CN103012706A - Melamine-dialdehyde condensation product and synthetic method and application thereof - Google Patents

Melamine-dialdehyde condensation product and synthetic method and application thereof Download PDF

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CN103012706A
CN103012706A CN201210478103XA CN201210478103A CN103012706A CN 103012706 A CN103012706 A CN 103012706A CN 201210478103X A CN201210478103X A CN 201210478103XA CN 201210478103 A CN201210478103 A CN 201210478103A CN 103012706 A CN103012706 A CN 103012706A
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trimeric cyanamide
compound
aldehyde
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aldehyde condensate
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蒲巧生
高小童
周雷
郭锦秀
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Lanzhou University
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Abstract

The invention discloses a melamine-dialdehyde condensation product. The structure of the melamine-dialdehyde condensation product disclosed by the invention is shown in a general formula (I) in the specification. A new organic nanomaterial of the melamine-dialdehyde condensation product has strong fluorescence and further has very strong resonance Rayleigh scattering, and nanoparticles emit fluorescence of different colours such as white, blue, green, yellow, orange and red by adjusting the excitation wavelength. The nanoparticles have the particle size distribution of 2nm to 80nm, and can be applied to dye sensitized solar cells and white LED (Light Emitting Diode).

Description

A kind of trimeric cyanamide-two aldehyde condensate and synthetic method thereof and application
Technical field
The present invention relates to a kind of fluorescent nano material and its preparation method and application.
Background technology
Along with developing rapidly of nanosecond science and technology since the nineties in 20th century, nano material has become of this field most one of the abundantest subscience of rich vigor, Research connotation.And fluorescent nano material is because its distinctive luminescence mechanism and photoelectric properties become the focus that people fall over each other to study.Present research and comparison widely fluorescent nano material mainly comprises pure Nano semiconductor luminescent material, the nano-oxide of rare earth ion and doped transition metal ions, sulfide, composite oxides and various inorganic salt luminescent materials etc.Particularly inorganic semiconductor nanometer material is because its surface effects, quantum size effect, small-size effect, physics, chemical property that macro quanta tunnel effect etc. are unique, thereby be widely used in field (the Angew. Chem. Int. Ed. 2008 such as chemistry, biology, medical science, 47,7602-7625).For example, the quantum dots such as CdTe, CdS, CdSe be widely used in the living matters such as DNA, RNA and protein fluorescent mark (J. Am. Chem. Soc.2001,123,4103-4104) and bio-imaging (Science 2002,298,1759-1762).
In recent years, the organic fluorescence nano material is owing to have optics and the electric property that is different from semiconductor nano material, the advantages such as dimensional effect that had simultaneously fast response time concurrently, can carry out molecular designing and nano material constantly are subject to investigator's favor, as long as effectively improve the performances such as the thermostability of material and mechanics of machinery, the organic fluorescence nano material will have huge potential application foreground aspect Novel Optoelectronic Device.Develop rapidly along with the photoelectric device nanotechnology, the integrated dimension to device and scantling thereof of system has proposed to receive the requirement of littleization, the photoelectric properties of organic nano material become the focus (J. Am. Chem. Soc.2001,123,1434) that people pay close attention to gradually.The organic fluorescence nano material is different from semi-conductor and Metallic Solids, to be combined into by weak model ylid bloom action power, rising material to its photoelectric property is not the Wannier exciton of semi-conductor and Metallic Solids, but charge transfer (charge-transfer) exciton in Frenkel exciton or the organic molecule semi-conductor.Because its complicated molecule composition and structures etc. are in the fundamental research that the organic fluorescence nano material is scarcely out of swaddling-clothes.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defective, and a kind of novel organism nano material with high fluorescence and strong resonance Rayleigh scattering character is provided;
Another object of the present invention provides synthetic method and the application thereof of above-mentioned materials.
Purpose of the present invention is come specific implementation by the following technical programs:
A kind of trimeric cyanamide-two aldehyde condensate, its structure is as leading to formula I:
Figure 572242DEST_PATH_IMAGE001
