CN110684223A - Erasable room temperature phosphorescent composite material of benzoquinone-based carbon dot/vinyl pyrrolidone polymer and preparation method and application thereof - Google Patents
Erasable room temperature phosphorescent composite material of benzoquinone-based carbon dot/vinyl pyrrolidone polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN110684223A CN110684223A CN201911027588.9A CN201911027588A CN110684223A CN 110684223 A CN110684223 A CN 110684223A CN 201911027588 A CN201911027588 A CN 201911027588A CN 110684223 A CN110684223 A CN 110684223A
- Authority
- CN
- China
- Prior art keywords
- benzoquinone
- room temperature
- erasable
- composite material
- based carbon
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000004057 1,4-benzoquinones Chemical class 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229920002799 BoPET Polymers 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001701 chloroform Drugs 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ADNXYZUJPHVRPJ-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;styrene Chemical compound C=CN1CCCC1=O.C=CC1=CC=CC=C1 ADNXYZUJPHVRPJ-UHFFFAOYSA-N 0.000 claims description 4
- JKLYZOGJWVAIQS-UHFFFAOYSA-N 2,3,5,6-tetrafluorocyclohexa-2,5-diene-1,4-dione Chemical compound FC1=C(F)C(=O)C(F)=C(F)C1=O JKLYZOGJWVAIQS-UHFFFAOYSA-N 0.000 claims description 4
- RDQSIADLBQFVMY-UHFFFAOYSA-N 2,6-Di-tert-butylbenzoquinone Chemical compound CC(C)(C)C1=CC(=O)C=C(C(C)(C)C)C1=O RDQSIADLBQFVMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 4
- -1 -tert-butyl parabenzoquinone Chemical compound 0.000 claims description 3
- HLKZFSVWBQSKKH-UHFFFAOYSA-N but-3-enoic acid;1-ethenylpyrrolidin-2-one Chemical compound OC(=O)CC=C.C=CN1CCCC1=O HLKZFSVWBQSKKH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000001259 photo etching Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 59
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 238000003756 stirring Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 17
- 238000001296 phosphorescence spectrum Methods 0.000 description 16
- 230000005284 excitation Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 7
- 101100063942 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) dot-1 gene Proteins 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000005562 fading Methods 0.000 description 7
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000005281 excited state Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000008033 biological extinction Effects 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- LWHDQPLUIFIFFT-UHFFFAOYSA-N 2,3,5,6-tetrabromocyclohexa-2,5-diene-1,4-dione Chemical compound BrC1=C(Br)C(=O)C(Br)=C(Br)C1=O LWHDQPLUIFIFFT-UHFFFAOYSA-N 0.000 description 3
- ZZYASVWWDLJXIM-UHFFFAOYSA-N 2,5-di-tert-Butyl-1,4-benzoquinone Chemical compound CC(C)(C)C1=CC(=O)C(C(C)(C)C)=CC1=O ZZYASVWWDLJXIM-UHFFFAOYSA-N 0.000 description 3
- LNXVNZRYYHFMEY-UHFFFAOYSA-N 2,5-dichlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C(Cl)=CC1=O LNXVNZRYYHFMEY-UHFFFAOYSA-N 0.000 description 3
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 description 3
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-UHFFFAOYSA-N 0.000 description 3
- XHKUTQNVGAHLPK-UHFFFAOYSA-N 2-fluorocyclohexa-2,5-diene-1,4-dione Chemical compound FC1=CC(=O)C=CC1=O XHKUTQNVGAHLPK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000688 Poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SJQISFXXYCYMIK-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate;1-ethenylpyrrolidin-2-one Chemical compound C=CN1CCCC1=O.CN(C)CCOC(=O)C(C)=C SJQISFXXYCYMIK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003996 delayed luminescence Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- 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
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
Abstract
The invention discloses a benzoquinone-based carbon dot/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material, and preparation and application thereof, and belongs to the technical field of composite materials and organic room temperature phosphorescent materials. The method comprises the following steps of (1) blending benzoquinone-based carbon points and vinyl pyrrolidone polymers prepared by a solvothermal method by using a benzoquinone derivative and organic polyamine as raw materials to prepare an erasable room temperature phosphorescent composite material; and the method is applied to the anti-counterfeiting aspect of the photoetching pattern. The storage time of the room temperature phosphorescence pattern in the material is regulated and controlled by adjusting the matrix molecular weight and/or the sealing processing condition; the invention can realize the regulation and control of erasable phosphorescence retention time by the modulation of carbon dot raw materials, a substrate and sealing processing conditions so as to meet diversified application requirements.
Description
Technical Field
The invention belongs to the technical field of composite materials and organic room temperature phosphorescent materials, and particularly relates to a benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material, and a preparation method and application thereof.
Background
Phosphorescence is the process by which a luminescent molecule is excited to a singlet excited state, then undergoes intersystem crossing to form a triplet excited state and further passes through forbidden (T)1→S0) The photophysical phenomenon of transition luminescence. Phosphorescence has a longer emission lifetime (μ s-h) than short-lived fluorescence (ns) due to forbidden transition from the triplet excited state to the ground state. On the other hand, phosphorescent emission generally requires lower temperatures (e.g., 77K) to avoid non-radiative losses due to longer triplet excited state lifetimes, which are easily quenched by non-radiative losses.
The room temperature phosphorescent material is a material capable of realizing phosphorescent emission at room temperature, and common room temperature phosphorescent materials mostly contain heavy metal coordination ions or rigid crystal structures containing heavy metals. The existence of heavy metal ions can promote spin-orbit coupling, the rigid structure can reduce the non-radiative loss of the triplet excited state, and the two can effectively enhance the phosphorescence of the material at room temperature.
In recent years, the development of pure organic room temperature phosphorescent materials has gained more and more attention because inorganic room temperature phosphorescent materials containing heavy metals still have some problems in toxicity and cost. Compared with the former, the pure organic room temperature phosphorescent material realizes triplet state luminescence by constructing an organic crystal or a specific host-guest structure, and does not depend on heavy metal elements with higher toxicity and higher cost. Among them, phosphorescent composites based on carbon dot polymers are being developed rapidly in recent years. The carbon dots are a type of luminous nano-particles which have the size below 10nm and mainly consist of light elements such as carbon, nitrogen, oxygen and the like. As the carbon dot surface usually has rich functional groups such as amino/carboxyl/hydroxyl, etc., the carbon dot surface can be effectively fixed by some polymer matrixes (such as polyvinyl alcohol, polyacrylic acid, polyvinyl, pyrrolidone, etc.) with stronger hydrogen bonding effect, the non-radiative transition loss of a triplet excited state is greatly reduced, and the room-temperature phosphorescence is realized.
