CN100404501C - Di sulfonated aromatic diamine and preparation method thereof - Google Patents
Di sulfonated aromatic diamine and preparation method thereof Download PDFInfo
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- CN100404501C CN100404501C CNB2006100308164A CN200610030816A CN100404501C CN 100404501 C CN100404501 C CN 100404501C CN B2006100308164 A CNB2006100308164 A CN B2006100308164A CN 200610030816 A CN200610030816 A CN 200610030816A CN 100404501 C CN100404501 C CN 100404501C
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- amino
- benzene
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Abstract
The invention discloses a disulf aromatic diamine and preparing method, which is characterized by the following: the sulfonic group in each molecular of disulf aromatic diamine is gathered on one benzene ring, which displays obvious hydrophilic and hydrophobic part; the molecular is beneficial to conduct, which can be key intermediate of soluble dye.
Description
Technical field
The present invention relates to a kind of sulfonated polymer and preparation method thereof, relate in particular to a kind of di sulfonated aromatic diamine and preparation method thereof.
Background technology
In recent years, sulfonated polymer is owing to its application prospect in high-molecular electrolyte fuel battery receives much attention.Wherein sulfonated polyimide is because of its excellent film forming properties, the good mechanical performance, and resistance toheat and solvent resistance become a class material that is hopeful to obtain practical application most.Sulfonated diamine is the important monomer of preparation sulfonated polyimide.The structure of sulfonated diamine affects the performance of prepared sulfonated polyimide significantly.In the sulfonated diamine of having reported, contained two or more sulfonic groups all are to be connected on the different phenyl ring in each molecule.The sulfonated polyimide that is made by these sulfonated diamines relatively disperses owing to sulfonic distribution, is difficult for forming the phase separation structure of microcosmic, thereby can not carries out proton conduction efficiently.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of di sulfonated aromatic diamine and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Di sulfonated aromatic diamine of the present invention, its general structure is shown below:
Preferred di sulfonated aromatic diamine is:
4,6-two (4-amino-benzene oxygen) benzene-1,3-disulfonic acid
Or 4,6-two (4-amino-benzene sulfydryl) benzene-1,3-disulfonic acid.
The preparation method of di sulfonated aromatic diamine of the present invention comprises the steps:
(1) with two halogeno-benzenes and oleum reaction, 50～150 ℃ were reacted 5～20 hours, and reaction is poured reaction system in the frozen water into after finishing, to wherein adding carbonate, emit then, filter until no gas, with the filtrate evaporate to dryness, the vacuum-drying of gained solid obtains the two halogeno-benzenes of two sulfonation;
Wherein: the mol ratio of the sulphur trioxide in two halogeno-benzenes and the oleum is 1: 2～1: 8, and the weight concentration of sulphur trioxide is 10%～60% in the oleum;
Preferred carbonate is selected from lime carbonate or barium carbonate;
Said pair of halogeno-benzene structure is shown below:
X＝F，Cl，Br
Preferred m-difluorobenzene, Meta Dichlorobenzene or m-dibromobenzene;
(2) under nitrogen protection, with the two halogeno-benzenes of two above-mentioned sulfonation, equimolar amino phenol or amino thiophenol, anhydrous carbonate, the mixture heating up to 100 of organic solvent and aromatic hydrocarbons～200 ℃ steam aromatic hydrocarbons and water, reacted 5～40 hours, reaction is chilled to 10～30 ℃ with reaction system after finishing, and pours in the acetone then, suction filtration, resulting solid is soluble in water, add acidic substance and be acidified to pH=3～6, collect the target product di sulfonated aromatic diamine then;
The structure of said amino phenol and amino thiophenol is shown below:
Preferred p-aminophenol, to amino thiophenol, Metha Amino Phenon, 4-amino-1-naphthols, 5-amino-1-naphthols, 6-amino-1-naphthols, 5-amino-beta naphthal or 8-amino-beta naphthal;
Said anhydrous carbonate comprises Anhydrous potassium carbonate or anhydrous sodium carbonate, and its consumption is 1～5 times of mole number of amino phenol or amino thiophenol;
Said organic solvent comprises N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO);
The used aromatic hydrocarbons of the present invention comprises benzene, toluene or dimethylbenzene, and the consumption of aromatic hydrocarbons is 1: 10～1: 1 with the volume of organic solvent ratio;
Said acidic substance are selected from hydrochloric acid or sulfuric acid;
In the reaction system, the total concentration by weight of the two halogeno-benzenes of two sulfonation and amino phenol or amino thiophenol is 5～60%.
Sulfonated aromatic diamine of the present invention, its constitutional features concentrates on the phenyl ring sulfonic group in each molecule, by the prepared sulfonated polyimide of this class di sulfonated aromatic diamine, because sulfonic group is more concentrated, hydrophilic segment and hydrophobic part distribute obviously, therefore thereby expection easily forms the efficient conduction that the micron-scale phase separation structure helps proton, and this compounds also can be used as the important intermediate of preparation water-soluble dye etc. in addition.The di sulfonated aromatic diamine of gained of the present invention and two anhydride reactants can prepare sulfonated polyimide, and sulfonated polyimide is because its good film forming properties, excellent mechanical property, resistance toheat and solvent resistance have widely application with proton conductive membrane, separatory membrane and chlorine industry with aspects such as ion-exchange membranees at fuel cell.
