CN108191915A - Luminous ionic four-coordination manganese compound and its preparation method and application - Google Patents
Luminous ionic four-coordination manganese compound and its preparation method and application Download PDFInfo
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- CN108191915A CN108191915A CN201810069029.3A CN201810069029A CN108191915A CN 108191915 A CN108191915 A CN 108191915A CN 201810069029 A CN201810069029 A CN 201810069029A CN 108191915 A CN108191915 A CN 108191915A
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- 150000002697 manganese compounds Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- -1 propylene glycol-polyethylene Chemical group 0.000 claims description 4
- RIWQWHDNZIGXOI-UHFFFAOYSA-M [P].[Br-].C1(=CC=CC=C1)[P+](CC)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[Br-].C1(=CC=CC=C1)[P+](CC)(C1=CC=CC=C1)C1=CC=CC=C1 RIWQWHDNZIGXOI-UHFFFAOYSA-M 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 3
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 25
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of preparations and its application of luminous ionic four-coordination manganese compound, the present invention is prepared for a kind of luminous ionic four-coordination manganese compound to solve various energy resources and pollution problem caused by print paper disposably reads use in the prior art, which can be used for pure water copying and printing paper field to provide strong support for following green printing；And the synthesis step of the organophosphor ligand involved in the present invention is simple, mild condition, the ionic four-coordination manganese compound of acquisition have the advantages that it is at low cost, be easily obtained and performance stabilization.
Description
Technical field
The invention belongs to organic photoelectric functional material technical fields, and in particular to a kind of luminous ionic four-coordination manganese
Close the preparation and application of object.
Background technology
In past several centuries, paper serves as mankind's record, propagates the most important medium of information always, and most
Print paper can only all pass through disposable read and use.The production of paper and the felling of forest bring serious social concern.
In recent years, reversible stimuli responsive material gets more and more people's extensive concerning, by such material application on printing paper i.e.
Low cost, environmentally protective paper capable of repeat printing can be obtained, alleviates forest indiscriminate felling of trees, fixed-end forces difficulty, environmental pollution
The problems such as seriously, energy consumption is huge, the birth of this kind of material can be undoubtedly that society bring prominent contribution and huge
Economic interests.At present, have many team and have investigated paper capable of repeat printing, but there is also many shortcomings, such as the poison of dyestuff
Property it is high, materials synthesis is complicated and involves great expense.
Ionic four-coordination manganese compound because its have the characteristics that it is at low cost, be easily obtained with performance stablize, be constantly subjected to
The favor of people.However the application in terms of printing, it does not report also at present.Therefore, it is necessary to reasonably regulate and control the light of manganese complex
Physical property, works out that novel, quick, easily method realizes that its luminescent color in the case where spun lacing swashs changes, and realizes information
Printing and erasing.
Invention content
In view of the above problems, the present invention is intended to provide a kind of ionic four-coordination manganese compound and preparation method thereof
With application of the compound in rewritable paper, strong support will be provided for further development green printing.
To achieve these goals, the technical solution adopted in the present invention is as follows：The present invention relates to a kind of luminous ions
Type four-coordination manganese compound, the luminous ionic four-coordination manganese compound have the following structure general formula：
Wherein
X is：Br4 2-、Cl4 2-、Br2Cl2 2-、Br2I2 2-、Cl2I2 2-、I4 2-
The structure of R is：Wherein n, m 1-5
Between positive integer.
