CN103554398A - Preparation method of metal porphyrin-phenolic aldehyde resin - Google Patents
Preparation method of metal porphyrin-phenolic aldehyde resin Download PDFInfo
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Abstract
The invention discloses a preparation method of metal porphyrin-phenolic aldehyde resin. The method comprises the following step: enabling meta-tetra(p-hydroxyl phenyl) metal porphyrin and phenol which are used as donors of hydroxyl to carry out dehydration condensation reaction with formaldehyde to obtain metal porphyrin-phenolic aldehyde resin. A material obtained by the preparation method disclosed by the invention has the special advantages of the metal porphyrin, and becomes efficient phenolic aldehyde resin. The material obtained after roasting has good practical value and business outlook on a non-noble-metal fuel battery negative electrode material catalyst.
Description
Technical field
The present invention relates to the technical field of organic synthesis, specifically using m-four (p-hydroxybenzene) metalloporphyrins and phenol as the body that provides of hydroxyl, carry out dehydration condensation with formaldehyde, obtain a kind of metalloporphyrin-resol.
Background technology
Resol is a kind of large class synthetic resins making through polycondensation with phenolic compound and aldehyde compound, is the class thermosetting resin that the mankind synthesize the earliest.In recent years, no matter the production of resol and exploitation, aspect Yield and quality and kind, especially all having significant change aspect new Application Areas developing.At present, resol is mainly used in Material Fields such as manufacturing plastics, paint raw materials, sizing agent, fire-resistant resistance to ablation.
Metal-nitrogen-carbon material is considered to the base metal eelctro-catalyst of at present tool application prospect, aspect the Pt base eelctro-catalyst using at present in replacement, have a clear superiority in, can improve resource scarcity and the expensive restriction to Proton Exchange Membrane Fuel Cells commercialization process of Pt base eelctro-catalyst.Current its most frequently used preparation method loads on precursor the load thermolysis process that then carries out pyrolysis on the high-specific surface area carbon supports such as carbon black, oxide compound or gac.Porphyrin is the macrocylc compound that a class has hydrogen reduction catalytic activity, and in having the porphyrin of metal-complexing, part metals particle is in pyrolytic process, from metal-N
4in discharge.Metal-the N at center
4structural transformation becomes pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen species, has formed the metallics of surface coverage metal oxide film simultaneously, forms new catalytic active site, shows high catalytic activity.
Based on phenol formaldehyde condensation, react, use for reference the synthetic of mesoporous phenolic resin, the metalloporphyrin of phenolic hydroxyl group functionalization of take is formant, metalloporphyrin-formaldehyde resin meso-hole structure of the synthetic rich nitrogen of innovation, and in thermal treatment, open mesopore orbit, create and generate micropore hole wall, prepare multi-stage porous metal-nitrogen-carbon material.
All in all; develop new presoma preparation method; seek there is commercial prospect oxygen electrical catalyze reduction is had to metal-nitrogen-carbon base metal eelctro-catalyst of high reactivity, highly selective and high stability, to reducing proton membrane fuel battery cost, advance its commercialization and promoting that the aspects such as environment protection, rational use of energy are significant.
Summary of the invention
The object of the invention is to have proposed for the kind of existing resol a kind of synthetic method of metalloporphyrin-resol.
The concrete technical scheme that realizes the object of the invention is:
M-four (p-hydroxybenzene) metalloporphyrins and the phenol that is rich in hydroxyl of take is hydroxyl donor, carries out dehydration condensation with formaldehyde, obtains metalloporphyrin-resol.Specifically comprise the following steps:
Synthesizing of a, metalloporphyrin
Press synthetic m-four (p-hydroxybenzene) porphyrin of method of document, and with column chromatography purification; Get m-four (p-hydroxybenzene) porphyrins and metal acetate salt and be dissolved in DMF, at 100～200 ℃, reflux is 30～90 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12～36 hours, decompress filter, washing; Products therefrom recrystallizing methanol 2～5 times, obtain m-four (p-hydroxybenzene) metalloporphyrin; Wherein, the ratio of the amount of substance of m-four (p-hydroxybenzene) porphyrins and metal acetate salt is 1～10; M-four (p-hydroxybenzene) porphyrin is 0.001～0.005 with the ratio of the amount of substance of DMF;
Synthesizing of b, resol
M-four (p-hydroxybenzene) metalloporphyrin is dissolved in NaOH solution, add deionized water to be diluted to pH=8～14, add phenol and formaldehyde, the waters bath with thermostatic control of 40～90 ℃, stir after 20～60 minutes, joined in the solution containing tensio-active agent, in 60～90 ℃ of waters bath with thermostatic control, stirred 3～7 days; Filter, obtain metalloporphyrin-resol; Wherein, m-four (p-hydroxybenzene) metalloporphyrin is 0.1～10 with the ratio of the amount of substance of NaOH; M-four (p-hydroxybenzene) metalloporphyrin is 0.1～5 with the ratio of the amount of substance of phenol, and the amount of substance sum of m-four (p-hydroxybenzene) metalloporphyrins and phenol equals the amount of substance of formaldehyde; Tensio-active agent is polyethylene oxide-poly(propylene oxide)-polyethylene oxide, and strength of solution is 50～250g/L.
