CN103467739A - Preparation method of aminoanthraquinone polymer - Google Patents
Preparation method of aminoanthraquinone polymer Download PDFInfo
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- CN103467739A CN103467739A CN 201210186814 CN201210186814A CN103467739A CN 103467739 A CN103467739 A CN 103467739A CN 201210186814 CN201210186814 CN 201210186814 CN 201210186814 A CN201210186814 A CN 201210186814A CN 103467739 A CN103467739 A CN 103467739A
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Abstract
The invention relates to a preparation method of a novel aminoanthraquinone polymer having a structural formula shown in the specification. A quinone compound is prepared by a one-step reaction of 5-amino-2,3-dihydro-1,4-dyhydroxy anthraquinone (ADDAQ) as a raw material and an oxidizing agent in a solvent. The compound can be used for positive pole materials of high specific capacity lithium batteries, and can also be used for optoelectronic device materials, dyeing agents and the like. The preparation method is simple and easy, a pure product can be obtained without purification, and the yield is more than 80%.
Description
Technical field
The present invention relates to a kind of novel quinones polymkeric substance and preparation method thereof.This polymkeric substance can be used for the positive electrode material of high-capacity lithium battery, also can be used for material for optoelectronic devices and staining agent etc.
Background technology
The energy is the valuable source of national economy and social development, coal, oil etc. be widely used the requirement that does not meet low-carbon economy, and the Nonrenewable resources such as fossil energy reduce increasingly, unsustainable.Therefore, develop and rationally utilize renewable energy source just to become the matter of fundamental importance involved the interests of the state and the people.Lithium secondary battery, due to characteristics such as its specific energy are high, have extended cycle life, becomes one of key of following renewable energy utilization.In numerous anode material of lithium battery, inorganic transition metal oxide is current study hotspot, yet there is following shortcoming in this class positive electrode material for following power supply: the one, and theoretical specific capacity is on the low side, LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4deng theoretical specific capacity all below 300mA h/g, actual available specific storage is no more than 170mAh/g, room for promotion is very limited; The 2nd, raw material is limited at the occurring in nature reserves, and there is the problem of heavy metal contamination environment in a part of material, and exploit them needs lot of energy simultaneously, does not meet the requirement of low-carbon economy and Sustainable development; The 3rd, still there is hidden danger at secure context, when over-charging of battery, easily produce high valence state metal oxide, and follow the release of oxygen, violent thermopositive reaction occurs.Relative inorganic materials, organic quinones as lithium electricity positive electrode material have that theoretical specific capacity is higher, the advantage such as abundant raw material, structure designability are strong, in addition, it should be noted that some quinones substance also can directly extract and obtain [124] from plant, therefore, quinones is the ergastic substances that a class has wide application prospect.
Because the functional group of playing redoxomorphism in quinones is carbonyl and hydroxyl, its content is more, and the capacity of material is higher.As electrode materials, wish that its solubleness in electrolytic solution is little in addition, to guarantee the stable of in charge and discharge cycles process electrode structure, improve the cycle performance of battery.Based on above consideration, we design and have prepared a kind of novel many quinones polymkeric substance---poly-5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (PADAQ), this polymkeric substance has quinonyl, hydroxyl and polyaniline chain concurrently, this structure has the following advantages: the one, and the form that anthraquinone is prepared into to polymkeric substance can reduce its solubleness in electrolytic solution, thus the stabilized electrodes structure improves cyclical stability; The 2nd, the class polyaniline structure has good electroconductibility, can improve the electroconductibility of anthraquinone material, improves its electrochemical activity; The 3rd, class polyaniline structure itself can provide capacity by electrochemical doping, contributes to improve the whole volume of material.This polymkeric substance has following structural:
Except can be used as electrochemical energy storage materials, the novel quinones polymkeric substance of this class, due to its good photovoltaic effect and coloring function, can also be applied to the fields such as light emitting diode, intelligent display and sensor and staining agent.
Summary of the invention
The objective of the invention is to prepare many quinones polymkeric substance with a kind of simple preparation method, as high specific energy anode material of lithium battery and photoelectric material and colour development material.
The present invention is amino-2 with 5-, and 3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (ADDAQ) is raw material, by its dissolving or be partially dissolved in solvent, and polymerization under the effect of oxygenant afterwards, the polymkeric substance of formation is precipitated out from solution.This kind of method can obtain clean product without purifying.The reaction formula for preparing this polymkeric substance is as follows:
N in formula >=2; The preparation method is that 3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone ADDAQ is raw material with 5-amino-2, with oxygenant, in solvent, through single step reaction, makes; The add-on weight percent of oxygenant is 10%～2000% of material quantity; Temperature of reaction is-5 ℃～200 ℃; Reaction times is 0.5～24h.
