Polyimide containing porphyrin, preparation method and application thereof
A technology of polyimide and polyamic acid is applied in the field of porphyrin-based polymer compounds, which can solve the problems of backward application of materials and the failure to effectively utilize the excellent optoelectronic properties of porphyrin, achieve good thermal stability and avoid fluorescence quenching. good effect of quenching, thermal stability and chemical stability
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Embodiment 1
[0053] (1) Synthesis of porphyrin-containing polyimide
[0054] Preparation of 5,15-diaminotetraphenylporphyrin (trans-DATPP) and 5,10-diaminotetraphenylporphyrin (cis-DATPP) monomers: in 0.326 mmol tetraphenylporphyrin (TPP) Add 10mL trifluoroacetic acid (TFA) and 2.65mmol sodium nitrite, stir magnetically at room temperature for 90s, add 100mL water, extract 6 times with dichloromethane, each time 25mL, the extracted dichloromethane organic layer with saturated After washing with aqueous sodium bicarbonate solution (100 mL), dry over anhydrous sodium sulfate for 24 h, and evaporate the solvent to obtain a solid. Then 3.55 mmol of stannous chloride and 50 mL of hydrochloric acid were added, heated to 65° C. for 1 h under magnetic stirring, and then the reaction was stopped. After the system was cooled, 100 mL of water was added, neutralized with ammonia water to pH=8, extracted 6 times with dichloromethane, each time 25 mL, and the extracted dichloromethane organic layer was...
Embodiment 2
[0063] (1) Synthesis of porphyrin-containing polyimide
[0064] The synthetic steps of 5,15-diaminotetraphenylcadmium porphyrin (trans-CdDATPP) monomer are the same as in Example 1, except that the metal salt Zn(OAc) 2 2H 2 Replace O with Cd(OAc) 2 2H 2 O makes trans-CdDATPP.
[0065] Under nitrogen protection, 5,15-diaminotetraphenylcadmium porphyrin and 4,4'-diaminodiphenyl ether (ODA) as diamine monomers were dissolved in N,N-dimethylethyl ether in an ice-water bath. In amide (DMAc), the molar ratio of trans-CdDATPP to ODA is 0.1:1, and electromagnetic stirring is used to dissolve it to obtain a homogeneous system, and then 4,4'- (Hexafluoroisopropyl) diphthalic acid dianhydride (6FDA) monomer was added to the reaction system twice, with half an hour between the two additions; 4,4'-(hexafluoroisopropyl) bis The ratio of the added amount of phthalic dianhydride (6FDA) to N,N-dimethylacetamide (DMAc) was 50 mg / mL. After continuing to react for 4 hours in an ice-water ba...
Embodiment 3
[0073] (1) Synthesis of porphyrin-containing polyimide
[0074] 5, the synthesis steps of 15-diaminotetraphenyl copper porphyrin (trans-CuDATPP) monomer are the same as in Example 1, except that the metal salt Zn(OAc) 2 2H 2 O is replaced by CuCl 2 The trans-CuDATPP was prepared.
[0075] Under nitrogen protection, 5,15-diaminotetraphenylcopper porphyrin and 4,4'-diaminodiphenyl ether (ODA) were dissolved in N,N-dimethylethyl ether as diamine monomers in an ice-water bath. In amide (DMAc), the molar ratio of trans-CuDATPP to ODA is 0.15:1, and electromagnetic stirring is used to dissolve it to obtain a homogeneous system, and then the molar amount of 4,4'- (2,2,2-trifluoro-1-phenylethylene)diphthalic anhydride (3FDA) monomer was added to the reaction system twice, wherein the interval between two additions was half an hour; 4,4'-(2 , The ratio of the added amount of 2,2-trifluoro-1-phenylethylene) diphthalic anhydride (3FDA) to N,N-dimethylacetamide (DMAc) was 50 mg / mL. A...
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