Among the reported purely organic room temperature phosphorescent materials, most of the materials show stable room temperature phosphorescence characteristics, following a simple luminescence process of "excitation → phosphorescence emission". However, in many specific application scenarios, the intelligence, environmental responsiveness, and editability of the luminescent material are increasingly required. In response to this demand, erasable room temperature phosphorescent materials have been produced in recent years (Wan S, Lu W. Angewandte Chemie International Edition, 2017, 56 (7): 17841788.; Gu L, Shi H, Gu M, et al.2018, 57 (28): 84258431.; Gmelch M, Thomas H, FriesF, et al.science advances, 2019, 5 (2): eaau 7310.). The material can change the photophysical characteristics of the irradiated part reversibly by light irradiation in advance during use, and local room temperature phosphorescence luminescence is formed under the action of subsequent exciting light, so that a rewritable room temperature phosphorescence pattern is realized.
At present, the success of pure organic erasable room temperature phosphorescent materials is very few, and the regulation and control of the performance of the materials are limited by synthesis means/cost due to the dependence on small molecular organic dyes. Most carbon dot-based room temperature phosphorescent materials have the advantages of low cost and adjustable performance, but erasable room temperature phosphorescence of carbon dot-based composite materials is not reported until now. How to use the carbon dot-based material to realize low-cost adjustable pure organic erasable room temperature phosphorescence has important academic value and practical significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of how to use a carbon dot-based material to realize a low-cost adjustable pure organic erasable room temperature phosphorescent composite material. In order to solve the technical problems, the invention aims to provide a benzoquinone-based carbon dot/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material; the invention also aims to provide a preparation method of the erasable room temperature phosphorescent composite material of the benzoquinone-based carbon dot/vinyl pyrrolidone polymer; the invention also aims to provide application of the benzoquinone-based carbon dot/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone type polymer erasable room temperature phosphorescent composite material comprises the steps of mixing the benzoquinone-based carbon point and the vinyl pyrrolidone type polymer in a solvent, volatilizing the solvent to form a film through heat treatment, and sealing to obtain the benzoquinone-based carbon point/vinyl pyrrolidone type polymer erasable room temperature phosphorescent composite material; the benzoquinone-based carbon point is synthesized by taking a benzoquinone derivative and organic polyamine as raw materials through a solvothermal method; the solvent used in the preparation of the composite material is any one or a mixture of ethanol, water, methanol, dichloromethane, trichloromethane, tetrahydrofuran, formamide, N-dimethylformamide or N, N-dimethylacetamide; the molecular weight of the vinyl pyrrolidone polymer is 5000-2000000; the mass ratio of the benzoquinone-based carbon points to the vinyl pyrrolidone polymer is 1: 99-1: 199; mixing the benzoquinone-based carbon points and the vinyl pyrrolidone polymer in a solvent to obtain a solution with the solid content of 1-5%; the temperature for volatilizing the heat treatment solvent to form the film is 40-180 ℃, and the time is 0.5-48 h. And the sealing processing is to carry out plastic package treatment on the polymer film by using a PET (polyethylene terephthalate) film with the thickness of 50-150 mu m.
The preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material comprises the step of preparing a mixture of one or more of polyvinyl pyrrolidone, a poly (vinyl pyrrolidone dimethylaminoethyl methacrylate) copolymer, a poly (vinyl pyrrolidone styrene) copolymer or a poly (vinyl pyrrolidone vinyl acetate) copolymer.
The preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material comprises the following steps of (1) preparing a film, wherein the film is a self-supporting film or a film attached to the surface of a substrate; the substrate is quartz or PET; the film forming method comprises the steps of drop coating, drying and film forming, spin coating and film forming or dip coating and drawing.
The preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material comprises the step of heating by any one or combination of hot air heating, vacuum heating, contact heating, illumination or microwave radiation in the heat treatment solvent volatilization process.
The preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material comprises the following steps of enabling the molar ratio of the benzoquinone derivative to the organic polyamine to be 1: 0.02-1: 10; the dispersion concentration of the p-benzoquinone derivative in the solvent is 1-100 mmol/L; the solvent used in the solvothermal method is any one or a mixture of ethanol, water, methanol, dichloromethane, trichloromethane, tetrahydrofuran, formamide, N-dimethylformamide or N, N-dimethylacetamide; the reaction temperature of the solvothermal method is 40-260 ℃, and the reaction time is 1-72 h.
According to the preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material, the benzoquinone derivative conforms to the following general formula (I):
in the formula (I), R1、R2、R3And R4is-H, -CH3, -t-Bu, -OH, -F, -Cl, -Br or-I.
The benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material is prepared by a method for preparing the benzoquinone derivative, wherein the benzoquinone derivative is any one of p-benzoquinone, 2-methyl-p-benzoquinone, 2-chloro-p-benzoquinone, 2-fluoro-p-benzoquinone, 2, 5-dihydroxy-p-benzoquinone, 2, 5-dichloro-p-benzoquinone, 2, 5-di-tert-butyl-p-benzoquinone, 2, 6-disubstituted-p-benzoquinone, 2, 6-di-tert-butyl-p-benzoquinone, 2, 3, 5, 6-tetrachloro-p-benzoquinone, 2, 3, 5, 6-tetrafluoro-p-benzoquinone or 2, 3, 5, 6-tetrabromo-p-benzoquinone.
The preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material comprises the following steps of:
in the formula (II), n is 1 to 200.
The erasable room temperature phosphorescent composite material of the benzoquinone-based carbon point/vinyl pyrrolidone polymer is prepared by the preparation method of the erasable room temperature phosphorescent composite material of the benzoquinone-based carbon point/vinyl pyrrolidone polymer.
The benzoquinone-based carbon dot/vinyl pyrrolidone polymer erasable room temperature phosphorescent composite material is applied to the anti-counterfeiting of a photoetching pattern.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) after the composite material prepared by the invention is intensively irradiated for a period of time by using exciting light with the wavelength of 300-450 nm, the room-temperature phosphorescence of the irradiated part is converted from nothing to nothing due to the excited consumption of triplet oxygen; when the whole material is irradiated again, only the portion irradiated in advance exhibits room-temperature phosphorescence, and the rest does not exhibit delayed luminescence visible to the naked eye. After a period of time of standing or heating, the phosphorescence at room temperature gradually decays until the phosphorescence disappears, and the process is reversible; the erasable room-temperature phosphorescence in the flexible transparent film is realized, and the application range of the erasable room-temperature phosphorescence material is expanded.