Synthetic method, the performance of P-M-X is similar, and by taking P-Mn as an example, the preparation process of P-Mn is mainly：1. organophosphor ligand
Synthesis：Bromoethane and triphenyl phosphorus in molar ratio 1：1 is uniformly mixed in toluene solution, is heated to reflux for 24 hours, adding at 120 DEG C
Enter ether sedimentation, you can obtain ethyltriphenylphosphonium bromide phosphorus ligand, the structural formula of organophosphor ligand is：
2. the synthesis of ionic four-coordination manganese compound：In acetone solvent system, by the hydration bromines of organophosphor ligand P and four
Change manganese in molar ratio 1:1 reacts 2h in 65 DEG C, and filtering is spin-dried for, the structural formula of P-Mn is：
In terms of ionic four-coordination manganese compound of the present invention can be applicable to pure water printing carbon paper, based on the present invention
The preparation method of the ionic four-coordination manganese compound carbon paper, which is characterized in that concrete operation step is as follows：
1. coated on filter paper be dissolved in dichloromethane polyethylene glycol propylene glycol-polyethylene glycol (PEG-PPG-PEG) it is molten
Liquid, drying is as first layer；
2. the manganese complex for being dissolved in dichloromethane and PEG-PPG-PEG mixed liquors are uniformly applied to first described in step 1
Layer top is used as the second layer；
3. coating PEG-PPG-PEG is as third layer on the second layer prepared in step 2.
The beneficial effects of the invention are as follows：The present invention disposably reads use to solve print paper in the prior art and causes
Forest indiscriminate felling of trees, fixed-end forces are difficult, environmental pollution is serious and the various problems such as energy consumption is big are prepared for a kind of shine
Ionic four-coordination manganese compound, the present invention by the way that it is combined with PEG-PPG-PEG constructs novel rewritable paper, this
Quenching fluorescence can be swashed by spun lacing by rewriteeing paper, realize the target of pure water printing, and strong branch is provided for following green printing
Support；And the synthesis step of the organophosphor ligand involved in the present invention is simple, mild condition, the ionic four-coordination manganese of acquisition is closed
Object have the advantages that it is at low cost, be easily obtained and performance stablize；Printing image on the rewritable paper of pure water prepared by the present invention can
To retain for a long time, compared with prior art, breakthrough progress is achieved.
Description of the drawings
Fig. 1 is a concentration of 1.0 × 10-5Emission spectrum of the P-Mn weak solutions of M in different solvents；
Fig. 2 is a concentration of 1.0 × 10-5Emission spectrum of the P-Mn n-hexanes and water mixed solution of M under different water contents；
Fig. 3 is the concentration of P-Mn and the relation map of cell activity；
Fig. 4 is emission spectrum of the P-Mn of same concentration under different humidity；
Fig. 5 is that ionic four-coordination manganese compound disclosed by the invention applies the design sketch in water printing；
Fig. 6 is the launching light spectrogram on paper before and after water prints；
Fig. 7 is the variation diagram of water printing effect in a heated condition.
Specific embodiment
In order to which those of ordinary skill in the art is made to be better understood on technical scheme of the present invention, below in conjunction with the accompanying drawings and
Embodiment is further described technical scheme of the present invention.
With reference to attached drawing 1-6
A kind of luminous ionic four-coordination manganese compound, has the following structure general formula：
Wherein
X is：Br4 2-、Cl4 2-、Br2Cl2 2-、Br2I2 2-、Cl2I2 2-、I4 2-
The structure of R is：Wherein n, m 1-5
Between positive integer.
Synthetic method, the performance of P-M-X is similar, and by taking P-Mn as an example, the preparation process of P-Mn is mainly：1. organophosphor ligand
Synthesis：Bromoethane and triphenyl phosphorus in molar ratio 1：1 is uniformly mixed in toluene solution, is heated to reflux for 24 hours, adding at 120 DEG C
Enter ether sedimentation, you can obtain ethyltriphenylphosphonium bromide phosphorus ligand, the structural formula of organophosphor ligand is：
2. the synthesis of ionic four-coordination manganese compound：In acetone solvent system, by the hydration bromines of organophosphor ligand P and four
Change manganese in molar ratio 1:1 reacts 2h in 65 DEG C, and filtering is spin-dried for；The structural formula of ionic four-coordination manganese compound P-Mn is：
Specific synthetic route is as follows：
In terms of ionic four-coordination manganese compound of the present invention can be applicable to pure water printing carbon paper, based on the present invention
The preparation method of the ionic four-coordination manganese compound carbon paper, concrete operation step are as follows：
1. coated on filter paper be dissolved in dichloromethane polyethylene glycol propylene glycol-polyethylene glycol (PEG-PPG-PEG) it is molten
Liquid, drying is as first layer；
2. the ionic four-coordination manganese compound for being dissolved in dichloromethane and PEG-PPG-PEG mixed liquors are uniformly applied to step
The second layer is used as above first layer described in 1；
3. coating PEG-PPG-PEG is as third layer on the second layer prepared in step 2.