Described metal acetate salt is Cobaltous diacetate, neutralized verdigris, Iron diacetate, zinc acetate or manganese acetate.
Compare with background technology, the present invention has the following advantages:
1, metalloporphyrin-resol of the present invention is a kind of new type resin material, be easy to preparation, and calcining after product there is hydrogen reduction catalytic activity, can be used as fuel battery cathod catalyst material.
2, the related metalloporphyrin-resol of the present invention passes through feed change ratio, realizes and forms regulation and control and rich nitrogenize.
Accompanying drawing explanation
Fig. 1 is schema of the present invention;
Fig. 2 is metalloporphyrin-resol infrared spectrogram of the embodiment of the present invention 4 preparations.
Embodiment
the invention will be further described by the following examples:
Embodiment 1
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.4g Cobaltous diacetate of getting 1g were dissolved in the DMF of 50mL, 120 ℃ of reflux 60 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 2 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) cobalt porphyrin is dissolved in NaOH solution, add deionized water to be diluted to pH=8, add 0.4g phenol, 0.15g formaldehyde, the water bath with thermostatic control heated and stirred of 60 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 80g/L, in 60 ℃ of waters bath with thermostatic control, heated and stirred is 7 days.Filter, obtain metalloporphyrin-resol.
Embodiment 2
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.8g Cobaltous diacetate of getting 1g were dissolved in the DMF of 50mL, 150 ℃ of reflux 50 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 1g m-four (p-hydroxybenzene) cobalt porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.5g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 65 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 100g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 5 days.Filter, obtain metalloporphyrin-resol.
Embodiment 3
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1.2g Cobaltous diacetate of getting 1g were dissolved in the DMF of 50mL, 170 ℃ of reflux 40 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) cobalt porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.6g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 70 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 150g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 3 days.Filter, obtain metalloporphyrin-resol.
Embodiment 4
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1g Cobaltous diacetate of getting 1g were dissolved in the DMF of 50mL, 190 ℃ of reflux 20 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 36 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 2g m-four (p-hydroxybenzene) cobalt porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.5g phenol, 0.25g formaldehyde, the water bath with thermostatic control heated and stirred of 80 ℃ 20 minutes, joined in the surfactant soln that 50mL concentration is 200g/L, in 90 ℃ of waters bath with thermostatic control, heated and stirred is 4 days.Filter, obtain metalloporphyrin-resol; Its infrared spectrogram as shown in Figure 2.
Embodiment 5
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.4g iron acetate of getting 1g were dissolved in the DMF of 50mL, 120 ℃ of reflux 60 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 2 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) iron porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.4g phenol, 0.15g formaldehyde, the water bath with thermostatic control heated and stirred of 60 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 80g/L, in 60 ℃ of waters bath with thermostatic control, heated and stirred is 7 days.Filter, obtain metalloporphyrin-resol.
Embodiment 6
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.8g iron acetate of getting 1g were dissolved in the DMF of 50mL, 150 ℃ of reflux 50 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 1g m-four (p-hydroxybenzene) iron porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.5g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 65 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 100g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 5 days.Filter, obtain metalloporphyrin-resol.
Embodiment 7
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1.2g iron acetate of getting 1g were dissolved in the DMF of 50mL, 170 ℃ of reflux 40 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) iron porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.6g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 70 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 150g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 3 days.Filter, obtain metalloporphyrin-resol.
Embodiment 8
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1g iron acetate of getting 1g were dissolved in the DMF of 50mL, 190 ℃ of reflux 20 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 36 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 2g m-four (p-hydroxybenzene) iron porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.5g phenol, 0.25g formaldehyde, the water bath with thermostatic control heated and stirred of 80 ℃ 20 minutes, joined in the surfactant soln that 50mL concentration is 200g/L, in 90 ℃ of waters bath with thermostatic control, heated and stirred is 4 days.Filter, obtain metalloporphyrin-resol.
