CN109988315A - A kind of covalent organic frame compound, preparation method and application - Google Patents
A kind of covalent organic frame compound, preparation method and application Download PDFInfo
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- CN109988315A CN109988315A CN201711475730.7A CN201711475730A CN109988315A CN 109988315 A CN109988315 A CN 109988315A CN 201711475730 A CN201711475730 A CN 201711475730A CN 109988315 A CN109988315 A CN 109988315A
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Abstract
The present invention provides a kind of covalent organic frame compound, preparation method and application.The organic frame compound is formed by TPE-Ph-CHO and TAPM aldimine condensation, preparation method is simple, and covalent organic frame compound obtained has good fluorescent characteristic, and white light LEDs can be obtained coated on blue-ray LED surface, obtained white light LEDs quality white light is good, has a good application prospect.
Description
Technical field
The invention belongs to porous material preparation and organic photoelectric field (LED) more particularly to a kind of covalent organic frames
Close object, preparation method and application.
Background technique
Covalent organic frame compound (COFs) is the organic porous material of a quasi-crystalline, usually with density is small, compares table
The features such as area is high, thermal stability is good, functionalization can design, is now widely used in gas absorption, separation, catalysis, sensing, photoelectricity
The fields such as material and energy stores.But COFs is rarely reported in terms of white light LEDs.
Summary of the invention
Present invention aims at the limitations for breaking through COFs application, provide a kind of covalent organic frame compound, its preparation side
Method and application.
The technical solution adopted by the invention is as follows:
A kind of covalent organic frame compound, which is characterized in that its structural formula are as follows:
Structural formula Wave line indicates periodic extended structure.
Further, the covalent organic frame compound is total made of TPE-Ph-CHO and TAPM aldimine condensation
Valence organic frame compound；
The structural formula of TPE-Ph-CHO are as follows:
The structural formula of TAPM are as follows:
A kind of preparation method of covalent organic frame compound, which is characterized in that it is by TPE-Ph-CHO and TAPM aldehyde amine
It is condensed.
Further, the preparation method of covalent organic frame compound described in described one kind, which is characterized in that including as follows
Step:
(1) TPE-Ph-CHO and TAPM are placed in reaction vessel, o-dichlorohenzene and mesitylene mixed solution is added, surpassed
Sonication is uniformly mixed it；
(2) acetum is added into reaction vessel, then by reaction vessel liquid nitrogen frozen, vacuumizes, in vacuum item
Sealed reaction vessel under part；
(3) it under the conditions of 120 DEG C, sufficiently reacts；
(4) after the reaction was completed, it is down to room temperature, suction filtration obtains powder, after powder ethyl alcohol, acetone washing, successively with four
Hydrogen furans, methanol, methylene chloride, acetone extraction, vacuum drying obtains final product later.
Further, the preparation method of the covalent organic frame compound, in step (1), the TPE-Ph-CHO and
The molar ratio of TAPM is 1:1.
Further, the preparation method of the covalent organic frame compound, in step (3), the reaction time is 168 small
When.
Covalent organic frame compound made from preparation method described in a kind of.
A kind of application of the covalent organic frame compound, which comprises the steps of:
(1) by the powder of the covalent organic frame compound sufficiently it is finely ground after, be uniformly mixed, obtain with uv-curable glue
Glue mixture is stood；
(2) glue mixture is uniformly applied on blue-ray LED, and solidified in the UV lamp, obtain white light LEDs.
Further, the application, the amount of the covalent organic frame compound are 10 mass parts, the uv-curable glue
Amount be 0.5 parts by volume, wherein 1 mass parts: 1 parts by volume=1mg:1mL.
Beneficial effect obtained by the present invention has: the covalent organic frame compound stability of preparation is high, and fluorescence is strong.System
Easy to operate and control is designed, cost is relatively low, and environmentally protective, easy to industrialized production.It is i.e. prepared by the present invention covalently to have
Machine frame compound can be used in White-light LED illumination technology.