(2) The invention can regulate and control the preservation time of the room temperature phosphorescence pattern in the material by changing the molecular weight of the polymer matrix and the sealing processing condition. And imprinting of specific complex patterns can be achieved by using a programmably moving light source or mask.
(3) The invention can also utilize the difference of the fading speed of the photoetched room temperature phosphorescent pattern at different temperatures to display whether the material has thermal history of being exposed for a certain time length at a certain temperature.
(4) The invention realizes the pure organic room temperature phosphorescence emission with longer wavelength (600 nm); the composite material has higher photoetching resolution (> 724 dpi).
(5) The invention can realize the regulation and control of erasable phosphorescence retention time by the modulation of carbon dot raw materials, a substrate and heat treatment temperature so as to meet diversified application requirements.
Drawings
FIG. 1 is a schematic diagram of the design and synthesis of a benzoquinone-based carbon dot/vinylpyrrolidone polymer erasable room temperature phosphorescent composite material;
FIG. 2 is a transmission electron micrograph and a particle size distribution curve of carbon dot 1 in example 1;
FIG. 3 is a graph of the steady state and phosphorescence spectra and phosphorescence lifetime of the material 1 of example 1, wherein FIG. 3a is a graph of the steady state spectra/room temperature phosphorescence spectra, and FIG. 3b is a graph of the phosphorescence lifetime;
FIG. 4 is a graph of the variation of the phosphorescence intensity at room temperature under different illumination light intensities of the material 1, wherein FIG. 4a is a graph of the variation of the phosphorescence intensity at room temperature with illumination time, and FIG. 4b is a graph of the average power of the illumination light versus the point where the phosphorescence intensity at room temperature reaches the strongest value 1/2; a plot of room temperature phosphorescence intensity versus time at different excitation light intensities;
FIG. 5 is a diagram of example 1 in which material 1 is repeatedly erased and written to form a photo-imprinted anti-counterfeit pattern;
FIG. 6 is a pictorial representation of material 1 from example 1 taken under an optical microscope after it has been photolithographically imprinted using a USAF1951 image resolution standard mask;
FIG. 7 is a physical representation of the decay of the phosphorescent pattern after photo-imprinting of materials 1 and 4 from example 7;
FIG. 8 is a schematic diagram and a physical diagram of an application of the thermal history label according to embodiment 8, in which FIG. a is a schematic diagram and FIG. b is a physical diagram;
FIG. 9 is a steady state and room temperature phosphorescence spectrum for materials 9-14 of examples 9-14, wherein FIG. 9a is a steady state and room temperature phosphorescence spectrum for material 9, FIG. 9b is a steady state and room temperature phosphorescence spectrum for material 10, FIG. 9c is a steady state and room temperature phosphorescence spectrum for material 11, FIG. 9d is a steady state and room temperature phosphorescence spectrum for material 12, FIG. 9e is a steady state and room temperature phosphorescence spectrum for material 13, and FIG. 9f is a steady state and room temperature phosphorescence spectrum for material 14;
FIG. 10 is a graph showing phosphorescence lifetime of materials 9-14 in examples 9-14, where FIG. 10a is a graph showing phosphorescence lifetime of material 9, FIG. 10b is a graph showing phosphorescence lifetime of material 10, FIG. 10c is a graph showing phosphorescence lifetime of material 11, FIG. 10d is a graph showing phosphorescence lifetime of material 12, FIG. 10e is a graph showing phosphorescence lifetime of material 13, and FIG. 10f is a graph showing phosphorescence lifetime of material 14.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
FIG. 1 is a schematic diagram of the design and synthesis of a benzoquinone-based carbon dot/vinyl pyrrolidone type polymer erasable room temperature phosphorescent composite material, which is prepared according to FIG. 1. 2mmol of p-benzoquinone (216mg) was weighed and dissolved in 100mL of absolute ethanol to obtain a 20mM ethanol solution of p-benzoquinone, and 4mmol of ethylenediamine (240mg, 1: 4) was added to the above solution with stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 120 ℃ for 10h, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 10% methanol/ethyl acetate mixed solvent) to obtain carbon point 1. The TEM (transmission electron microscopy) morphology of carbon dot 1 is shown in fig. 2: the average particle size of the carbon dots 1 is 6.4nm, and the particle size distribution shows a log-normal distribution rule. The high resolution lattice image showed it to have a partially crystalline morphology with a typical lattice fringe spacing of 0.24 nm.
Weighing 5mg of carbon dot 1 and 995mg of polyvinylpyrrolidone with the average molecular weight of 130 ten thousand, stirring to dissolve the two in 19mL of deionized water together to obtain a solution 1 with the solid content of 5%, weighing 8mL of the solution, dripping the solution on a circular culture dish mould with the diameter of 6cm, heating the solution by using a blast oven at 40 ℃ for 10h to remove most of the solvent, transferring the solution to a vacuum oven at 120 ℃ for vacuum heating and drying for 2h, and marking the obtained flexible film as a film 1. Carrying out plastic package on the film 1 by using a PET film with the thickness of 80 mu m to obtain a material 1; steady state/room temperature phosphorescence spectrum (fig. 3a) and phosphorescence lifetime plot (fig. 3b) for material 1. It is shown from FIG. 3a that the material 1 has a stationary spectral peak at 470nm and exhibits blue-green light emission and a phosphorescent peak at 580nm and exhibits orange-yellow light emission. As can be seen from FIG. 3b, the phosphorescence lifetime of material 1 is 476 ms.
The power density of the power consumption is 0.8mW/cm2，0.6mW/cm2，0.4mW/cm2，0.2mW/cm2，0.08mW/cm2The material 1 was continuously irradiated with the excitation light, and the change in the phosphorescence intensity at room temperature was recorded. The results are shown in FIG. 4. FIG. 4a shows that the room temperature phosphorescence intensity at the irradiated part of the material 1 is gradually increased with the increase of the irradiation time, and the increasing speed and the irradiation light intensity show a positive correlation; FIG. 4b plots the average power of the illumination light against the room temperature phosphorescence intensity at the maximum 1/2 (t1/2) and shows that the t1/2 value decreases with increasing power, and the slope of the logarithmic plot of the two coordinates is approximately-1, i.e., the t1/2 value is inversely proportional to the average power of the illumination light.
The material 1 was covered with a mask and then applied with a power density of 100mW/cm2After continuously irradiating for 10s with exciting light of 400nm, removing the light source to form the photoetched room temperature phosphorescence pattern. Then the power density is 10mW/cm2The 400nm exciting light is irradiated for a short time (less than 2s), and the light source is removed to correspondingly form the photoetching room temperature phosphorescence pattern in the hollow area of the original mask. Further, heating the material 1 (120 ℃, 10min) can erase the original lithographic pattern and can perform the next writing. The write read erase process can be repeated with the results shown in FIG. 5. The obtained photoetching pattern can be applied to encryption and anti-counterfeiting.