According to the spectrogram of this compound, referring to Fig. 5-Fig. 6, the structure of final nano particle by 13C and 15N solid-state NMR further determines. 13C CP-MAS NMR(Fig. 5) in, chemical shift is the nuclear-magnetism peak of the C atom on the trimeric cyanamide triazine ring at the peak at 167.06 ppm places, and chemical shift corresponding at the peak at 47.96 ppm places be that primary amine on the trimeric cyanamide carries out three grades of C atoms in the aminal structure that nucleophilic addition(Adn) forms to the aldehyde radical on the oxalic dialdehyde.In addition, exist 15N CP-MAS NMR(Fig. 6) in, chemical shift is the nuclear-magnetism peak of N atom on the triazine ring at the peak between the 174.58-179.75 ppm, and chemical shift should be attributed to the N atom on the secondary amine in the aminal structure at the peak of 89.16-103.96 ppm.
The synthetic method of above-mentioned trimeric cyanamide-two aldehyde condensate: trimeric cyanamide and twain-aldehyde compound compound are put into colorimetric cylinder according to the mixed in molar ratio of 1-5:3, then add the solvent dimethyl sulfoxide (DMSO), ultrasonic dissolution to solution is clarified fully, solution is heated to 160-190 ℃ at last, reaction 2-10h gets final product.
As the preferred version of the synthetic method of above-mentioned trimeric cyanamide-two aldehyde condensate, described twain-aldehyde compound compound is selected oxalic dialdehyde or glutaraldehyde or terephthalic aldehyde.
More excellent, described twain-aldehyde compound compound is oxalic dialdehyde, wherein, trimeric cyanamide and oxalic dialdehyde mol ratio be 4:3; Or described twain-aldehyde compound compound is glutaraldehyde, and wherein, the mol ratio of trimeric cyanamide and glutaraldehyde is 1:1.
Preferably, described reaction is heated to 180 ℃ in the pyroreaction still, reaction 3h.
Described trimeric cyanamide-two aldehyde condensate is as the application of fluorescent nano material.
Described trimeric cyanamide-two aldehyde condensate is as the application of dye sensitization solar battery.To lead to the formula I compound serves as dye sensitizing agent and carries out opto-electronic conversion or replace the unabsorbed sunlight of light scattering layer recapture to absorb sunlight.
Described trimeric cyanamide-two aldehyde condensate is made the application of white light LEDs, will lead to the formula I compound and excite to make white light LEDs, and the excitation wavelength of described logical formula I compound is 300-400 nm, and maximum excitation wavelength is 330nm.
With the synthetic product that obtains, be a kind of calamity light nano material, with 200 times of DMSO dilutions, with the excitation light irradiation of different wave length, obtain the fluorescence of different colours, its key property is exactly: (1) can transmitting white; (2) along with the change of excitation wavelength, nano particle sends the fluorescence of white, blueness, green, yellow, the different colours such as orange, red.Specifically can be with reference to this fluorescent nano material being excited rear captured photo (accompanying drawing 11):
Wavelength corresponding on the photo is excitation wavelength, and when excitation wavelength was 390nm, this fluorescent nano material sent white fluorescent; When excitation wavelength was 450nm, this fluorescent nano material sent green fluorescence; When excitation wavelength was 490nm, this fluorescent nano material sent yellow fluorescence; When excitation wavelength was 510nm, this fluorescent nano material sent fluorescent orange; When excitation wavelength was 570nm, this fluorescent nano material sent red fluorescence.
Beneficial effect of the present invention:
According to the fluorescence emission spectrum of logical formula I compound, high-resolution-ration transmission electric-lens photo, atomic force microscopy, Resonance Rayleigh Scattering Spectra (referring to Fig. 1-Fig. 4), as seen, novel organism nano material of the present invention not only has stronger fluorescence but also have very strong Resonance Rayleigh Scattering, and the adjusting excitation wavelength, nano particle sends white, blueness, green, yellow, orange, the red fluorescence that waits different colours.The size distribution of nano particle is 2nm～80nm, can be applied to dye sensitization solar battery and white light LEDs.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification sheets, is used for together with embodiments of the present invention explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the fluorescence emission spectrogram of logical formula I compound;
Fig. 2 is the high-resolution-ration transmission electric-lens photo of logical formula I compound;
Fig. 3 is the atomic force microscopy of logical formula I compound;
Fig. 4 is the Resonance Rayleigh Scattering Spectra of logical formula I compound;
Fig. 5 is logical formula I compound 13C solid state nmr collection of illustrative plates;
Fig. 6 is logical formula I compound 15N solid state nmr collection of illustrative plates;
Fig. 7 is the fluorescence emission spectrogram by the logical formula I compound of synthesis condition gained of embodiment 1;
Fig. 8 is the fluorescence emission spectrogram by the logical formula I compound of synthesis condition gained of embodiment 2;
Fig. 9 is the fluorescence emission spectrogram by the logical formula I compound of synthesis condition gained of embodiment 3;
Figure 10 is the fluorescence emission spectrogram by the logical formula I compound of synthesis condition gained of embodiment 4;
Figure 11 is the photo that mutual-through type (I) compound excites rear shooting.
 