1. covalent organic frame compound, preparation method and application, whole system are a purely organic system, no rare earth from
Son participates in, environmentally protective.
2. the covalent organic frame compound fluorescence of preparation is strong, especially yellow fluorescence (visible all band covering).
3. System Design is simple, only with commercially available blue-ray LED with covalent organic frame chemical combination prepared by the present invention
Object is compound.
4. covalent organic frame compound stability is good, in use substantially without apparent aging phenomenon.
Detailed description of the invention
Fig. 1 are as follows: the XRD spectrum of covalent organic frame compound prepared by the present invention；
Fig. 2 are as follows: be powered and emit white light after blue-ray LED coating；
Fig. 3 are as follows: the luminescent spectrum figure of the blue-ray LED after blue LED lamp, and coating；
Fig. 4 are as follows: the CIE spectrum after blue-ray LED, 3D-TPE-COF (450nm excitation) and blue-ray LED coating 3D-TPE-COF
Figure；
Fig. 5 are as follows: the stability data of the white light LEDs of 3D-TPE-COF preparation.
Specific embodiment
Embodiment
The preparation method of covalent organic frame compound, includes the following steps: in the present invention
(1) 50mg (0.067mmol) TPE-Ph-CHO and 25mg (0.067mmol) TAPM is placed in ampoule bottle, is added
2ml o-dichlorohenzene and 2ml mesitylene solution, ultrasonic treatment are uniformly mixed it；
(2) the acetum 0.6mL that 6mol/L is added into ampoule bottle is vacuumized then by ampoule bottle liquid nitrogen frozen,
Sealed ampoule bottle under vacuum conditions；
(3) it under the conditions of 120 DEG C, sufficiently reacts, the reaction time is 168 hours；
(4) after the reaction was completed, it is down to room temperature, suction filtration obtains powder, after powder ethyl alcohol, acetone washing, successively with four
Hydrogen furans, methanol, methylene chloride, acetone extraction, vacuum drying obtains final product later, as covalent organic frame chemical combination
Object.
The reaction equation of TPE-Ph-CHO and TAPM is as follows:
The covalent organic frame compound of this law preparation is in three-dimensional structure, is named as 3D-TPE-COF.
Heretofore described covalent organic frame compound application, includes the following steps:
(1) by the powder of the covalent organic frame compound sufficiently it is finely ground after, take the 10mg covalent organic frame chemical combination
Object powder is uniformly mixed with 0.5mL uv-curable glue, obtains glue mixture, stands 10min；
(2) glue mixture is uniformly applied on blue-ray LED, and solidifies 2min in the UV lamp, obtain white light LEDs.
Fig. 1 is that XRD diagram shows that 3D-TPE-COF has many sharp peaks, shows that spatially long-range has 3D-TPE-COF
Sequence has good crystallinity.
Non-lit up blue LED lamp is followed successively by Fig. 2 from left to right, blue LED lamp surface uniformly coats 3D-TPE-COF
The white LED lamp of opaque yellow is presented afterwards, lights the state of white LED lamp.White led lamps issue white radiance, are by indigo plant
What the yellow fluorescence that the blue light and COF that light LED is issued are stimulated by blue light sending was compounded to form.
In Fig. 3, square hollow and lines are the light emitting region of blue-ray LED (450nm), and hollow round and lines are 3D-
The light emitting region (450nm excitation) of TPE-COF, hollow triangle and lines are the LED light by 3D-TPE-COF coating processing
Spectral region.White light LEDs after the bright COF coating of this chart are that the fluorescence generated by blue light and COF is compounded to form.
Fig. 4 is after this test blue-ray LED, 3D-TPE-COF (450nm excitation) and blue-ray LED coat 3D-TPE-COF
CIE spectrogram.Wherein coordinate position of the blue-ray LED on CIE diagram is A (0.15,0.03), falls in blue region；450nm excitation
Coordinate position of the 3D-TPE-COF on CIE diagram is that B (0.38,0.57) substantially belongs to yellow range；Blue-ray LED coats 3D-
LED luminous position after TPE-COF falls in C (0.30,0.35), close to pure white light (0.33,0.33), illustrates that the present invention covalently has
Machine frame compound 3D-TPE-COF can be good at blue-ray LED being transformed into white light LEDs.
Fig. 5 shows white light LEDs obtained after blue-ray LED coating 3D-TPE-COF, and it is small continuously to light 3 at room temperature
When, it observes that the light intensity of white LED lamp does not have significant change, shows that the stability of this lamp is preferable, sustainable use.
Claims (9)
1. a kind of covalent organic frame compound, which is characterized in that its structural formula are as follows:
Structural formula Wave line indicates periodic extended structure.
2. covalent organic frame compound according to claim 1, which is characterized in that it is TPE-Ph-CHO and TAPM aldehyde
Covalent organic frame compound made of amine condensation；
The structural formula of TPE-Ph-CHO are as follows:
The structural formula of TAPM are as follows:
3. a kind of preparation method of covalent organic frame compound, which is characterized in that it is contracted by TPE-Ph-CHO and TAPM aldehyde amine
It closes.
4. a kind of preparation method of covalent organic frame compound as claimed in claim 3, which is characterized in that including walking as follows
It is rapid:
(1) TPE-Ph-CHO and TAPM are placed in reaction vessel, addition o-dichlorohenzene and mesitylene mixed solution, at ultrasound
Reason is uniformly mixed it；
(2) acetum is added into reaction vessel, then by reaction vessel liquid nitrogen frozen, vacuumizes, under vacuum conditions
Sealed reaction vessel；
(3) it under the conditions of 120 DEG C, sufficiently reacts；
(4) after the reaction was completed, it is down to room temperature, suction filtration obtains powder, after powder ethyl alcohol, acetone washing, successively uses tetrahydro furan
It mutters, methanol, methylene chloride, acetone extraction, vacuum drying obtains final product later.
5. the preparation method of covalent organic frame compound according to claim 4, which is characterized in that in step (1), institute
The molar ratio for stating TPE-Ph-CHO and TAPM is 1:1.
6. the preparation method of covalent organic frame compound according to claim 4, which is characterized in that in step (3), instead
It is 168 hours between seasonable.
7. covalent organic frame compound made from preparation method described in a kind of claim 3 to 6 any one.
8. the application of covalent organic frame compound described in a kind of claims 1 or 2 or 7, which is characterized in that including walking as follows
It is rapid:
(1) by the powder of the covalent organic frame compound sufficiently it is finely ground after, be uniformly mixed with uv-curable glue, obtain glue
Mixture is stood；
(2) glue mixture is uniformly applied on blue-ray LED, and solidified in the UV lamp, obtain white light LEDs.