As shown in FIG. 6, the material 1 was photo-imprinted using a mask prepared according to USAF1951 image resolution Standard (USAF1951 resolution target), and stripes having a width of 53 μm were clearly resolved under an optical microscope, with a line resolution of 724dpi or more.
Example 2
The preparation of carbon dots 1 is described as follows in example 1. Weighing 5mg of carbon dot 1 and 995mg of polyvinylpyrrolidone with the average molecular weight of 36 ten thousand, dissolving the two in 19mL of deionized water together under stirring to obtain a solution 1 with the solid content of 5%, weighing 8mL of the solution, dripping the solution on a circular culture dish mould with the diameter of 6cm, heating the solution by using a blast oven at 40 ℃ for 10h to remove most of the solvent, transferring the solution to a vacuum oven at 130 ℃ for vacuum heating and drying for 1h, and plastically packaging by using a PET film with the thickness of 80 mu m to obtain a material 2.
Example 3
The preparation of carbon dots 1 is described as follows in example 1. Weighing 5mg of carbon dot 1 and 995mg of polyvinylpyrrolidone with the average molecular weight of 5.8 ten thousand, dissolving the two in 19mL of deionized water together under stirring to obtain a solution 1 with the solid content of 5%, weighing 8mL of the solution, dripping the solution on a circular culture dish mould with the diameter of 6cm, heating the solution by using a blast oven at 40 ℃ for 10h to remove most of the solvent, transferring the solution to a vacuum oven at 130 ℃ for vacuum heating and drying for 1h, and plastically packaging by using a PET film with the thickness of 80 mu m to obtain a material 3.
Example 4
The preparation of carbon dots 1 is described as follows in example 1.5 mg of carbon dot 1 and 995mg of polyvinylpyrrolidone having an average molecular weight of 8000 were weighed and dissolved together with stirring in 19mL of deionized water to obtain a solution having a solid content of 5%. 8mL of the solution is weighed and dripped on a circular culture dish mould with the diameter of 6cm, heated for 10h at 40 ℃ by using a blast oven to remove most of the solvent, transferred to a vacuum oven with the temperature of 130 ℃ for vacuum heating and drying for 1h, and plastically packaged by using a PET film with the thickness of 80 mu m to obtain a material 4. The power density of the power supply is 10mW/cm2The 400nm exciting light continuously irradiates the materials 1-4 for 30s until the phosphorescence intensity reaches the maximum respectively, then the materials 1-4 are stored in a dark place at room temperature, and the room temperature phosphorescence relative intensity change is tested every 15min (the initial intensity is 100%, and the baseline stable intensity is 0%). As shown in Table 1, the erasable phosphorescence fading rate of the composite material is related to the molecular weight of the polymer matrix, and the fading rate of the phosphorescence can be adjusted by changing the molecular weight of the matrix. Generally, the rate of room temperature phosphorescence decay slows as the molecular weight of the matrix increases, increasing the time required for complete elimination.
Table 1 test results of room temperature phosphorescence fading rates of composite materials 1-4
| Storage time/ | Material | 1 | |
Material 3 | Material 4 |
| 0 | 100.0％ | 100.0％ | 100.0％ | 100.0％ | |
| 15 | 83.7％ | 66.1％ | 47.3％ | 3.5％ | |
| 30 | 63.5％ | 39.7％ | 22.7％ | 0.0％ | |
| 45 | 47.0％ | 26.1％ | 8.3％ | / | |
| 60 | 31.3％ | 16.5％ | 0.0％ | / | |
| 75 | 18.8％ | 6.6％ | / | / | |
| 90 | 9.3％ | 0.0％ | / | / | |
| 105 | 2.0％ | / | |||
| 120 | 0.0％ | / |
Example 5
The power density of the power supply is 10mW/cm2The 400nm exciting light continuously irradiates the material 1 for 30s until the phosphorescence intensity reaches the maximum, then the material 1 is respectively placed at-20 ℃ (253K), 4 ℃ (277K) and 25 ℃ (298K) and stored in a dark place, and the room temperature phosphorescence is tested at regular intervalsRelative intensity change (100% from initial intensity). The results are shown in Table 2. Compared with the room temperature storage, the room temperature phosphorescence fading rate of the composite material under the low temperature storage (4 ℃ and-20 ℃) is obviously slowed down, the room temperature phosphorescence maintaining time of the material 1 at 4 ℃ is more than 6 hours, and the room temperature phosphorescence maintaining time at-20 ℃ is more than 48 hours.
TABLE 2 test results of room temperature phosphorescence extinction Rate at Low temperature storage of composite Material 1
Example 6
The film 1 prepared in example 1 was subjected to plastic sealing using 50A, 100. mu.m, 125A and 150A PET films to obtain materials 5, 6, 7 and 8, respectively.
The power density of the power supply is 10mW/cm2The 400nm exciting light continuously irradiates the materials 1, 5-8 for 30s until the phosphorescence intensity reaches the maximum respectively, then the materials 1, 5-8 are placed at 25 ℃ and kept in a dark place, and the room temperature phosphorescence relative intensity change (with the initial intensity as 100%) is tested every 15 min. The results are shown in Table 3. The results show that the room temperature phosphorescence extinction rate of the material is related to the sealing condition, and the room temperature phosphorescence extinction rate of the material is slowed down as the thickness of the sealing film is increased, and the time required for complete elimination is increased.
TABLE 3 test results of room temperature phosphorescence extinction rate of the composite material 1, 5-8 stored at room temperature
Example 7
For materials 1 and 4, respectively, a power density of 1mW/cm was used2The excitation light of 400nm is continuously irradiated for 30s through a mask to obtain a photoetching pattern, and the room temperature phosphorescence pattern is photographed. Standing at room temperature for 30min, and using power density of 10mW/cm2Excitation at 400nmThe residual room temperature phosphorescence pattern was photographed after a brief illumination (0.5s) of light. The result of the obtained physical photograph is shown in FIG. 7. Corresponding to the results obtained in example 6, the room temperature phosphorescent pattern in the material 1 is completely preserved, and the room temperature phosphorescent pattern in the material 4 almost completely disappears within 30min, which shows that the difference of the molecular weight of the polymer matrix can affect the fading rate of the composite material phosphorescence, thereby showing that the fading rate of the composite material phosphorescence can be controlled by changing the molecular weight of the polymer matrix, so as to be conveniently applied in actual needs.
