueous solution of 0.5wt%, in the ice bath with 3000rpm high speed shear 1min.After shearing finishes, immediately emulsion is added to the PVA aqueous solution that the 50ml massfraction is 10wt%, in the ice bath behind the magnetic agitation 2min, after finishing with 5000rpm high speed shear 2min shearing immediately, film with 500 μ m specification spreaders, institute films and puts into cold compartment of refrigerator, takes out behind the 12h, 24h is preserved in the room temperature dark place, obtains polymer dispersed organogel photochromic film.
Embodiment 6:
0.005g Luo oxazine SO2 room temperature lucifuge is dissolved among the 1g PPG1000, and the organic solution that makes is added to the 20ml methylene dichloride, add 0.03g DMDBS simultaneously, the room temperature lucifuge stirs.After treating that DMDBS dissolves fully, get above-mentioned solution 2ml on the one hand, splash into to circular silica glass groove, treat that methylene dichloride volatilization makes organogel fully, get 0.5ml on the other hand, being added to the 7.5ml massfraction is the Gimini tensio-active agent 12-6-12PB aqueous solution of 2wt%, in the ice bath with 2800rpm high speed shear 1min.After shearing finishes, immediately emulsion is added to the PVA aqueous solution that the 75ml massfraction is 8wt%, in the ice bath behind the magnetic agitation 2min, immediately with 6000rpm high speed shear 2min.After shearing finishes, film with 400 μ m specification spreaders, institute films and puts into cold compartment of refrigerator, takes out behind the 12h, and 24h is preserved in the room temperature dark place, obtains polymer dispersed organogel photochromic film.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment and accompanying drawing.So everyly do not break away from the equivalence of finishing under the spirit disclosed in this invention or revise, all fall into the scope of protection of the invention.
Embodiment 1-6 material addition and proportionlity table thereof
Annotate: " volume ratio 1 " refers to include homogeneous solution and the water phase surfactant mixture volume ratio of photochromic compound, polypropylene glycol and gelifying agent in the table; " volume ratio 2 " refers to the described volume ratio that includes composite emulsion and the polyvinyl alcohol water solution of photochromic compound, polypropylene glycol and gelifying agent.
Claims (10)
1. the preparation method of a polymer dispersed organogel photochromic film in turn includes the following steps:
(1) photochromic compound is dissolved under the lucifuge condition in the low-molecular-weight polypropylene glycol (PPG), obtains the PPG solution of photochromic compound;
(2) solution and the Low Molecular-Weight Gel agent with step (1) gained joins in the low boiling point organic solvent, mixes under the lucifuge condition, obtains including the homogeneous solution of photochromic compound, polypropylene glycol and gelifying agent;
(3) homogeneous solution with step (2) joins in the deionized water that contains tensio-active agent, and high speed shear is disperseed under the condition of ice bath, obtains including the composite emulsion of photochromic compound, polypropylene glycol and gelifying agent;
(4) composite emulsion with step (3) gained is added in polyvinyl alcohol (PVA) aqueous solution, and the back high speed shear that stirs under the condition of ice bath is disperseed, and obtains including the composite emulsion of photochromic compound, polypropylene glycol, gelifying agent and PVA;
(5) the resultant composite emulsion of step (4) is placed on the clean sheet glass, knifing, after the freezing preservation, the lucifuge drying obtains polymer dispersed organogel photochromic film.
2. the preparation method of polymer dispersed organogel photochromic film according to claim 1, it is characterized in that: the content of photochromic compound is 0.1-5wt% in the described PPG solution.
3. the preparation method of polymer dispersed organogel photochromic film according to claim 1, it is characterized in that: the volume ratio of the PPG solution of described low boiling point organic solvent and photochromic compound is 5: 1-25: 1, and the mass ratio of the PPG solution of described Low Molecular-Weight Gel agent and photochromic compound is 1: 20-1: 200.
4. the preparation method of polymer dispersed organogel photochromic film according to claim 1, it is characterized in that: in the step (3), in the described deionized water that contains tensio-active agent, the massfraction of tensio-active agent is 0.15-5wt%, and the volume that contains the deionized water of tensio-active agent is 1-15 times of described homogeneous solution volume.
5. the preparation method of polymer dispersed organogel photochromic film according to claim 1, it is characterized in that: in the step (4), in the described polyvinyl alcohol water solution, the polyvinyl alcohol massfraction is 8-15wt%, and polyvinyl alcohol water solution and the described volume ratio that includes the composite emulsion of photochromic compound, polypropylene glycol and gelifying agent are 1: 1-10: 1.