The relevant research of application prospect has been carried out below for for ionic four-coordination manganese compound of the present invention
1. the characterization of compound P and the application of P-Mn：
(1) compound P (5-10mg) is dissolved in the deuterated reagent of 0.5mL, chemical combination is characterized respectively using 400Hz nuclear magnetic resonance spectrometers
The structure of object；
The characterization of organophosphor ligand P：
1H NMR (400MHz, CDCl3)
δ 7.62-7.89 (m, 15H), 3.83 (m, 2H), 8.21-8.07 (m, 2H), 3.83 (dq, 2H), 1.37 (m, 2H).
13C NMR (400MHz, CDCl3)
δ 134.6,133.04,130.02,117.34,16.55,6.29.
(2) compound concentration is 1.0 × 10-5The P-Mn weak solutions of M measure it in different solvents such as ethyl alcohol (Ethnol), two
Methylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), water (H2O), n-hexane, P- n-hexanes, tetrahydrofuran (THF) and dichloro
Methane (CH2Cl2) in emission spectrum, the results are shown in Figure 1 for specific experiment：
As shown in Figure 1, in addition to the P-Mn green lights (excitation wavelength in hexane solution：254nm, emission peak：522nm),
Remaining solution is all fluorescent quenching state.
(3) compound concentration is 1.0 × 10-5The P-Mn n-hexanes and water mixed solution of M measures it under different water contents
Emission spectrum, experimental result are as shown in Figure 2：
As shown in Figure 2, with the reduction of water content, emissive porwer gradually rises.Illustrate that water plays quenching fluorescence
Effect, the result just represent based on ionic four-coordination manganese compound of the present invention be expected to realize water printing.
(3) Study of cytotoxicity of P-Mn is assessed with Hela cells, experimental result is as shown in Figure 3：
From the figure 3, it may be seen that the cell activity of P-Mn is held at 80%, this just illustrates that the toxicity of P-Mn is low, relative to existing
The higher dyestuff of toxicity in technology, compound of the present invention have more preferably application prospect in terms of water printing.
The photophysical property research of humidity measurement and water the printing carbon paper of 2.P-Mn
(1) compound concentration is bis- solutions of chlorine of P-Mn of 5mg/mL, is then spin coated onto on quartz plate.It is surveyed under different humidity
Emission spectrum, the results are shown in Figure 4：
As shown in Figure 4, with the increase of humidity, the emission peak at 522nm slowly declines, and illustrates the fluorescence that water causes P-Mn
Quenching, this just provides possibility for the printing of next step water.
(2) water printing effect is studied：As shown in figure 5, clarity does not occur significantly the information of water printing after one year
Variation, printing image can retain longer time on paper, this is achieved compared with the rewritable paper of pure water of the prior art
Breakthrough progress.
(3) variation of emission spectrum and display effect on paper before and after water printing, as shown in fig. 6-7：It can be sent out from figure
The variation of the emissive porwer of carbon paper changes basically identical with Fig. 4 before and after existing water printing, and water causes the fluorescent quenching of P-Mn, reaches
Ideal effect is advantageously implemented the target of pure water printing.
Claims (4)
1. a kind of luminous ionic four-coordination manganese compound, it is characterised in that its general structure is as follows：
Wherein
X is：Br4 2-、Cl4 2-、Br2Cl2 2-、Br2I2 2-、Cl2I2 2-、I4 2-
The structure of R is：Wherein n, m between 1-5 just
Integer.