Example 8
Two 2cm by 1cm films were cut from the material 1 prepared in example 1, and these were labeled as sample A and sample B, respectively. Respectively using power density of 10mW/cm2The sample A and the sample B were continuously irradiated with the excitation light of 400nm through a mask for 30 seconds to obtain a lithographic pattern, and the two were stored at-20 ℃. For sample B, the sample was stored at-20 ℃ for 11 hours, then taken out, exposed to a room temperature environment (25 ℃) for 1 hour, and then stored again by freezing. The preservation effects of the room temperature phosphorescent patterns at 0h, 12h and 24h after the initial preservation are shown in FIG. 8. Obviously, after 1h of room temperature exposure, the room temperature phosphorescence pattern intensity in the sample B is attenuated, and after the preservation time reaches 24h, the phosphorescence pattern in the sample A is still completely preserved, but the pattern in the sample B almost completely disappears and is unrecognizable, and the temperature-sensitive display under low temperature can be realized based on the principle.
Example 9
2mmol of 2-methyl-p-benzoquinone (244mg) was weighed and dissolved in 100mL of methanol to obtain a 20mM ethanol solution of 2-methyl-p-benzoquinone, and 8mmol of ethylenediamine (480mg, 1: 4) was added to the above solution under stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 260 ℃ for 1h, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 10% methanol/ethyl acetate mixed solvent) to obtain carbon point 2.
5mg of C2 and 495mg of poly (1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate) copolymer with an average molecular weight of 40 ten thousand were weighed and dissolved in 19.5g of 10% ethanol/water mixed solvent under stirringTo obtain a solution 2 with a solid content of 5%, 5mL of the solution was measured and dropped on a circular quartz plate with a diameter of 4cm, and heated at 55 ℃ for 24 hours to remove most of the solvent, thereby obtaining a quartz-based supporting film. Transferring the mixture to a 150 ℃ forced air oven, heating and drying for 0.5h, taking out, and then plastically packaging by using a 80-micrometer PET film to obtain a material 9. The material 9 was placed at 10mW/cm2The steady state and phosphorescence spectrum were measured after the excitation light of 365nm was continuously irradiated for 1min to the maximum phosphorescence intensity at room temperature, and the results are shown in FIG. 9 a. The phosphorescence lifetime is shown in figure 10 a.
Example 10
2mmol of 2, 5-dihydroxy-p-benzoquinone (280mg) was weighed and dissolved in 50mL of deionized water to obtain a 40mM aqueous solution of 2, 5-dihydroxy-p-benzoquinone, and 2mmol of ethylenediamine (120mg, 1: 1) was added to the above solution under stirring until uniformly dispersed. The mixed solution was transferred to a 100mL hydrothermal reaction kettle, sealed, heated at 40 ℃ for 48 hours, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 10% methanol/ethyl acetate mixed solvent) to obtain carbon point 3.
A solid mixture of 5mg carbon dots 3 and 995mg of 8000 and 130 ten thousand molecular weight PVP, 1: 20, was weighed and co-dissolved in 49g N, N dimethylformamide with stirring to give a solution with a solids content of 2%, 0.5mL of the solution was weighed and applied dropwise to a 2cm X2 cm PET substrate, and heated on a heating plate at 45 ℃ for 24h to remove most of the solvent to give a PET substrate supporting film. Transferring the mixture to a vacuum oven at 100 ℃, heating and drying for 2h, taking out, and then plastically packaging by using a PET film of 80 mu m to obtain the material 10. The material 10 was placed at 5mW/cm2The steady state and phosphorescence spectrum were measured after continuous irradiation with the excitation light of 450nm for 5min to the maximum phosphorescence intensity at room temperature, and the results are shown in FIG. 9 b. The phosphorescence lifetime is shown in FIG. 10 b.
Example 11
4mmol of 2-chloro-p-benzoquinone (564mg) was weighed out and dissolved in 40mL of N, N-dimethylformamide to obtain a solution of 100mM of 2-chloro-p-benzoquinone, and 2mmol of ethylenediamine (120mg, 2: 1) was added to the above solution under stirring until uniformly dispersed. The mixed solution was transferred to a 100mL hydrothermal reaction kettle, sealed, heated at 50 ℃ for 48 hours, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 5% methanol/ethyl acetate mixed solvent) to obtain carbon point 4.
A1: 1 solid mixture of 5mg of carbon dot 4 and 995mg of 130 million molecular weight PVP and a poly (1-vinylpyrrolidone co 2-dimethylaminoethyl methacrylate) copolymer having an average molecular weight of 40 million was weighed, co-dissolved in 99g of formamide with stirring to give a solution having a solids content of 1%, 0.5mL of the solution was weighed and applied dropwise onto a 1.5cm by 1.5cm glass substrate, and heated at 60 ℃ for 24 hours to remove most of the solvent to give a glass substrate supporting film. Transferring the mixture to a 110 ℃ air-blast oven for heating and drying for 48 hours to obtain a material 11. The material 11 was placed at 10mW/cm2The steady state and phosphorescence spectrum were measured after the excitation light of 400nm was continuously irradiated for 1min to the maximum phosphorescence intensity at room temperature, and the results are shown in FIG. 9 c. The phosphorescence lifetime is shown in FIG. 10 c.
Example 12
0.1mmol of 2-fluoro-p-benzoquinone (12.6mg) was weighed and dissolved in 100mL of ethanol to obtain a 1mM solution of 2-fluoro-p-benzoquinone, and 1mmol of ethylenediamine (60mg, 1: 10) was added to the above solution under stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 90 ℃ for 72 hours and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 5% methanol/ethyl acetate mixed solvent) to obtain carbon point 5.
1mg of carbon point 5 and 199mg of PVP with an average molecular weight of 130 ten thousand are weighed and dissolved in 3.8g of dichloromethane together with stirring to obtain a solution with a solid content of 5%, 0.5mL of the solution is weighed and dripped on a glass substrate with the thickness of 1.5cm multiplied by 1.5cm, and the glass substrate is irradiated under a 100W infrared lamp for 6 hours to remove most of the solvent to obtain the glass substrate supporting film. Transferring the mixture to a forced air oven at 110 ℃ and heating and drying the mixture for 2 hours to obtain a material 12. Place material 12 at 10mW/em2The steady state and phosphorescence spectrum were measured after the excitation light of 400nm was continuously irradiated for 1min to the maximum phosphorescence intensity at room temperature, and the results are shown in FIG. 9 d. The phosphorescence lifetime is shown in FIG. 10 d.