6. according to the preparation method of arbitrary described polymer dispersed organogel photochromic film in the claim 1 to 5, it is characterized in that: described photochromic compound is spiro-pyrans compounds Huo spirooxazine compounds.
7. according to the preparation method of the described polymer dispersed organogel of claim 6 photochromic film, it is characterized in that described photochromic compound is the one of the following kind: 8-nitro-1 ', 3 ', 3 '-trimethylammonium spiral shell indoline chromene, 1 ' ,-(3-methyl butyl)-3 ', 3 '-dimethyl-6-nitro-chromene, 1,3,3-tri-methyl indole quinoline-Nai Bing oxazines, 1,3-dihydroxyl-1,3,3-trimethylammonium-spiral shell indoline-2,3 '-Nai Bing oxazine.
8. according to the preparation method of arbitrary described polymer dispersed organogel photochromic film in the claim 1 to 5, it is characterized in that:
Described polypropylene glycol (PPG) is selected from one of the following kind: PPG400, PPG1000, PPG2000, PPG3000, PPG4000, and their average weight-molecular mass is respectively 400,1000,2000,3000,4000;
Described low boiling point organic solvent is selected from the one of the following kind: methylene dichloride, chloroform, acetone, tetrahydrofuran (THF);
Described Low Molecular-Weight Gel agent is selected from one of the following kind: 1,3:2,4-O-two benzals-D-sorbyl alcohol, 1,3:2,4-O-two (4-methyl benzal)-D-sorbyl alcohol, 1,3:2,4-O-two (3,4-dimethyl benzal)-D-sorbyl alcohol.
9. according to the preparation method of arbitrary described polymer dispersed organogel photochromic film in the claim 1 to 5, it is characterized in that: described tensio-active agent is quaternary amine coupling type Gimini tensio-active agent, nitrogen heterocyclic coupling type Gimini tensio-active agent or polyvinyl alcohol (PVA), wherein, the average weight-molecular mass of polyvinyl alcohol (PYA) is 13000～23000, and alcoholysis degree is 87～89%.
10. according to the preparation method of claim 1 and 2 described polymer dispersed organogel photochromic films, it is characterized in that the mean polymerisation degree of the polyvinyl alcohol (PYA) described in the step (4) is 2600, alcoholysis degree is 97-98.8%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021268A (en) * | 2018-09-04 | 2018-12-18 | 山东大学 | A kind of preparation method of the photochromic gel membrane material of quick response |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
| CN111793107A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院化学研究所 | DMSO-free cryopreservation liquid and preparation method thereof |
| TWI780043B (en) * | 2016-03-10 | 2022-10-11 | 日商三菱瓦斯化學股份有限公司 | Synthetic resin laminate having photochromic properties and lens using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105682A (en) * | 1994-01-17 | 1995-07-26 | 毛永根 | Colour plasticity composition |
-
2013
- 2013-04-24 CN CN201310144815.2A patent/CN103254453B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105682A (en) * | 1994-01-17 | 1995-07-26 | 毛永根 | Colour plasticity composition |
Non-Patent Citations (2)
| Title |
|---|
| 刘浪等: ""PMMA分散螺吡喃薄膜的微结构与光致变色行为"", 《高等学校化学学报》 * |
| 龙世军等: ""聚丙二醇/螺毗喃凝胶的制备及其光致变色行为"", 《两岸三地高分子液晶态与超分子有序结构学术研讨会》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI780043B (en) * | 2016-03-10 | 2022-10-11 | 日商三菱瓦斯化學股份有限公司 | Synthetic resin laminate having photochromic properties and lens using the same |
| CN109021268A (en) * | 2018-09-04 | 2018-12-18 | 山东大学 | A kind of preparation method of the photochromic gel membrane material of quick response |
| CN109021268B (en) * | 2018-09-04 | 2021-04-23 | 山东大学 | Preparation method of quick-response photochromic gel membrane material |
| CN111793107A (en) * | 2019-04-09 | 2020-10-20 | 中国科学院化学研究所 | DMSO-free cryopreservation liquid and preparation method thereof |
| CN111793107B (en) * | 2019-04-09 | 2022-04-12 | 中国科学院化学研究所 | DMSO-free cryopreservation liquid and preparation method thereof |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
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