Zinc metalloporphyrin copolyimide and application thereof as photoelectric information storage material
A zinc porphyrin copolyimide and porphyrin technology, which is applied to the zinc metalloporphyrin copolyimide and its application field as a photoelectric information storage material, and can solve the problem of poor high and low temperature resistance, difficult operation and the like of the electric storage material. problem, to achieve the effect of facilitating mass production, easy operation and high yield
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Embodiment 1
[0044] Preparation of DATPP
[0045] Put 1g of tetraphenylporphyrin TPP in a single-necked flask, add 20ml of trifluoroacetic acid (TFA) into a 100ml single-necked flask, and dissolve at 25°C for 30min. Then weigh the NaNO 2 0.909g, put into the dissolved TPP to react for 1.5min, then quickly pour the solution into deionized water to terminate the reaction. Then dichloromethane was added for extraction, and the lower organic layer was collected. Slowly add ammonia NH to the organic solution dropwise 3 ·H 2 O until the solution turns purple. After the product was spin-dried, put 0.2g of palladium carbon and 20ml of absolute ethanol into it, and raise the temperature in a nitrogen atmosphere. When the temperature rose to 55°C, hydrazine hydrate was added dropwise at a rate of 10 seconds per drop using a constant pressure dropping funnel, and the temperature rose to 95°C and react for 24h. Suction filtration under reduced pressure while hot, and the obtained filtrate was r...
Embodiment 2
[0048] Preparation of Zn-cis-DATPP
[0049] Dissolve 5,15-bis(4-aminophenyl)-10,20-diphenylporphyrin (DATPP) in chloroform to obtain a 6mg / ml solution, and then slowly add 20mg / ml methanolic solution of zinc acetate dihydrate Add it dropwise to the DATPP solution, stir and react at 25° C. for 3-4 hours under nitrogen atmosphere, and then add a large amount of deionized water to terminate the reaction. After that, chloroform was added for extraction, and the filtrate of the lower layer was obtained by rotary evaporation to obtain a blue-purple solid, and finally the porphyrin diamine containing zinc metal was extracted by column chromatography.
[0050] Infrared (potassium bromide KBr tablet): 3445cm -1 ,3370cm -1 (N-H symmetric and asymmetric stretching vibration), 994cm -1 (N-Zn in the middle of the porphyrin ring), such as image 3 shown.
Embodiment 3
[0052] Preparation of coPI-Zn-DATPP-DSDA50
[0053] Under the protection of nitrogen atmosphere, Zn-cis-DATPP, cis-DATPP and DSDA were added to the three-necked flask according to the molar ratio of 0.5:0.5:1, and m-cresol (solid content was about 10%) was also added to the three-necked flask. As a solvent, the mass volume ratio of Zn-cis-DATPP to m-cresol is 8mg / ml, the temperature of the oil bath is set to 50°C, and the magnetic stirring is turned on and heated for 3-4 hours. Add isoquinoline into the liquid funnel as a catalyst, the mass volume ratio of Zn-cis-DATPP to isoquinoline is 1mg / l, add slowly and set the oil bath temperature to 190°C, and react for 12 hours. Pour the solution in the flask into methanol, a purple-green precipitate occurs, filter, wash with methanol three times, filter, and vacuum dry for 12 hours to obtain coPI-Zn-DATPP-DSDA50 system copolyimide.
[0054] Infrared (potassium bromide KBr tablet): 3313cm -1 (N-H in the middle of the porphyrin ring)...
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