Solvent of the present invention is acetic acid, dimethyl sulfoxide (DMSO), acetonitrile, N-Methyl pyrrolidone, DMF, acetone, ethanol, the vitriol oil, ethyl acetate or sherwood oil.
Reaction oxygenant of the present invention is (NH
4)
2s
2o
8, H
2o
2, KMnO
4, FeCl
3, CrO
3, MnO
2, KClO
3, HClO
4, AlCl
3, PbO
2, SnCl
4, Na
2s
2o
3, O
2or air.
The present invention relates to a kind of novel polyaminoanthraquinone and preparation method thereof.Containing quinonyl, phenolic hydroxyl group and amino group in the monomer of this new polymers, is the combination of organic quinones and amino polymer, has enriched the structure type of polymkeric substance.Simultaneously, preparation process is simple, is applicable to preparation in batches.
The accompanying drawing explanation
Fig. 1 is 5-amino-2,3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (a) and poly-5-amino-2,3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (b)
1h-NMR figure
Fig. 2 is 5-amino-2,3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (a) and poly-5-amino-2, the FT-IR figure of 3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (b)
Fig. 3 is 5-amino-2,3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (a) and poly-5-amino-2, the UV-vis figure of 3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (b)
Fig. 4 is 5-amino-2,3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (a) and poly-5-amino-2, the SEM figure of 3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone (b)
Embodiment
Example 1
ADDAQ (500mg, 1.95mmol) is dissolved in the 40ml ethyl acetate, adds 3 equivalent Anhydrous Ferric Chlorides (1.03g), stirring at room 6h, the point sample analysis, without the raw material point, adds a large amount of distilled water, filter, washing to obtain the brown product by alcohol, productive rate approximately 80%.
Example 2
Under room temperature (25 ℃), by ADDAQ (500mg, 1.95mmol), be dissolved in 50ml acetic acid, be cooled to 0 ℃, slowly drip (NH
4)
2s
2o
8the saturated aqueous solution 5ml of (1.2g, 5.26mmol) stirs 4h in ice bath, and the point sample analysis is without the raw material point, after add a large amount of distilled water, standing over night after stirring, filtration washing obtains the sorrel powdery product, productive rate approximately 85%.
Example 3
By the vitriol oil of 2.17ml 98%, slowly be added drop-wise in DMF, be configured to 40ml DMF sulphuric acid soln, sulfuric acid concentration is 1mol/L, the ADDAQ of 2mmol is joined in 30ml DMF sulphuric acid soln, then by its ultrasonic dispersion 15min, impel monomer to dissolve fully, 200mg (2mmol) chromium trioxide is dissolved in 10ml DMF sulphuric acid soln, oxygenant is dropwise joined in the monomer solution that continues to stir, reaction at room temperature (20 ℃) reaction 24h is carried out.Reacted solution is carried out to suction filtration, then with DMF, product is rinsed, obtain the brown product, productive rate approximately 78%.
According to nuclear magnetic spectrum (Fig. 1), ADDAQ's
1h-NMR shows two hydrogen atoms on δ=14.104, the corresponding hydroxyl of 13.640 difference, δ=6.955 are corresponding to two hydrogen atoms on amino, δ=7.545～7.366 correspond respectively to ring upper 6,7, three hydrogen atoms on 8 carbon, four hydrogen atoms in the corresponding molecule in δ=3.038 on the upper prosposition carbon of ring.PADAQ shows that δ=7.2～7.3 are for the hydrogen of the upper carbon of ring and the hydrogen atom on amino, polymerization system makes the hydrogen of the upper carbon of ring mobile to low, compare P-2, ring upper 2 in polymer molecule, on 3 carbon, corresponding hydrogen atom obviously reduces, because extent of polymerization is more thorough, the numbers of hydrogen atoms on amino is also obviously less simultaneously.