Example 13
2mmol of 2, 5-dichloro-p-benzoquinone (352mg) was weighed out and dissolved in 100mL of ethanol to obtain a solution of 20mM of 2, 5-dichloro-p-benzoquinone, and 4mmol of ethylenediamine (240mg, 1: 2) was added to the above solution under stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 120 ℃ for 12h, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 5% methanol/ethyl acetate mixed solvent) to obtain carbon point 6.
5mg of carbon dot 6 and 995mg of PVP with an average molecular weight of 130 ten thousand are weighed, and dissolved in 19g of dichloromethane together with stirring to obtain a solution with a solid content of 5%, 0.5mL of the solution is weighed and applied dropwise onto a glass substrate of 1.5cm × 1.5cm, and heated at 40 ℃ for 24 hours to remove most of the solvent, thereby obtaining a glass substrate supporting film. Transferring the mixture to a vacuum oven at 130 ℃, and heating and drying the mixture for 2h to obtain a material 13. The material 13 was placed at 10mW/em2The steady state and phosphorescence spectrum were measured after the excitation light of 400nm was continuously irradiated for 1min to the maximum phosphorescence intensity at room temperature, and the results are shown in FIG. 9 e. The phosphorescence lifetime is shown in figure 10 e.
Example 14
2mmol of 2, 3, 5, 6-tetrachlorop-benzoquinone (488mg) was weighed out and dissolved in 100mL of ethanol to obtain a solution of 20mM of 2, 3, 5, 6-tetrachlorop-benzoquinone, and 4mmol of ethylenediamine (240mg, 1: 2) was added to the above solution with stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 120 ℃ for 12h, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 5% methanol/ethyl acetate mixed solvent) to obtain carbon point 7.
5mg of carbon dot 7 and 995mg of PVP with an average molecular weight of 130 ten thousand were weighed, and were co-dissolved in 19g of methanol with stirring to obtain a solution with a solid content of 5%, 0.5mL of the solution was weighed and dropped on a glass substrate of 1.5cm X1.5 cm, and heated at 40 ℃ for 24 hours to remove most of the solvent, thereby obtaining a glass substrate supporting film. Transferring the mixture to a forced air oven at 130 ℃ for heat treatment for 12h to obtain a material 14. The material 14 was placed at 10mW/cm2The steady state and phosphorescence spectrum were measured after the excitation light of 400nm was continuously irradiated for 1min to the maximum phosphorescence intensity at room temperature, and the results are shown in FIG. 9 f. The phosphorescence lifetime is shown in FIG. 10 f.
Example 15
2mmol of 2, 3, 5, 6-tetrafluoro-p-benzoquinone (360mg) was weighed and dissolved in 100mL of formamide to obtain a solution of 20mM of 2, 3, 5, 6-tetrafluoro-p-benzoquinone, and 4mmol of diethylenetriamine (412mg, 1: 2) was added to the above solution with stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 120 ℃ for 12h, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 30% methanol/ethyl acetate mixed solvent) to obtain carbon point 8.
5mg of a mixture of carbon number 8 and 995mg of PVP with an average molecular weight of 130 ten thousand and a poly (vinylpyrrolidone styrene) copolymer in a mass ratio of 1: 1 were weighed out, co-dissolved in 19g of deionized water with stirring to give a solution with a solids content of 5%, 0.5mL of the solution was measured and applied dropwise to a 1.5cm X1.5 cm glass substrate, and heated on a heating plate at 40 ℃ for 24h to remove most of the solvent to give a glass substrate supporting film. It was transferred to a 100 ℃ forced air oven, heated 10 ℃ to 180 ℃ every 0.5h and held for 30min to give material 15.
Example 16
2mmol of 2, 3, 5, 6-tetrabromo-p-benzoquinone (840mg) was weighed out and dissolved in 100mL of tetrahydrofuran to obtain a solution of 20mM 2, 3, 5, 6-tetrabromo-p-benzoquinone, and 400mg of PEI having a molecular weight of 600 was added to the above solution with stirring until uniform dispersion was achieved. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 120 ℃ for 12h, and naturally cooled to room temperature. Filtering, rotary evaporating to remove solvent, collecting product, and purifying by silica gel column chromatography (eluent: 50% methanol/ethyl acetate mixed solvent) to obtain carbon point 9.
5mg of carbon dot 9 and 995mg of poly (vinylpyrrolidone styrene) copolymer were weighed, and were co-dissolved in 19g of ethanol with stirring to obtain a solution having a solid content of 5%, 0.5mL of the solution was weighed and dropped on a glass substrate of 1.5 cm. times.1.5 cm, and the substrate was heated on a heating plate at 40 ℃ for 24 hours to remove most of the solvent, thereby obtaining a glass substrate supporting film. Transferring the mixture into a vacuum oven at 130 ℃, heating and drying for 0.5h to obtain a material 16.
Example 17
2mmol of 2, 5-di-tert-butyl-p-benzoquinone (440mg) was weighed and dissolved in 100mL of chloroform to obtain a solution of 20mM 2, 5-di-tert-butyl-p-benzoquinone, and 400mg of PEI having a molecular weight of 10000 was added to the above solution with stirring until uniform dispersion was achieved. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 120 ℃ for 12h, and naturally cooled to room temperature. The product was collected by filtration, rotary evaporated to remove the solvent, dispersed in water and lyophilized to give carbon dots 10.
5mg of C10 and 995mg of poly (vinylpyrrolidone-vinyl acetate) copolymer were weighed, and were co-dissolved in 19g of chloroform with stirring to obtain a solution having a solid content of 5%, 0.5mL of the solution was weighed and dropped on a glass substrate of 1.5 cm. times.1.5 cm, and heated at 40 ℃ for 24 hours to remove most of the solvent, thereby obtaining a glass substrate supporting film. Transferring the mixture to a vacuum oven at 130 ℃ and heating and drying the mixture for 1h to obtain a material 17.
Example 18
2mmol of 2, 6-di-tert-butyl-p-benzoquinone (440mg) was weighed and dissolved in 100mL of a 1: 1 mixed solvent of ethanol and N, N-dimethylacetamide to obtain a 20mM solution of 2, 6-di-tert-butyl-p-benzoquinone, and 146mg of triethylenetetramine (1mmol, 1: 0.5) was added to the above solution under stirring until uniformly dispersed. The mixed solution is transferred to a 200mL hydrothermal reaction kettle, sealed, heated at 180 ℃ for 8h, and naturally cooled to room temperature. The product was collected by filtration, rotary evaporated to remove the solvent, dispersed in water and lyophilized to give carbon dots 11.
