CN103965082B - Contain the preparation method of the Phenylsulfonic acid sulfonate of amino and phenolic group - Google Patents
Contain the preparation method of the Phenylsulfonic acid sulfonate of amino and phenolic group Download PDFInfo
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Abstract
Contain the preparation method of the Phenylsulfonic acid sulfonate of amino and phenolic group, the present invention relates to two kinds of Phenylsulfonic acid sulfonate compounds containing amino phenolic group, it will solve the problem of the poor heat resistance of ion-exchange membrane that existing use obtains containing Phenylsulfonic acid monomer polymerization that is amino and hydroxyl or proton exchange membrane.It is 3 that the present invention contains Phenylsulfonic acid sulfonate that is amino and phenolic group, 5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate, preparation method is for raw material with 2,4-diaminophenol hydrochloride or 4,6-diaminoresorcinol hydrochloride, oleum is sulphonating agent, and frozen water is prepared as precipitation agent.By above two kinds of monomer synthesize polybenzoxazole base polymers, the polymer heat-resistant obtained is high, and use temperature brings up to more than 120 DEG C, can apply this base polymer and use as the proton exchange membrane of fuel cell.
Description
Technical field
The present invention relates to two kinds of Phenylsulfonic acid sulfonate compounds containing amino phenolic group, be specifically related to 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of fuel cell producing electric power and heating power with hydrogen-containing fuel and air effect, take macromolecule proton exchange membrane as conductive medium, without any chemical liquid, pure water and heat is produced after generating, and have that efficiency of conversion is high, start-up temperature is low and advantages of environment protection, thus be widely used in the fields such as space flight, military affairs, the energy and traffic.Macromolecule proton exchange membrane is wherein solid-state polymer electrolysis material, in order to transmit proton, and palpus deadens electronics and gas passes through, now widely used proton exchange membrane is Nafion film, but Nafion film also exists that proton conductivity under high temperature and low humidity is low, methanol permeability is high and makes the shortcomings such as difficulty is expensive.
The people such as Zhao Liang 2009 " chemical journal " the 9th phase exercise question be describe with 4 in the document of " syntheses and properties of novel sulfonated polyimide film ", 4'-bis-(m-aminophenyl oxygen base) biphenyl-3,3'-disulfonic acid, 2-(to aminocarbonyl phenyl) benzoxazole-5-amine and Isosorbide-5-Nitrae, 5, the polymeric amide of 8-naphthalenetetracarbacidic acidic dianhydride copolymerization Han You oxazole ring, along with the increase of sulfonation degree, proton conductivity improves, and its electric conductivity is 5.62 × 10
-3s/cm, close to the electric conductivity of Nafion117, but its resistance toheat and proton conductivity need to be improved further.
Summary of the invention
The problem of the poor heat resistance of the ion-exchange membrane that the Phenylsulfonic acid monomer polymerization that the object of the invention is to contain amino and hydroxyl to solve existing use obtains or proton exchange membrane, and Phenylsulfonic acid sulfonate containing amino and phenolic group and preparation method thereof is provided.
It is 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate that the present invention contains Phenylsulfonic acid sulfonate that is amino and phenolic group, and its structure formula I is:
It is 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate that the present invention contains Phenylsulfonic acid sulfonate that is amino and phenolic group, and its structure formula II is:
The preparation method that the present invention contains Phenylsulfonic acid sulfonate 3, the 5-diamino-2-hydroxy benzenesulfonic acid sulfonate of amino and phenolic group follows these steps to realize:
Nitrogen is passed in reaction vessel, then oleum and 2 are pressed, the mass ratio of 4-diaminophenol hydrochloride is (5 ~ 10): 1 adds oleum and 2,4-diaminophenol hydrochloride, heating reflux reaction was down to room temperature after 4 ~ 8 hours, then added frozen water, leave standstill crystal to separate out, finally by filtration, vacuum-drying obtains 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate.
The preparation method that the present invention contains Phenylsulfonic acid sulfonate 3,5-diamino-2, the 6-dihydroxy benzenes sulfonic acid sulfonate of amino and phenolic group follows these steps to realize:
Nitrogen is passed in reaction vessel, then oleum and 4 are pressed, the mass ratio of 6-diamino resorcin hydrochlorate is (5 ~ 10): 1 adds oleum and 4,6-diaminoresorcinol hydrochloride, and heating reflux reaction was down to room temperature after 4 ~ 6 hours, add frozen water again, leave standstill crystal to separate out, finally by filtration, vacuum-drying obtains 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate.