Fig. 2 be ADDAQ and PADAQ infrared spectrogram.ADDAQ wherein, 3479cm
-1, 3356cm
-1for the N-H stretching vibration, because conjugative effect makes cloud density equalization in conjugated system, the cloud density at the two keys of the original C=O of result place reduces, and force constant reduces, so vibrational frequency reduces, therefore, the characteristic peak of carbonyl is at 1611cm
-1, 1515,1464cm
-1the characteristic absorbance of aromatic ring, 1209cm
-1the stretching vibration of carbon oxygen singly-bound, 782cm
-1be the three hydrogen out-of-plane deformation vibration that is connected on phenyl ring, due to the existence of hydrogen on prosposition, make the fingerprint region more complicated that seems.For PADAQ, 3429cm
-1for the stretching vibration of imino-N-H, polymerization makes conjugative effect reduce, and the cloud density at the two keys of C=O place increases, and vibrational frequency increases, so the stretching vibration of carbonyl returns to 1719cm
-1, 1580,1491,1452cm
-1deng the characteristic absorbance that is aromatic ring, 1205cm
-1for the stretching vibration of carbon oxygen singly-bound, 796cm
-1the connected out-of-plane deformation vibration of three hydrogen on upper 6,7,8 carbon of ring, 835cm
-1for encircling the connected out-of-plane deformation vibration of two hydrogen on upper prosposition carbon, also illustrated that in the monomer molecule, the hydrogen on prosposition carbon is oxidized.
The uv-vis spectra that Fig. 3 is ADDAQ and PADAQ, ADDAQ, in the UV and visible spectra district, has presented more intense ultraviolet characteristic, due to amino existence, makes the compound color be orange-yellow.Compare ADDAQ, whole group of peak shape generation red shift of PADAQ molecule, make compound absorb and move to long wavelength's direction, caused the intensification of color, and wherein polymkeric substance is sorrel.
The SEM that Fig. 4 is ADDAQ, synthetic ADDAQ material appearance is orange/yellow solid, and electromicroscopic photograph shows that particle is corynebacterium, and yardstick is more even; The particle that PADAQ is club shaped structure, pattern is more regular, and the part particle agglomeration together, is compared monomer, the obvious variation of crystallization degree.
Claims (3)
1. novel amino anthraquinone polymkeric substance and preparation method thereof, the reaction formula that it is characterized in that preparing this polymkeric substance is as follows:
N in formula >=2; The preparation method is that 3-dihydro-Isosorbide-5-Nitrae-dihydroxyanthraquinone ADDAQ is raw material with 5-amino-2, with oxygenant, in solvent, through single step reaction, makes; The add-on weight percent of oxygenant is 10%～2000% of material quantity; Temperature of reaction is-5 ℃～200 ℃; Reaction times is 0.5～24h.
2. polyaminoanthraquinone according to claim 1 and preparation method thereof, is characterized in that solvent is acetic acid, dimethyl sulfoxide (DMSO), acetonitrile, N-Methyl pyrrolidone, DMF, acetone, ethanol, the vitriol oil, ethyl acetate or sherwood oil.
3. novel amino anthraquinone polymkeric substance according to claim 1 and preparation method thereof, is characterized in that reacting oxygenant for (NH
4)
2s
2o
8, H
2o
2, KMnO
4, FeCl
3, CrO
3, MnO
2, KClO
3, HClO
4, AlCl
3, PbO
2, SnCl
4, Na
2s
2o
3, O
2or air.
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| CN 201210186814 CN103467739A (en) | 2012-06-08 | 2012-06-08 | Preparation method of aminoanthraquinone polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461752A (en) * | 2018-03-12 | 2018-08-28 | 华南师范大学 | A kind of side chain carries triphen amine polymer and the preparation and application of conjugated carbonyl compound |
| CN108948328A (en) * | 2018-06-04 | 2018-12-07 | 东华大学 | A kind of preparation method of poly- 1,5- diamino-anthraquinone nanometer rods |
-
2012
- 2012-06-08 CN CN 201210186814 patent/CN103467739A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461752A (en) * | 2018-03-12 | 2018-08-28 | 华南师范大学 | A kind of side chain carries triphen amine polymer and the preparation and application of conjugated carbonyl compound |
| CN108461752B (en) * | 2018-03-12 | 2020-07-03 | 华南师范大学 | Triphenylamine polymer with side chain having conjugated carbonyl compound, preparation and application thereof |
| CN108948328A (en) * | 2018-06-04 | 2018-12-07 | 东华大学 | A kind of preparation method of poly- 1,5- diamino-anthraquinone nanometer rods |
| CN108948328B (en) * | 2018-06-04 | 2021-05-11 | 东华大学 | Preparation method of poly (1, 5-diaminoanthraquinone) nanorods |
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Application publication date: 20131225 |