5mg of carbon dot 11 and 995mg of PVP with an average molecular weight of 5.8 ten thousand were weighed, co-dissolved in 19g N, N dimethylacetamide under stirring to give a solution with a solid content of 5%, 0.5mL of the solution was weighed and dropped on a glass substrate of 1.5cm by 1.5cm, and heated at 40 ℃ for 24 hours to remove most of the solvent to give a glass substrate supporting film. It was transferred to a 100W microwave oven and heated in a microwave at 10% power for 30min to give material 18.
Example 19
The preparation of carbon dots 1 is described as follows in example 1. 50mg of carbon dot 1 and 9.95g of polyvinylpyrrolidone with the average molecular weight of 130 ten thousand are weighed, mixed and blended, and then injection molding is carried out to form a film, and the film is plastically packaged by using a 150 mu mPE film to obtain the material 19.
Claims (10)
1. The preparation method of the benzoquinone-based carbon point/vinyl pyrrolidone type polymer erasable room temperature phosphorescent composite material is characterized in that the benzoquinone-based carbon point/vinyl pyrrolidone type polymer erasable room temperature phosphorescent composite material is obtained by mixing the benzoquinone-based carbon point and the vinyl pyrrolidone type polymer in a solvent, volatilizing the solvent to form a film through heat treatment and carrying out sealing processing; the benzoquinone-based carbon point is synthesized by taking a benzoquinone derivative and organic polyamine as raw materials through a solvothermal method; the solvent used in the preparation of the composite material is any one or a mixture of ethanol, water, methanol, dichloromethane, trichloromethane, tetrahydrofuran, formamide, N-dimethylformamide or N, N-dimethylacetamide; the molecular weight of the vinyl pyrrolidone polymer is 5000-2000000; the mass ratio of the benzoquinone-based carbon points to the vinyl pyrrolidone polymer is 1: 99-1: 199; mixing the benzoquinone-based carbon points and the vinyl pyrrolidone polymer in a solvent to obtain a solution with the solid content of 1-5%; the temperature for volatilizing the heat treatment solvent to form a film is 40-180 ℃, and the time is 0.5-48 h; and the sealing processing condition is to use a PET film with the thickness of 50-150 mu m to carry out plastic package processing on the polymer film.
2. The method for preparing a benzoquinone-based carbon dot/vinyl pyrrolidone-based polymer erasable room temperature phosphorescent composite material as claimed in claim 1, wherein the vinyl pyrrolidone-based polymer is one or more of polyvinylpyrrolidone, poly (vinylpyrrolidone-dimethylaminoethyl methacrylate) copolymer, poly (vinylpyrrolidone-styrene) copolymer or poly (vinylpyrrolidone-vinyl acetate) copolymer.
3. The method for preparing a benzoquinone-based carbon dot/vinylpyrrolidone polymer-based erasable room temperature phosphorescent composite material as claimed in claim 1, wherein the film is a self-supporting film or a film attached to a surface of a substrate; the substrate is quartz or PET; the film forming method comprises the steps of drop coating, drying and film forming, spin coating and film forming or dip coating and drawing.
4. The method for preparing the erasable room temperature phosphorescent composite material of the benzoquinone-based carbon dot/vinyl pyrrolidone polymer as claimed in claim 1, wherein the heating means used in the solvent volatilization process of the heat treatment is any one or a combination of hot air heating, vacuum heating, contact heating, illumination or microwave radiation.
5. The method for producing a benzoquinone-based carbon dot/vinylpyrrolidone-based polymer erasable room temperature phosphorescent composite material according to claim 1, wherein the molar ratio of the p-benzoquinone derivative to the organic polyamine is 1: 0.02 to 1: 10; the dispersion concentration of the p-benzoquinone derivative in the solvent is 1-100 mmol/L; the solvent used in the solvothermal method is any one or a mixture of ethanol, water, methanol, dichloromethane, trichloromethane, tetrahydrofuran, formamide, N-dimethylformamide or N, N-dimethylacetamide; the reaction temperature of the solvothermal method is 40-260 ℃, and the reaction time is 1-72 h.
6. The method for preparing a benzoquinone-based carbon dot/vinylpyrrolidone polymer-erasable room temperature phosphorescent composite material according to claim 1, wherein the benzoquinone derivative is represented by the following general formula (I):
in the formula (I), R1、R2、R3And R4is-H, -CH3, -t-Bu, -OH, -F, -Cl, -Br or-I.
7. The method of producing a benzoquinone-based carbon dot/vinylpyrrolidone-based polymer erasable room temperature phosphorescent material as claimed in claim 1, wherein said parabenzoquinone derivative is any one of parabenzoquinone, 2-methyl parabenzoquinone, 2-chloro parabenzoquinone, 2-fluoro parabenzoquinone, 2, 5-dihydroxy parabenzoquinone, 2, 5-dichloro parabenzoquinone, 2, 5-di-tert-butyl parabenzoquinone, 2, 6-di-tert-butyl parabenzoquinone, 2, 3, 5, 6-tetrachloroparabenzoquinone, 2, 3, 5, 6-tetrafluoroparabenzoquinone or 2, 3, 5, 6-tetrabromo parabenzoquinone.
8. The method of preparing a benzoquinone based carbon dot/vinylpyrrolidone based polymer erasable room temperature phosphorescent composite material of claim 1, wherein the organic polyamine corresponds to the following general formula (II):
in the formula (II), n is 1 to 200.
9. The erasable room temperature phosphorescent composite material of the benzoquinone-based carbon dot/vinyl pyrrolidone-based polymer prepared by the method for preparing the erasable room temperature phosphorescent composite material of the benzoquinone-based carbon dot/vinyl pyrrolidone-based polymer according to any one of claims 1 to 8.