2. the preparation method of ionic four-coordination manganese compound to shine as described in claim 1, which is characterized in that P-M-X
Performance it is similar, by taking P-Mn as an example, preparation method comprises the steps of：
(1) synthesis of organophosphor ligand：First, by bromoethane and triphenyl phosphorus in molar ratio 1：1 mixes in toluene solution
It is even, it then, is heated to reflux at 120 DEG C for 24 hours, later, adds in ether and settled, you can obtain ethyltriphenylphosphonium bromide phosphorus and match
Body, the structural formula of organophosphor ligand are：
(2) synthesis of ionic four-coordination manganese compound：First, in acetone solvent system, organophosphor ligand P and four is hydrated
Manganous bromide in molar ratio 1:1 reacts 2h in 65 DEG C, then filters, is spin-dried for；The structural formula of ionic four-coordination manganese compound P-Mn
For：
3. application of the ionic four-coordination manganese compound as claimed in claim 1 or 2 in terms of pure water prints carbon paper.
4. the preparation method of ionic four-coordination manganese compound carbon paper as claimed in claim 1 or 2, which is characterized in that tool
Body operating procedure is as follows：
(1) polyethylene glycol propylene glycol-polyethylene glycol (PEG-PPG-PEG) solution for being dissolved in dichloromethane is coated on filter paper,
Drying is as first layer；
(2) the ionic four-coordination manganese compound for being dissolved in dichloromethane and PEG-PPG-PEG mixed liquors are uniformly applied to step 1 institute
As the second layer above the first layer stated；
(3) PEG-PPG-PEG is coated on the second layer prepared in step 2 as third layer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256497A (en) * | 2019-06-06 | 2019-09-20 | 宁波大学 | A kind of manganese complex luminescent material and its preparation method and application |
| CN112341491A (en) * | 2020-11-09 | 2021-02-09 | 中国计量大学 | Organic-inorganic hybrid long afterglow material, preparation method thereof and application thereof in ink-jet printing |
| US11034709B2 (en) * | 2019-05-29 | 2021-06-15 | The Hong Kong University Of Science And Technology | Organic long persistence luminescence compositions |
| CN114057796A (en) * | 2021-11-12 | 2022-02-18 | 郑州大学 | Hybrid material based on organic-metal manganese halide and preparation method thereof |
| CN114634528A (en) * | 2022-02-11 | 2022-06-17 | 华南理工大学 | Efficient narrow-band green light emitting metal halide and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3014621B1 (en) * | 1980-04-16 | 1981-04-23 | MD Papierfabriken Heinrich Nicolaus GmbH, 8060 Dachau | Response carbon paper |
| US5508180A (en) * | 1993-04-19 | 1996-04-16 | Enzymol International, Inc. | Biocatalytic oxidation using soybean peroxidase |
| JP4325314B2 (en) * | 2003-08-12 | 2009-09-02 | 東洋インキ製造株式会社 | Resin production method and ink |
-
2018
- 2018-01-24 CN CN201810069029.3A patent/CN108191915B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11034709B2 (en) * | 2019-05-29 | 2021-06-15 | The Hong Kong University Of Science And Technology | Organic long persistence luminescence compositions |
| CN110256497A (en) * | 2019-06-06 | 2019-09-20 | 宁波大学 | A kind of manganese complex luminescent material and its preparation method and application |
| CN112341491A (en) * | 2020-11-09 | 2021-02-09 | 中国计量大学 | Organic-inorganic hybrid long afterglow material, preparation method thereof and application thereof in ink-jet printing |
| CN114057796A (en) * | 2021-11-12 | 2022-02-18 | 郑州大学 | Hybrid material based on organic-metal manganese halide and preparation method thereof |
| CN114057796B (en) * | 2021-11-12 | 2023-05-16 | 郑州大学 | Hybrid material based on organic-metal manganese halide and preparation method thereof |
| CN114634528A (en) * | 2022-02-11 | 2022-06-17 | 华南理工大学 | Efficient narrow-band green light emitting metal halide and preparation method and application thereof |
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