Embodiment
Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment 1:
A kind of trimeric cyanamide-two aldehyde condensate, its structure is as leading to formula I:
Figure 351980DEST_PATH_IMAGE002
Its synthetic method is:
The 0.3784g trimeric cyanamide is put into the 25mL colorimetric cylinder, slowly splash into the glyoxal solution of 1.306g 40% again, add at last solvent dimethyl sulfoxide (DMSO) (DMSO) 20ml, ultrasonic dissolution to solution is clarified fully.Solution is slowly heated up, be heated to 180 ℃, reaction 3h.The fluorescence spectrum of the compound of synthetic logical formula I as shown in Figure 7 under this reaction conditions.
Embodiment 2:
A kind of trimeric cyanamide-two aldehyde condensate, its structure is as leading to formula I:
Figure 684872DEST_PATH_IMAGE003
Its synthetic method is:
Take by weighing the 0.3784g trimeric cyanamide and put into the 25mL colorimetric cylinder, add 0.4353g 40% glyoxal solution again, add at last 20mL DMSO, ultrasonic dissolution to solution is clarified fully.Place autoclave to be heated to 180 ℃ solution, reaction 3h.The fluorescence spectrum of the compound of synthetic logical formula I as shown in Figure 8 under this reaction conditions.
Embodiment 3:
A kind of trimeric cyanamide-two aldehyde condensate, its structure is as leading to formula I:
Figure 499244DEST_PATH_IMAGE004
Its synthetic method is:
Take by weighing the 0.3784g trimeric cyanamide and put into the 25mL colorimetric cylinder, add 0.2612g 40% glyoxal solution again, add at last 20mL DMSO, ultrasonic dissolution to solution is clarified fully.Place autoclave to be heated to 180 ℃ solution, reaction 3h.The fluorescence spectrum of the compound of synthetic logical formula I as shown in Figure 9 under this reaction conditions.
Embodiment 4:
A kind of trimeric cyanamide-two aldehyde condensate, its structure is as leading to formula I:
Its synthetic method is:
Take by weighing the 0.3784g trimeric cyanamide and put into the 25mL colorimetric cylinder, add 0.6g 50% glutaraldehyde solution again, add at last 20mL DMSO, ultrasonic dissolution to solution is clarified fully.Place autoclave to be heated to 160 ℃ solution, reaction 10h.The fluorescence spectrum of the compound of synthetic logical formula I as shown in figure 10 under this reaction conditions.
Embodiment 5:
A kind of trimeric cyanamide-two aldehyde condensate, its structure is as leading to formula I:
Its synthetic method is:
The 0.3784g trimeric cyanamide is put into the 25mL colorimetric cylinder, slowly splash into the glyoxal solution of 0.3265g 40% again, add at last solvent dimethyl sulfoxide (DMSO) (DMSO) 20ml, ultrasonic dissolution to solution is clarified fully.Solution is slowly heated up, be heated to 180 ℃, reaction 3h.
 