10. The use of the benzoquinone-based carbon dot/vinylpyrrolidone-based polymer erasable room temperature phosphorescent composite material of claim 9 in anti-counterfeiting of a lithographic pattern.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911027588.9A CN110684223B (en) | 2019-10-25 | 2019-10-25 | Erasable room temperature phosphorescent composite material of benzoquinone-based carbon dot/vinyl pyrrolidone polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911027588.9A CN110684223B (en) | 2019-10-25 | 2019-10-25 | Erasable room temperature phosphorescent composite material of benzoquinone-based carbon dot/vinyl pyrrolidone polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110684223A true CN110684223A (en) | 2020-01-14 |
| CN110684223B CN110684223B (en) | 2021-06-08 |
Family
ID=69114716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911027588.9A Active CN110684223B (en) | 2019-10-25 | 2019-10-25 | Erasable room temperature phosphorescent composite material of benzoquinone-based carbon dot/vinyl pyrrolidone polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110684223B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684807A (en) * | 2022-03-15 | 2022-07-01 | 浙江大学医学院附属第四医院 | Room-temperature-driven long-wavelength emission fluorescent carbon dot and preparation method and application thereof |
| CN114851657A (en) * | 2022-05-12 | 2022-08-05 | 深圳大学 | Editable dynamic phosphorescent flexible film and application method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192602A (en) * | 2018-01-22 | 2018-06-22 | 吉林大学 | It is a kind of with room temperature phosphorimetry property without metal-containing polymer carbon dots, preparation method and applications |
| CN108659831A (en) * | 2018-04-03 | 2018-10-16 | 郑州大学 | A kind of method that one kettle way prepares Solid substrate room temperature phosphorescence carbon dots |
| CN109082050A (en) * | 2018-08-15 | 2018-12-25 | 武汉理工大学 | A kind of preparation method of CQDs@PVP/PVDF compound dielectric film |
| CN109652058A (en) * | 2019-01-11 | 2019-04-19 | 南京大学 | A kind of preparation method of carbon quantum dot and its phosphorescence composite material |
-
2019
- 2019-10-25 CN CN201911027588.9A patent/CN110684223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192602A (en) * | 2018-01-22 | 2018-06-22 | 吉林大学 | It is a kind of with room temperature phosphorimetry property without metal-containing polymer carbon dots, preparation method and applications |
| CN108659831A (en) * | 2018-04-03 | 2018-10-16 | 郑州大学 | A kind of method that one kettle way prepares Solid substrate room temperature phosphorescence carbon dots |
| CN109082050A (en) * | 2018-08-15 | 2018-12-25 | 武汉理工大学 | A kind of preparation method of CQDs@PVP/PVDF compound dielectric film |
| CN109652058A (en) * | 2019-01-11 | 2019-04-19 | 南京大学 | A kind of preparation method of carbon quantum dot and its phosphorescence composite material |
Non-Patent Citations (4)
| Title |
|---|
| FRANCESCO RIGODANZA ET AL.: ""Customizing the Electrochemical Properties of Carbon Nanodots by Using Quinones in Bottom-Up Synthesis"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| HUILIN GOU ET AL.: ""Lifetime-tunable room-temperature phosphorescence of polyaniline carbon dots in adjustable polymer matrices"", 《NANOSCALE》 * |
| QIAN QIAN ZHANG ET AL.: ""A functional preservation strategy for the production of highly photoluminescent emerald carbon dots for lysosome targeting and lysosomal pH imaging"", 《NANOSCALE》 * |
| SHIGANG WAN AND WEI LU: ""Reversible Photoactivated Phosphorescence of Gold(I) Arylethynyl Complexes in Aerated DMSO Solutions and Gels"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684807A (en) * | 2022-03-15 | 2022-07-01 | 浙江大学医学院附属第四医院 | Room-temperature-driven long-wavelength emission fluorescent carbon dot and preparation method and application thereof |
| CN114684807B (en) * | 2022-03-15 | 2023-08-04 | 浙江大学医学院附属第四医院 | Long wavelength emission fluorescent carbon dot driven at room temperature and preparation method and application thereof |
| CN114851657A (en) * | 2022-05-12 | 2022-08-05 | 深圳大学 | Editable dynamic phosphorescent flexible film and application method thereof |
| WO2023217215A1 (en) * | 2022-05-12 | 2023-11-16 | 深圳大学 | Editable dynamic phosphorescent flexible film and application method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110684223B (en) | 2021-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Poly (arylene piperidine) quaternary ammonium salts promoting stable long‐lived room‐temperature phosphorescence in aqueous environment | |
| Yu et al. | Luminescence anti‐counterfeiting: from elementary to advanced | |
| Muthamma et al. | Carbon dots as emerging luminophores in security inks for anti-counterfeit applications-An up-to-date review | |
| CN110684223B (en) | Erasable room temperature phosphorescent composite material of benzoquinone-based carbon dot/vinyl pyrrolidone polymer and preparation method and application thereof | |
| Liang et al. | Water-induced ultralong room temperature phosphorescence by constructing hydrogen-bonded networks | |
| Jin et al. | Orange-red, green, and blue fluorescence carbon dots for white light emitting diodes | |
| Zhai et al. | Carbon dots confined in 3D polymer network: Producing robust room temperature phosphorescence with tunable lifetimes | |
| Wang et al. | Photo-induced morphology transition of a multifunctional photochromic bisthienylethene molecule with switchable aggregation-induced emission | |
| Zheng et al. | Polymerization‐induced emission of color‐tunable room temperature phosphorescence | |
| Meng et al. | Ultralong room-temperature phosphorescence from polycyclic aromatic hydrocarbons by accelerating intersystem crossing within a rigid polymer network | |
| Wang et al. | Nanocomposites of CsPbBr3 perovskite quantum dots embedded in Gd2O3: Eu3+ hollow spheres for LEDs application | |
| CN113956869B (en) | Manufacturing method of dielectric microsphere patterned array up-conversion luminescence flexible film applied to anti-counterfeiting mark | |
| Zhang et al. | Rational molecular and doping strategies to obtain organic polymers with ultralong RTP | |
| Jin et al. | Colourful organic afterglow materials with super-wide color gamut and scaled processability from cellulose | |
| Tian et al. | Thermostably photoswitchable red fluorescent polymeric nanoparticles for rewritable fluorescence patterning and zebrafish imaging | |
| Sheng et al. | Modulation of a fluorescence switch based on photochromic spirooxazine in composite organic nanoparticles | |
| Liu et al. | Towards efficient and stable multi-color carbon nanoparticle phosphors synergy between inner polar groups and outer silica matrix | |
| Shen et al. | Manipulating the transition of aggregated states to control the photochromism in a new triphenylethylene derivative | |
| Li et al. | Photo-stimuli responsive phosphorescence from carbon dots in porous gelatin | |
| CN114907842B (en) | Fluorescent carbon quantum dot gel, preparation method thereof and information circulating storage method | |
| Meng et al. | Preparation and optical characterization of an organoeuropium-doped sol–gel transparent luminescence thin film | |
| CN114058045B (en) | Organic room temperature phosphorescent thin film material with hydrothermal stimulus response and excitation dependence, and preparation and application thereof | |
| CN113444523B (en) | Preparation method and application of matrix-free long afterglow carbon dots and afterglow type regulation and control method | |
| CN110964526B (en) | Up-conversion nanoparticles with core-shell structure, preparation method and application thereof | |
| Guan et al. | Novel eco-friendly dye-polymer composite films for white LEDs: syntheses, structures and luminescence properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |