CN101219996A - 4,4'-di(4-phthalazone base) diphenyl sulfone and method for producing the same - Google Patents
4,4'-di(4-phthalazone base) diphenyl sulfone and method for producing the same Download PDFInfo
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- CN101219996A CN101219996A CNA2007101712361A CN200710171236A CN101219996A CN 101219996 A CN101219996 A CN 101219996A CN A2007101712361 A CNA2007101712361 A CN A2007101712361A CN 200710171236 A CN200710171236 A CN 200710171236A CN 101219996 A CN101219996 A CN 101219996A
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Abstract
The invention discloses a 4, 4'-bis(4-phthalazone) sulfobenzide and a preparation method with a structural formula thereof shown on the right. The compound takes 4, 4'-bis(2-carboxylbenzoyl) phenyl sulfide as raw material and is synthesized via oxidation reaction and cyclodehydration reaction. The invention comprises double active hydrogen similar to hydroxyl hydrogen and can cause aromatic nucleophilic substitution reaction with inactive aromatic sulfonation dihalogenated compounds under alkaline conditions to prepare the sulfonated polymer with a diazonaphthenone structural unit. The sulfonated polymer membrane has excellent chemical stability and size stability, which is expected to apply in proton exchange membrane material and other functional materials.
Description
Technical field
The present invention relates to compound of a kind of chemical technology field and preparation method thereof, specifically is a kind of 4,4 '-two (4-naphthyridine ketone group) sulfobenzide and preparation method thereof.
Background technology
As everyone knows, in the operational process of Proton Exchange Membrane Fuel Cells, the oxygen of minute quantity sees through proton exchange membrane from negative electrode and enters anode and H-H reaction generation hydrogen peroxide, and hydrogen peroxide can form perhydroxyl radical under the electrode catalyst effect, hydrocarbon aliphatics of the easy attack of this free radical or activation benzene ring structure unit impel the degraded of non-fluorine proton exchange membrane polymer chain and cause work-ing life shorter.At present, the relevant research of non-fluorine proton exchange membrane is very active, but existing non-fluorine proton exchange membrane material still is difficult to satisfy the needs of practical application, and its main drawback is that scale resistance is relatively poor relatively, swelling ratio is higher.Studies show that in the non-fluorine proton exchange membrane polymer molecular chain and can significantly improve its oxidation resistent susceptibility after getting rid of hydrocarbon aliphatic structure unit or activation benzene ring structure unit.In addition, introduce the naphthyridine ketone structure unit in the non-fluorine proton exchange membrane polymer molecular chain, can significantly reduce its swelling ratio.
Find through literature search prior art, Xiao Guyu etc. were in " Polymer " (polymkeric substance) (2002,43 volumes, 5335～5339) " Synthesis of sulfonated poly (phthalazinone ethersulfone) the s by direct polymerization " that delivers on (preparation of direct polymerization method contains the sulfonated polyether sulfone of assorted naphthalenone structure), proposed in main polymer chain, to introduce assorted naphthalenone structure in this article, carbonyl group in this structure part can and sulfonic acid group on hydrogen atom between to form hydrogen bond crosslinked, thereby reduce the swelling ratio of proton exchange membrane.Its weak point is just to have improved the swelling property of proton exchange membrane and does not solve its oxidisability problem.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the invention provides a kind of 4,4 '-two (4-naphthyridine ketone group) sulfobenzide and preparation method thereof.Compound 4,4 '-two of the present invention (4-naphthyridine ketone group) sulfobenzide, it contains the reactive hydrogen of two similar hydroxyl hydrogens, can prepare the sulfonated polymer that contains the bis-phthalazinyl-ketone structural unit with the reaction of the sulfonated aromatic dihalo compound of passivation.
4,4 '-two (4-naphthyridine ketone group) sulfobenzide involved in the present invention, its structural formula is as follows:
The preparation method of 4,4 '-two (4-naphthyridine ketone group) sulfobenzide involved in the present invention, step is as follows:
(1) oxidizing reaction: in reaction vessel, add 4,4 '-two (2-carboxyl benzoyl) diphenyl sulfide and solvent, reflux, after treating that it dissolves fully, oxygenant is joined in the reaction system gradually, and after reacting completely, reaction mixture gets crude product through the Rotary Evaporators evaporate to dryness, crude product obtains 4,4 '-two (2-carboxyl benzoyl) sulfobenzide after acetate recrystallization, vacuum-drying.The equation of its chemical reaction is as follows:
(2) cyclodehydration reaction: with 4,4 '-two (2-carboxyl benzoyl) sulfobenzides and solvent add in three mouthfuls of round-bottomed flasks, under agitation be warmed up to reflux temperature gradually, wait to dissolve complete back and in reaction system, drip hydrazine hydrate with constant pressure funnel, dropwise the back and continue reaction to complete under reflux temperature, reaction mixture is with obtaining thick product behind the B suction filtration, after recrystallization, vacuum-drying, obtain 4,4 '-two (4-naphthyridine ketone group) sulfobenzide.The equation of its chemical reaction is as follows:
Above-mentioned oxidizing reaction stage solvent for use of the present invention is formic acid, acetate, trifluoroacetic acid or sulfuric acid.