Of the present invention 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate be in two kinds of molecules all containing benzene sulfonic acid compounds that is amino and hydroxyl, can be used for synthesis containing sulfonic acid or sulfonate benzoxazole and other benzene sulfonic acid compounds.With 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate is monomer, the polybenzoxazole-imide containing sulfonic acid or sulfonate can be synthesized, polybenzoxazole containing sulfonic acid or sulfonate, the thermotolerance of this two base polymer is high, Heat stability is good, apply its proton exchange membrane as fuel cell to use, the use temperature of proton exchange membrane can be brought up to more than 120 DEG C, solve Nafion film application of temperature lower than 80 DEG C, can not in the problem of applied at elevated temperature.In addition, by the polybenzoxazole-imide containing sulfonic acid or sulfonate of these two kinds of monomer synthesize, polybenzoxazole containing sulfonic acid or sulfonate, sulfonic acid group is directly connected on phenyl ring, with be first polymerized after the polymer phase ratio of sulfonation again, sulfonic acid group combines stable, and sulfonation degree is high, proton conductivity is high, Heat stability is good.
Accompanying drawing explanation
Fig. 1 is that the hydrogen nuclear magnetic resonance spectrogram of 3, the 5-diamino-2-hydroxy benzenesulfonic acid sulfonate that embodiment one obtains is (with D
2o is solvent);
Fig. 2 is that the hydrogen nuclear magnetic resonance spectrogram of 3,5-diamino-2, the 6-dihydroxy benzenes sulfonic acid sulfonate that embodiment two obtains is (with D
2o is solvent);
Fig. 3 is the thermogravimetric curve containing sulfonic acid polybenzoxazole-imide that Application Example one obtains;
Fig. 4 is the thermogravimetric curve containing sulfonic acid polybenzoxazole that Application Example two obtains.
Embodiment
Embodiment one: the preparation method that present embodiment contains Phenylsulfonic acid sulfonate 3, the 5-diamino-2-hydroxy benzenesulfonic acid sulfonate of amino and phenolic group follows these steps to realize:
Nitrogen is passed in reaction vessel, then oleum and 2 are pressed, the mass ratio of 4-diaminophenol hydrochloride is (5 ~ 10): 1 adds oleum and 2,4-diaminophenol hydrochloride, heating reflux reaction was down to room temperature after 4 ~ 8 hours, then added frozen water, leave standstill crystal to separate out, finally by filtration, vacuum-drying obtains 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate.
The temperature of reaction of present embodiment reflux is 140 ~ 160 DEG C.
The reaction equation of present embodiment 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate is as follows:
Embodiment two: present embodiment and embodiment one are unlike SO in oleum
3mass concentration be 20% ~ 70%.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are 60% unlike the mass concentration of ice in frozen water, and the consumption of frozen water is 20 ~ 30 times of 2,4-diaminophenol hydrochloride quality.Other step and parameter identical with embodiment one or two.
Embodiment four: the preparation method that present embodiment contains Phenylsulfonic acid sulfonate 3,5-diamino-2, the 6-dihydroxy benzenes sulfonic acid sulfonate of amino and phenolic group follows these steps to realize:
Nitrogen is passed in reaction vessel, then oleum and 4 are pressed, the mass ratio of 6-diamino resorcin hydrochlorate is (5 ~ 10): 1 adds oleum and 4,6-diaminoresorcinol hydrochloride, and heating reflux reaction was down to room temperature after 4 ~ 6 hours, add frozen water again, leave standstill crystal to separate out, finally by filtration, vacuum-drying obtains 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate.
The temperature of reaction of present embodiment reflux is 120 ~ 140 DEG C.
The reaction equation of present embodiment 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate is as follows:
Present embodiment and embodiment one are respectively with 2,4-diaminophenol hydrochloride or 4,6-diaminoresorcinol hydrochloride are raw material, and oleum is sulphonating agent, adopt frozen water as precipitation agent, obtained highly purified containing Phenylsulfonic acid sulfonate that is amino and phenolic group.3 of synthesis, 5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 3,5-diamino-2, sulfonic group in 6-dihydroxy benzenes sulfonic acid sulfonate is electron-withdrawing group, but it is in the ortho position of hydroxyl, conjugated system can not be formed by carbon on He oxazole ring, can not the nucleophilicity of carbon on Ti Gao oxazole ring, so stability to hydrolysis is high.In addition, 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate for the synthesis of separatory ion-exchange membrane, can also improve the thermotolerance of ion-exchange membrane.
Embodiment five: present embodiment and embodiment four are unlike SO in oleum
3mass concentration be 20% ~ 70%.Other step and parameter identical with embodiment four.
Embodiment six: present embodiment and embodiment four or five are 60% unlike the mass concentration of ice in frozen water, and the consumption of frozen water is 20 ~ 30 times of 4,6-diaminoresorcinol hydrochloride quality.Other step and parameter identical with embodiment four or five.
Embodiment seven: one of present embodiment and embodiment four to six are separated out unlike leaving standstill 3 ~ 4 days crystal.Other step and parameter identical with one of embodiment four to six.
Embodiment one: the preparation method of the present embodiment 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate follows these steps to implement:
Nitrogen is passed in reaction vessel, then add 30 gram mass concentration be 30% oleum and 3.96 gram 2,4-diaminophenol hydrochloride, room temperature is down to after 6 hours with 150 DEG C of heating reflux reactions, add 80 grams of frozen water again, leave standstill 3 days crystal and separate out, finally by filtration, vacuum-drying obtains 4.76 gram of 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate.
The hydrogen nuclear magnetic resonance spectrogram of 3, the 5-diamino-2-hydroxy benzenesulfonic acid sulfonate that the present embodiment obtains as shown in Figure 1.
Embodiment two: the preparation method of the present embodiment 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate follows these steps to implement:
Nitrogen is passed in reaction vessel, then add 36 gram mass concentration be 20% oleum and 4.26 gram 4,6-diamino resorcin hydrochlorate, be down to room temperature with 130 DEG C of heating reflux reactions after 5 hours, then add 90 grams of frozen water, leave standstill 3 days crystal and separate out, finally by filtration, vacuum-drying obtains 5.52 gram of 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate.
The hydrogen nuclear magnetic resonance spectrogram of 3,5-diamino-2, the 6-dihydroxy benzenes sulfonic acid sulfonate that the present embodiment obtains as shown in Figure 2.
Application Example one: adopt the preparation of 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate to follow these steps to implement containing the method for sulfonic acid polybenzoxazole-imide:
Under nitrogen protection, in 31.6 grams of polyphosphoric acid, add 4 gram 3 successively in 140 DEG C; 5-diamino-2-hydroxy benzenesulfonic acid sulfonate and 0.83 gram of terephthalic acid; 140 DEG C of reactions were warming up to 190 DEG C after 2 hours, then were cooled to 140 DEG C after reacting 4 hours, added 1.55 gram 3; 3 '; 4,4 '-oxydiphthalic, reacts after 4 hours and is warming up to 170 DEG C at 140 DEG C; be down to room temperature after reacting 2 hours again, obtained 3.52 grams of separating-purifying contains sulfonic acid polybenzoxazole-imide.
1 gram that is obtained by the present embodiment is dissolved in 15mL dimethyl sulfoxide (DMSO) containing sulfonic acid polybenzoxazole-imide, and heating for dissolving forms homogeneous solution, and filter, slowly volatilized by solvent, film is made in vacuum-drying.Containing sulfonic acid polybenzoxazole-imide film 20 DEG C time, proton conductivity is 1.21 × 10
-2s/cm, 80 DEG C time, proton conductivity is 1.77 × 10
-2s/cm, is better than the performance of Nafion film.Its thermogravimetric curve as shown in Figure 3, contains-the SO of sulfonic acid polybenzoxazole-imide as seen from the figure
3h radical decomposition temperature is higher than 270 DEG C, and the residual qualities of 500 DEG C about 48%, illustrate that containing sulfonic acid polybenzoxazole-imide has good thermostability.