9. application according to claim 8, which is characterized in that the amount of the covalent organic frame compound is 10 mass
Part, the amount of the uv-curable glue is 0.5 parts by volume, wherein 1 mass parts: 1 parts by volume=1mg:1mL.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894299A (en) * | 2019-12-09 | 2020-03-20 | 海南大学 | Method for synthesizing covalent organic framework material by using eutectic solvent |
| CN110922605A (en) * | 2019-12-09 | 2020-03-27 | 海南大学 | Method for preparing covalent organic framework material by using supercritical carbon dioxide |
| CN111875761A (en) * | 2020-08-12 | 2020-11-03 | 台州学院 | Organic porous framework polymer based on tetraphenylethylene structure and synthetic method thereof |
| CN112226143A (en) * | 2020-09-28 | 2021-01-15 | 厦门大学 | High-electromagnetic-wave-reflection unmanned automobile coating composition and application thereof |
| CN112250883A (en) * | 2020-10-30 | 2021-01-22 | 武汉大学 | Covalent organic framework material with respiration effect, preparation method and application thereof |
| CN113265057A (en) * | 2020-02-14 | 2021-08-17 | 台州学院 | Covalent-organic framework material and preparation method thereof |
| CN115093526A (en) * | 2022-06-27 | 2022-09-23 | 浙江工业大学 | Three-dimensional covalent organic framework compound with white light emission and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761488A (en) * | 2015-03-10 | 2015-07-08 | 兰州大学 | Three-dimensional bipyridine functionalized covalent organic frame material synthesis method |
| CN105860061A (en) * | 2015-05-29 | 2016-08-17 | 上海交通大学 | Imine bond linked covalent organic framework (COF) |
| CN106117259A (en) * | 2016-06-24 | 2016-11-16 | 兰州大学 | A kind of controllable method for preparing of covalent organic frame material different size crystal grain |
-
2017
- 2017-12-29 CN CN201711475730.7A patent/CN109988315B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761488A (en) * | 2015-03-10 | 2015-07-08 | 兰州大学 | Three-dimensional bipyridine functionalized covalent organic frame material synthesis method |
| CN105860061A (en) * | 2015-05-29 | 2016-08-17 | 上海交通大学 | Imine bond linked covalent organic framework (COF) |
| CN106117259A (en) * | 2016-06-24 | 2016-11-16 | 兰州大学 | A kind of controllable method for preparing of covalent organic frame material different size crystal grain |
Non-Patent Citations (4)
| Title |
|---|
| GUIQING LIN, ET AL: "3D Porphyrin-Based Covalent Organic Frameworks", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| GUIQING LIN, ET AL: "A Pyrene-based, Fluorescent Three-dimensional Covalent Organic Framework", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| WEIJUN LUO, ET AL: "A dynamic covalent imine gel as a luminescentsensor", 《CHEMICAL COMMUNICATIONS》 * |
| 励杭泉等: "《材料导论（第二版）》", 30 June 2013, 中国轻工业出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894299A (en) * | 2019-12-09 | 2020-03-20 | 海南大学 | Method for synthesizing covalent organic framework material by using eutectic solvent |
| CN110922605A (en) * | 2019-12-09 | 2020-03-27 | 海南大学 | Method for preparing covalent organic framework material by using supercritical carbon dioxide |
| CN110894299B (en) * | 2019-12-09 | 2021-06-15 | 海南大学 | Method for synthesizing covalent organic framework material by using eutectic solvent |
| CN113265057A (en) * | 2020-02-14 | 2021-08-17 | 台州学院 | Covalent-organic framework material and preparation method thereof |
| CN111875761A (en) * | 2020-08-12 | 2020-11-03 | 台州学院 | Organic porous framework polymer based on tetraphenylethylene structure and synthetic method thereof |
| CN112226143A (en) * | 2020-09-28 | 2021-01-15 | 厦门大学 | High-electromagnetic-wave-reflection unmanned automobile coating composition and application thereof |
| CN112226143B (en) * | 2020-09-28 | 2021-08-24 | 厦门大学 | High-electromagnetic-wave-reflection unmanned automobile coating composition and application thereof |
| CN112250883A (en) * | 2020-10-30 | 2021-01-22 | 武汉大学 | Covalent organic framework material with respiration effect, preparation method and application thereof |
| CN112250883B (en) * | 2020-10-30 | 2022-01-28 | 武汉大学 | Covalent organic framework material with respiration effect, preparation method and application thereof |
| CN115093526A (en) * | 2022-06-27 | 2022-09-23 | 浙江工业大学 | Three-dimensional covalent organic framework compound with white light emission and preparation and application thereof |
| CN115093526B (en) * | 2022-06-27 | 2023-05-23 | 浙江工业大学 | Three-dimensional covalent organic framework compound with white light emission and preparation and application thereof |
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