Above-mentioned used oxygenant of oxidizing reaction stage of the present invention is permanganate, dichromate, chromic trioxide, nitric acid, peroxy acid, peracid salt, hydrogen peroxide, hypochlorite, Periodic acid, nitrogen tetroxide or ruthenium tetroxide.
The above-mentioned oxidizing reaction elementary reaction time of the present invention is 0.5 hour to 90 hours.
Above-mentioned cyclodehydration step of reaction solvent for use of the present invention is 1,4-dioxane, acetate, tetramethylene sulfone or sulfobenzide.
The above-mentioned cyclodehydration step of reaction reaction times of the present invention is 0.5 hour to 100 hours.
The sulfonated polymer that contains The compounds of this invention has good oxidation resistent susceptibility and swell-resistant energy concurrently.All aromatic nucleus on the molecular chain are all by the electron-withdrawing group passivation, and do not contain hydrocarbon aliphatics unit, be difficult for by the free radical attack, so oxidation resistent susceptibility are fine; And owing to introduce two naphthyridine ketone structure unit, provide more and can form the crosslinked site of hydrogen bond with sulfonic acid, its swell-resistant can be expected to more more superior than the swelling behavior of reports such as Xiao Guyu.The oxidation resistent susceptibility and the swell-resistant energy of non-fluorine proton exchange membrane have so just been improved simultaneously.The productive rate of the inventive method reaches more than 70%.
Description of drawings
Fig. 1: the infrared spectrogram of 4,4 '-two (2-carboxyl benzoyl) sulfobenzide
Fig. 2: 4,4 '-two (2-carboxyl benzoyl) sulfobenzide
1H NMR figure
Fig. 3: the infrared spectrogram of 4,4 '-two (4-naphthyridine ketone group) sulfobenzide
Fig. 4: 4,4 '-two (4-naphthyridine ketone group) sulfobenzide
1H NMR figure
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
(1) oxidizing reaction: in 500 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirring, reflux condensing tube are housed, add 5 grams 4,4 '-two (2-carboxyl benzoyl) diphenyl sulfide and 300 milliliters of Glacial acetic acid, reflux (125 ℃ of oil bath temperatures), treat that it dissolves fully after, with 15 milliliter 30% H
2O
2Be added drop-wise in the reaction system with constant pressure funnel with the mixed solution of 50 milliliters of Glacial acetic acid, dropwise in about 60 minutes, reacted 24 hours down in reflux state, reaction mixture gets crude product through the Rotary Evaporators evaporate to dryness, crude product obtains light yellow solid product 4 through acetate recrystallization, vacuum-drying after 24 hours, 4 '-two (2-carboxyl benzoyl) sulfobenzide, productive rate 70%.Product structure obtain infrared spectra and
1The affirmation of H NMR spectrum.
Characterization result is as follows:
Fig. 1 is 4, the infrared spectrum (KBr) of 4 '-two (2-carboxyl benzoyl) sulfobenzide: wherein 1304, and 1160cm
-1Be the absorption peak of sulfuryl, 1674cm
-1Be the absorption peak of carbonyl, 3075cm
-1Be-absorption peak of OH; Fig. 2 is it
1H NMR spectrum is (with DMSO-d
6Be solvent), indicated the ownership at each peak among the figure.
(2) cyclodehydration reaction: with 4.6 grams 4,4 '-two (2-carboxyl benzoyl) sulfobenzides and 64 milliliter 1, the 4-dioxane is added in 150 milliliters of three mouthfuls of round-bottomed flasks, under agitation be warmed up to reflux temperature (115 ℃ of oil bath temperatures) gradually, wait to dissolve complete back and in reaction system, drip hydrazine hydrate solution (2.6 milliliter 85% hydrazine hydrate with constant pressure funnel, 18 milliliter 1, the 4-dioxane), dropwise in about 30 minutes, reaction is 48 hours under reflux temperature, reaction mixture, with obtaining thick product behind the B suction filtration, through recrystallization, obtain linen 4,4 '-two (4-naphthyridine ketone group) sulfobenzide after the vacuum-drying, productive rate 80%.Product structure obtain infrared spectra and
1The affirmation of H NMR spectrum.
Characterization result is as follows:
Fig. 3 is 4, the infrared spectrum (KBr) of 4 '-two (4-naphthyridine ketone group) sulfobenzide: wherein 1327, and 1155cm
-1Be the absorption peak of sulfuryl, 1668cm
-1It is the absorption peak of carbonyl.Fig. 4 is it
1H NMR figure is (with DMSO-d
6Be solvent), indicated the ownership at each peak among the figure.
Embodiment 2:
(1) oxidizing reaction: in 500 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirring, reflux condensing tube are housed, add 3 grams 4,4 '-two (2-carboxyl benzoyl) diphenyl sulfide and 150 milliliters of Glacial acetic acid, reflux (125 ℃ of oil bath temperatures), treat that it dissolves fully after, with 9 milliliter 30% H
2O
2Be added drop-wise in the reaction system with constant pressure funnel with the mixed solution of 50 milliliters of Glacial acetic acid, dropwise in about 30 minutes, reacted 10 hours down in reflux state, reaction mixture gets crude product through the Rotary Evaporators evaporate to dryness, crude product obtains light yellow solid product 4 through acetate recrystallization, vacuum-drying after 24 hours, 4 '-two (2-carboxyl benzoyl) sulfobenzide, productive rate 73%.Product structure obtain infrared spectra and
1The affirmation of H NMR spectrum.Analyze among characterization result such as the embodiment 1.
(2) cyclodehydration reaction: with 2 grams 4,4 '-two (2-carboxyl benzoyl) sulfobenzides and 30 milliliter 1, the 4-dioxane is added in 100 milliliters of three mouthfuls of round-bottomed flasks, under agitation be warmed up to reflux temperature (115 ℃ of oil bath temperatures) gradually, wait to dissolve complete back and in reaction system, drip hydrazine hydrate solution (1.2 milliliter 85% hydrazine hydrate with constant pressure funnel, 8 milliliter 1, the 4-dioxane), dropwise in about 15 minutes, reaction is 12 hours under reflux temperature, reaction mixture, with obtaining thick product behind the B suction filtration, through recrystallization, obtain linen 4,4 '-two (4-naphthyridine ketone group) sulfobenzide after the vacuum-drying, productive rate 83%.Product structure obtain infrared spectra and
1The affirmation of H NMR spectrum.Analyze among characterization result such as the embodiment 1.
Embodiment 3:
(1) oxidizing reaction: in 1000 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirring, reflux condensing tube are housed, add 12 grams 4,4 '-two (2-carboxyl benzoyl) diphenyl sulfide and 600 milliliters of Glacial acetic acid, reflux (125 ℃ of oil bath temperatures), treat that it dissolves fully after, with 32 milliliter 30% H
2O
2Be added drop-wise in the reaction system with constant pressure funnel with the mixed solution of 110 milliliters of Glacial acetic acid, dropwise in about 130 minutes, reacted 80 hours down in reflux state, reaction mixture gets crude product through the Rotary Evaporators evaporate to dryness, crude product obtains light yellow solid product 4 through acetate recrystallization, vacuum-drying after 24 hours, 4 '-two (2-carboxyl benzoyl) sulfobenzide, productive rate 75%.Product structure obtain infrared spectra and
1The affirmation of H NMR spectrum.Analyze among characterization result such as the embodiment 1.
(2) cyclodehydration reaction: with 9.2 grams 4,4 '-two (2-carboxyl benzoyl) sulfobenzides and 130 milliliter 1, the 4-dioxane is added in 500 milliliters of three mouthfuls of round-bottomed flasks, under agitation be warmed up to reflux temperature (115 ℃ of oil bath temperatures) gradually, wait to dissolve complete back and in reaction system, drip hydrazine hydrate solution (5.2 milliliter 85% hydrazine hydrate with constant pressure funnel, 40 milliliter 1, the 4-dioxane), dropwise in about 70 minutes, reaction is 96 hours under reflux temperature, reaction mixture, with obtaining thick product behind the B suction filtration, through recrystallization, obtain linen 4,4 '-two (4-naphthyridine ketone group) sulfobenzide after the vacuum-drying, productive rate 85%.Product structure obtain infrared spectra and
1The affirmation of H NMR spectrum.Analyze among characterization result such as the embodiment 1.
Claims (9)
1. one kind 4,4 '-two (4-naphthyridine ketone group) sulfobenzide is characterized in that structural formula is as follows:
2. the preparation method as 4,4 '-two (4-naphthyridine ketone group) according to claim 1 sulfobenzide is characterized in that, comprises the steps:
(1) oxidizing reaction: in reaction vessel, add 4,4 '-two (2-carboxyl benzoyl) diphenyl sulfide and solvent, reflux, after treating that it dissolves fully, oxygenant is joined in the reaction system gradually, and after reacting completely, reaction mixture gets crude product through the Rotary Evaporators evaporate to dryness, crude product obtains 4,4 '-two (2-carboxyl benzoyl) sulfobenzide after acetate recrystallization, vacuum-drying;
(2) cyclodehydration reaction: with 4,4 '-two (2-carboxyl benzoyl) sulfobenzides and solvent join in the reaction vessel, under agitation be warmed up to reflux temperature gradually, wait to dissolve complete back and in reaction system, drip hydrazine hydrate with constant pressure funnel, dropwise the back and continue reaction to complete under reflux temperature, reaction mixture is with obtaining thick product behind the B suction filtration, after recrystallization, vacuum-drying, obtain 4,4 '-two (4-naphthyridine ketone group) sulfobenzide.
3. the preparation method of 4,4 '-two (4-naphthyridine ketone group) according to claim 2 sulfobenzide is characterized in that described oxidizing reaction is in the stage, and solvent for use is formic acid, acetate, trifluoroacetic acid or sulfuric acid.
4. according to claim 2 or 3 described 4, the preparation method of 4 '-two (4-naphthyridine ketone group) sulfobenzide, it is characterized in that, described oxidizing reaction is in the stage, and used oxygenant is permanganate, dichromate, chromic trioxide, nitric acid, peroxy acid, peracid salt, hydrogen peroxide, hypochlorite, Periodic acid, nitrogen tetroxide or ruthenium tetroxide.
5. according to the preparation method of claim 2 or 3 described 4,4 '-two (4-naphthyridine ketone group) sulfobenzide, it is characterized in that described oxidizing reaction is in the stage, the reaction times is 0.5 hour to 90 hours.
6. according to the preparation method of claim 2 or 3 described 4,4 '-two (4-naphthyridine ketone group) sulfobenzide, it is characterized in that described oxidizing reaction is in the stage, the reflux temperature is 125 ℃.
7. the preparation method of 4,4 '-two (4-naphthyridine ketone group) according to claim 2 sulfobenzide is characterized in that in the described cyclodehydration step of reaction, solvent for use is 1,4-dioxane, acetate, tetramethylene sulfone, sulfobenzide.
8. according to the preparation method of claim 2 or 7 described 4,4 '-two (4-naphthyridine ketone group) sulfobenzide, it is characterized in that in the described cyclodehydration step of reaction, the reaction times is 0.5 hour to 100 hours.
9. according to the preparation method of claim 2 or 7 described 4,4 '-two (4-naphthyridine ketone group) sulfobenzide, it is characterized in that in the described cyclodehydration step of reaction, reflux temperature is 115 ℃.
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| CNA2007101712361A CN101219996A (en) | 2007-11-29 | 2007-11-29 | 4,4'-di(4-phthalazone base) diphenyl sulfone and method for producing the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768271B (en) * | 2010-01-12 | 2011-09-28 | 山东理工大学 | Method for protecting terminated amine in polybenzimidazole molecule by carbon dioxide |
| CN113461943A (en) * | 2021-07-07 | 2021-10-01 | 大连理工大学 | Copolymerized aryl ether sulfone containing bis-phthalazinone structure and preparation method thereof |
-
2007
- 2007-11-29 CN CNA2007101712361A patent/CN101219996A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768271B (en) * | 2010-01-12 | 2011-09-28 | 山东理工大学 | Method for protecting terminated amine in polybenzimidazole molecule by carbon dioxide |
| CN113461943A (en) * | 2021-07-07 | 2021-10-01 | 大连理工大学 | Copolymerized aryl ether sulfone containing bis-phthalazinone structure and preparation method thereof |
| CN113461943B (en) * | 2021-07-07 | 2022-05-31 | 大连理工大学 | Copolymerized aryl ether sulfone containing bis-phthalazinone structure and preparation method thereof |
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Open date: 20080716 |