Embodiment 9
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.4g manganese acetate of getting 1g were dissolved in the DMF of 50mL, 120 ℃ of reflux 60 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 2 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) manganoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.4g phenol, 0.15g formaldehyde, the water bath with thermostatic control heated and stirred of 60 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 80g/L, in 60 ℃ of waters bath with thermostatic control, heated and stirred is 7 days.Filter, obtain metalloporphyrin-resol.
Embodiment 10
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.8g manganese acetate of getting 1g were dissolved in the DMF of 50mL, 150 ℃ of reflux 50 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 1g m-four (p-hydroxybenzene) manganoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.5g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 65 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 100g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 5 days.Filter, obtain metalloporphyrin-resol.
Embodiment 11
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1.2g manganese acetate of getting 1g were dissolved in the DMF of 50mL, 170 ℃ of reflux 40 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) manganoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.6g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 70 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 150g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 4 days.Filter, obtain metalloporphyrin-resol.
Embodiment 12
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1g manganese acetate of getting 1g were dissolved in the DMF of 50mL, 190 ℃ of reflux 20 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 36 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 2g m-four (p-hydroxybenzene) manganoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.5g phenol, 0.25g formaldehyde, the water bath with thermostatic control heated and stirred of 80 ℃ 20 minutes, joined in the surfactant soln that 50mL concentration is 200g/L, in 90 ℃ of waters bath with thermostatic control, heated and stirred is 4 days.Filter, obtain metalloporphyrin-resol.
Embodiment 13
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.4g neutralized verdigris of getting 1g were dissolved in the DMF of 50mL, 120 ℃ of reflux 60 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 2 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) copper porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.4g phenol, 0.15g formaldehyde, the water bath with thermostatic control heated and stirred of 60 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 80g/L, in 60 ℃ of waters bath with thermostatic control, heated and stirred is 7 days.Filter, obtain metalloporphyrin-resol.
Embodiment 14
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.8g neutralized verdigris of getting 1g were dissolved in the DMF of 50mL, 150 ℃ of reflux 50 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 1g m-four (p-hydroxybenzene) copper porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.5g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 65 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 100g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 5 days.Filter, obtain metalloporphyrin-resol.
Embodiment 15
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1.2g neutralized verdigris of getting 1g were dissolved in the DMF of 50mL, 170 ℃ of reflux 40 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) copper porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.6g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 70 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 150g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 3 days.Filter, obtain metalloporphyrin-resol.
Embodiment 16
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1g neutralized verdigris of getting 1g were dissolved in the DMF of 50mL, 190 ℃ of reflux 20 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 36 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 2g m-four (p-hydroxybenzene) copper porphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.5g phenol, 0.25g formaldehyde, the water bath with thermostatic control heated and stirred of 80 ℃ 20 minutes, joined in the surfactant soln that 50mL concentration is 200g/L, in 90 ℃ of waters bath with thermostatic control, heated and stirred is 4 days.Filter, obtain metalloporphyrin-resol.
Embodiment 17
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.4g zinc acetate of getting 1g were dissolved in the DMF of 50mL, 120 ℃ of reflux 60 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 2 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) zinc protoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.4g phenol, 0.15g formaldehyde, the water bath with thermostatic control heated and stirred of 60 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 80g/L, in 60 ℃ of waters bath with thermostatic control, heated and stirred is 7 days.Filter, obtain metalloporphyrin-resol.
Embodiment 18
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 0.8g zinc acetate of getting 1g were dissolved in the DMF of 50mL, 150 ℃ of reflux 50 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 24 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 1g m-four (p-hydroxybenzene) zinc protoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=8, add 0.5g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 65 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 100g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 5 days.Filter, obtain metalloporphyrin-resol.
Embodiment 19
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1.2g zinc acetate of getting 1g were dissolved in the DMF of 50mL, 170 ℃ of reflux 40 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 0.4g m-four (p-hydroxybenzene) zinc protoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.6g phenol, 0.2g formaldehyde, the water bath with thermostatic control heated and stirred of 70 ℃ 30 minutes, joined in the surfactant soln that 50mL concentration is 150g/L, in 80 ℃ of waters bath with thermostatic control, heated and stirred is 3 days.Filter, obtain metalloporphyrin-resol.
Synthesizing of a, metalloporphyrin
M-four (p-hydroxybenzene) porphyrins and the 1g zinc acetate of getting 1g were dissolved in the DMF of 50mL, 190 ℃ of reflux 20 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 36 hours, decompress filter, washing.Products therefrom recrystallizing methanol 3 times.
Synthesizing of b, resol
Getting 2g m-four (p-hydroxybenzene) zinc protoporphyrin is dissolved in NaOH solution, add deionized water to be diluted to PH=10, add 0.5g phenol, 0.25g formaldehyde, the water bath with thermostatic control heated and stirred of 80 ℃ 20 minutes, joined in the surfactant soln that 50mL concentration is 200g/L, in 90 ℃ of waters bath with thermostatic control, heated and stirred is 4 days.Filter, obtain metalloporphyrin-resol.