Application Example two: adopt the preparation of 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate to follow these steps to implement containing the method for sulfonic acid polybenzoxazole:
Under nitrogen protection; in 18.6 grams of polyphosphoric acid; 2.08 gram 3 is added successively in 140 DEG C; 5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate and 1.29 gram of 4,4'-dicarboxydiphenyl ether; 140 DEG C are reacted 2 hours; then be slowly warming up to 170 DEG C of reactions 2 hours, be down to room temperature, obtain 1.85 grams after separating-purifying containing sulfonic acid polybenzoxazole.
1 gram that is obtained by the present embodiment joins 15mL dimethyl sulfoxide (DMSO) containing sulfonic acid polybenzoxazole, and instillation 2mL triethylamine, heating for dissolving forms homogeneous solution, and filter, slowly volatilized by solvent, film is made in vacuum-drying.Containing sulfonic acid polybenzoxazole thin film 20 DEG C time, proton conductivity is 1.15 × 10
-2s/cm, 80 DEG C time, proton conductivity is 1.98 × 10
-2s/cm, is better than the performance of Nafion film.Its thermogravimetric curve as shown in Figure 4, contains-the SO of sulfonic acid polybenzoxazole as seen from the figure
3h radical decomposition temperature is higher than 370 DEG C, and the residual qualities of 600 DEG C is more than 50%, illustrates that containing sulfonic acid polybenzoxazole has good thermostability.
Claims (7)
1. contain the preparation method of the Phenylsulfonic acid sulfonate of amino and phenolic group, it is characterized in that the preparation method of 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate follows these steps to realize:
Nitrogen is passed in reaction vessel, then oleum and 2 are pressed, the mass ratio of 4-diaminophenol hydrochloride is (5 ~ 10): 1 adds oleum and 2,4-diaminophenol hydrochloride, heating reflux reaction was down to room temperature after 4 ~ 8 hours, then added frozen water, leave standstill crystal to separate out, finally by filtration, vacuum-drying obtains 3,5-diamino-2-hydroxy benzenesulfonic acid sulfonate.
2. the preparation method containing the Phenylsulfonic acid sulfonate of amino and phenolic group according to claim 1, is characterized in that SO in oleum
3mass concentration be 20% ~ 70%.
3. the preparation method containing the Phenylsulfonic acid sulfonate of amino and phenolic group according to claim 1, it is characterized in that the mass concentration of ice in frozen water is 60%, the consumption of frozen water is 20 ~ 30 times of 2,4-diaminophenol hydrochloride quality.
4. contain the preparation method of the Phenylsulfonic acid sulfonate of amino and phenolic group, it is characterized in that the preparation method of 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate follows these steps to realize:
Nitrogen is passed in reaction vessel, then oleum and 4 are pressed, the mass ratio of 6-diamino resorcin hydrochlorate is (5 ~ 10): 1 adds oleum and 4,6-diaminoresorcinol hydrochloride, and heating reflux reaction was down to room temperature after 4 ~ 6 hours, add frozen water again, leave standstill crystal to separate out, finally by filtration, vacuum-drying obtains 3,5-diamino-2,6-dihydroxy benzenes sulfonic acid sulfonate.
5. the preparation method containing the Phenylsulfonic acid sulfonate of amino and phenolic group according to claim 4, is characterized in that SO in oleum
3mass concentration be 20% ~ 70%.
6. the preparation method containing the Phenylsulfonic acid sulfonate of amino and phenolic group according to claim 4, it is characterized in that the mass concentration of ice in frozen water is 60%, the consumption of frozen water is 20 ~ 30 times of 4,6-diaminoresorcinol hydrochloride quality.
7. the preparation method containing the Phenylsulfonic acid sulfonate of amino and phenolic group according to claim 4, is characterized in that standing 3 ~ 4 days crystal are separated out.
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| GB597542A (en) * | 1944-09-01 | 1948-01-28 | Sandoz Ltd | Process for the preparation of new monoazodyestuffs |
| JP3398339B2 (en) * | 1999-06-07 | 2003-04-21 | 三井化学株式会社 | 2-sulfonic acid-4,6-dinitroresorcin and salts thereof and methods for producing them |
| CN1583752A (en) * | 2004-06-02 | 2005-02-23 | 哈尔滨工业大学 | Synthesis of benzoxazole |
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