The above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. trimeric cyanamide-two aldehyde condensate, its structure are such as logical formula I:
Figure 201210478103X100001DEST_PATH_IMAGE001
。
2. the synthetic method of trimeric cyanamide according to claim 1-two aldehyde condensate, it is characterized in that: trimeric cyanamide and twain-aldehyde compound compound are put into colorimetric cylinder according to the mixed in molar ratio of 1-5:3, then add the solvent dimethyl sulfoxide (DMSO), ultrasonic dissolution to solution is clarified fully, solution is heated to 160-190 ℃ at last, reaction 2-10h gets final product.
3. the synthetic method of trimeric cyanamide according to claim 2-two aldehyde condensate, it is characterized in that: described twain-aldehyde compound compound is selected oxalic dialdehyde or glutaraldehyde or terephthalic aldehyde.
4. the synthetic method of trimeric cyanamide according to claim 3-two aldehyde condensate, it is characterized in that: described twain-aldehyde compound compound is oxalic dialdehyde, wherein, trimeric cyanamide and oxalic dialdehyde mol ratio be 4:3.
5. the synthetic method of trimeric cyanamide according to claim 3-two aldehyde condensate, it is characterized in that: described twain-aldehyde compound compound is glutaraldehyde, wherein, the mol ratio of trimeric cyanamide and glutaraldehyde is 1:1.
6. the synthetic method of each described trimeric cyanamide-two aldehyde condensate according to claim 2-5, it is characterized in that: described reaction is heated to 180 ℃ in the pyroreaction still, reaction 3h.
7. trimeric cyanamide according to claim 1-two aldehyde condensate is as the application of fluorescent nano material.
8. trimeric cyanamide according to claim 1-two aldehyde condensate is as the application of dye sensitization solar battery.
9. application according to claim 8 is characterized in that: will lead to the formula I compound and serve as dye sensitizing agent and carry out opto-electronic conversion or replace the unabsorbed sunlight of light scattering layer recapture to absorb sunlight.
10.1 trimeric cyanamide according to claim 1-two aldehyde condensate is made the application of white light LEDs, it is characterized in that: will lead to the formula I compound and excite to make white light LEDs, the excitation wavelength of described logical formula I compound is 300-400 nm, and maximum excitation wavelength is 330nm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103923289A (en) * 2014-04-25 2014-07-16 黑龙江大学 Method for preparing reinforced resin material microsphere
CN103923288A (en) * 2014-04-25 2014-07-16 黑龙江大学 Preparation method of melamine glyoxal microsphere in child-mother shape

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MATTHIAS GEORG SCHWAB ET AL: "Catalyst-free Preparation of Melamine-Based Microporous Polymer Networks through Schiff Base Chemistry", 《JACS》 *
张旺: "纳米孔洞有机骨架材料的微波制备及其性质研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103923289A (en) * 2014-04-25 2014-07-16 黑龙江大学 Method for preparing reinforced resin material microsphere
CN103923288A (en) * 2014-04-25 2014-07-16 黑龙江大学 Preparation method of melamine glyoxal microsphere in child-mother shape
CN103923288B (en) * 2014-04-25 2015-09-09 黑龙江大学 A kind of preparation method with the trimeric cyanamide oxalic dialdehyde microballoon of primary and secondary pattern
CN103923289B (en) * 2014-04-25 2015-09-09 黑龙江大学 A kind of preparation method strengthening resin material microballoon

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