Claims (2)
1. the preparation method of a metalloporphyrin-resol, it is characterized in that it is hydroxyl donor that the method be take m-four (p-hydroxybenzene) metalloporphyrins and the phenol that is rich in hydroxyl, carry out dehydration condensation with formaldehyde, obtain metalloporphyrin-resol, specifically comprise the following steps:
Synthesizing of a, metalloporphyrin
Press synthetic m-four (p-hydroxybenzene) porphyrin of method of document, and with column chromatography purification; Get m-four (p-hydroxybenzene) porphyrins and metal acetate salt and be dissolved in DMF, at 100～200 ℃, reflux is 30～90 minutes, then, be poured in the deionized water of 2 times of volumes, be cooled to room temperature, ageing 12～36 hours, decompress filter, washing; Products therefrom recrystallizing methanol 2～5 times, obtain m-four (p-hydroxybenzene) metalloporphyrin; Wherein, the ratio of the amount of substance of m-four (p-hydroxybenzene) porphyrins and metal acetate salt is 1～10; M-four (p-hydroxybenzene) porphyrin is 0.001～0.005 with the ratio of the amount of substance of DMF;
Synthesizing of b, resol
M-four (p-hydroxybenzene) metalloporphyrin is dissolved in NaOH solution, add deionized water to be diluted to pH=8～14, add phenol and formaldehyde, the waters bath with thermostatic control of 40～90 ℃, stir after 20～60 minutes, joined in the solution containing tensio-active agent, in 60～90 ℃ of waters bath with thermostatic control, stirred 3～7 days; Filter, obtain metalloporphyrin-resol; Wherein, m-four (p-hydroxybenzene) metalloporphyrin is 0.1～10 with the ratio of the amount of substance of NaOH; M-four (p-hydroxybenzene) metalloporphyrin is 0.1～5 with the ratio of the amount of substance of phenol, and the amount of substance sum of m-four (p-hydroxybenzene) metalloporphyrins and phenol equals the amount of substance of formaldehyde; Tensio-active agent is polyethylene oxide-poly(propylene oxide)-polyethylene oxide, and strength of solution is 50～250g/L.
2. preparation method according to claim 1, is characterized in that described metal acetate salt is Cobaltous diacetate, neutralized verdigris, Iron diacetate, zinc acetate or manganese acetate.
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| CN109482235A (en) * | 2018-12-04 | 2019-03-19 | 合肥工业大学 | A kind of preparation method and applications of the metal nano catalyst of the doped meso-porous carbon load of N- |
| CN110560011A (en) * | 2019-08-27 | 2019-12-13 | 湖南君悦达科技有限公司 | adsorption resin for degrading phthalate ester and preparation method thereof |
| CN111530312A (en) * | 2020-05-12 | 2020-08-14 | 福建师范大学 | Preparation method of single-sheet type polysulfone bipolar membrane with side group bonded with porphyrin group |
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| CN103183594A (en) * | 2013-03-15 | 2013-07-03 | 北京工业大学 | Method for preparing p-cresol into p-hydroxy benzaldehyde by catalytic oxidation of metalloporphyrin-metal salt composite catalyst |
| CN103252248A (en) * | 2013-04-24 | 2013-08-21 | 华东师范大学 | Preparation method of ordered mesoporous non-noble-metal-nitrogen-graphitized carbon material |
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| CN109482235A (en) * | 2018-12-04 | 2019-03-19 | 合肥工业大学 | A kind of preparation method and applications of the metal nano catalyst of the doped meso-porous carbon load of N- |
| CN109482235B (en) * | 2018-12-04 | 2021-08-17 | 合肥工业大学 | Preparation method and application of N-doped mesoporous carbon supported metal nano catalyst |
| CN110560011A (en) * | 2019-08-27 | 2019-12-13 | 湖南君悦达科技有限公司 | adsorption resin for degrading phthalate ester and preparation method thereof |
| CN110560011B (en) * | 2019-08-27 | 2020-10-02 | 湖南君悦达科技有限公司 | Adsorption resin for degrading phthalate ester and preparation method thereof |
| CN111530312A (en) * | 2020-05-12 | 2020-08-14 | 福建师范大学 | Preparation method of single-sheet type polysulfone bipolar membrane with side group bonded with porphyrin group |
| CN111530312B (en) * | 2020-05-12 | 2022-04-05 | 福建师范大学 | Preparation method of single-sheet type polysulfone bipolar membrane with side group bonded with porphyrin group |
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