Description of drawings
Fig. 1 is 4,6-dichlorobenzene-1,3-disulfonic acid calcium
1H NMR (DMSO-d
6)
Fig. 2 is 4,6-dichlorobenzene-1, the infrared spectra IR (KBr) of 3-disulfonic acid calcium
Fig. 3 is 4,6-two (4-amino-benzene oxygen) benzene-1, the 3-disulfonic acid
1H NMR (DMSO-d
6), add triethylamine so that dissolving)
Fig. 4 is 4,6-two (4-amino-benzene oxygen) benzene-1, the 3-disulfonic acid infrared spectra IR (KBr)
Fig. 5 is 4,6-two (4-amino-benzene sulfydryl) benzene-1, the 3-disulfonic acid
1H NMR (DMSO-d
6O adds triethylamine so that dissolving)
Fig. 6 is 4,6-two (4-amino-benzene sulfydryl) benzene-1, the infrared spectra IR (KBr) of 3-disulfonic acid.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
4,6-dichlorobenzene-1, the preparation of 3-disulfonic acid calcium
The weight concentration that adds 14.7g (0.1mol) Meta Dichlorobenzene and 50mL sulphur trioxide in the exsiccant reaction flask is 30% oleum, with reaction system be heated to 120 ℃ and under this temperature the reaction 10 hours, after reaction finishes, reaction system is poured in the 500g frozen water, to wherein adding lime carbonate, emit then until no gas.
Filter, with the filtrate evaporate to dryness, the oven dry of gained solid obtains the 26g white solid product, and productive rate is 95%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum is seen Fig. 1; Infrared spectra is seen Fig. 2, proves that the synthetic product is 4,6-dichlorobenzene-1,3-disulfonic acid calcium.
Concrete characterization result is as follows:
Fig. 1 is 4,6-dichlorobenzene-1, the infrared spectra (KBr) of 3-disulfonic acid calcium: 3444cm wherein
-1Be the absorption peak of water, 1644cm
-1, 1574cm
-1, 1540cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton 1232cm
-1, 1204cm
-1Be-SO
3 -Absorption peak, 681cm
-1It is the Ar-Cl absorption peak; Fig. 2 is 4,6-dichlorobenzene-1,3-disulfonic acid calcium
1HNMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
4,6-two (4-amino-benzene oxygen) benzene-1, the preparation of 3-disulfonic acid
In nitrogen protection; under the magnetic agitation condition; in the exsiccant reaction flask, add 10.9g (0.1mol) p-aminophenol; 17.25g (0.05mol) by embodiment 1 make 4; 6-dichlorobenzene-1,3-disulfonic acid calcium, 10g Anhydrous potassium carbonate; 80mL N-Methyl pyrrolidone and 20mL toluene; reaction system is heated to 170 ℃, steams toluene and water, and under this temperature, reacted 20 hours; after reaction finishes; reaction system is chilled to room temperature, pours in the 300mL acetone suction filtration then into; the solid that obtains is dissolved in the 100mL water; be neutralized to acidity (PH=4) with concentrated hydrochloric acid, suction filtration is collected the throw out of being separated out; and be washed till neutrality with deionized water; oven dry obtains the 16.3g target product, and productive rate is 72%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum is seen Fig. 3; Infrared spectra is seen Fig. 4, proves that the synthetic product is 4,6-two (4-amino-benzene oxygen) benzene-1,3-disulfonic acid.
Concrete characterization result is as follows:
Fig. 3 is 4,6-two (4-amino-benzene oxygen) benzene-1, the infrared spectra of 3-disulfonic acid (KBr): 3452cm wherein
-1Be the absorption peak of water, 1629cm
-1, 1588cm
-1, 1508cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton 1226cm
-1, 1204cm
-1, 1052cm
-1Be-SO
3 -Absorption peak; Fig. 4 is 4,6-two (4-amino-benzene oxygen) benzene-1, the 3-disulfonic acid
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
4,6-two (4-amino-benzene sulfydryl) benzene-1, the preparation of 3-disulfonic acid
In nitrogen protection; under the magnetic agitation condition; in the exsiccant reaction flask, add 12.5g (0.1mol) to amino thiophenol; 17.25g (0.05mol) by embodiment 1 make 4; 6-dichlorobenzene-1,3-disulfonic acid calcium, 10g Anhydrous potassium carbonate; 80mLN-methyl-2-pyrrolidone and 20mL toluene; reaction system is heated to 170 ℃, steams toluene and water, and under this temperature, reacted 20 hours; after reaction finishes; reaction system is chilled to room temperature, pours in the 300mL acetone suction filtration then into; the solid that obtains is dissolved in the 100mL water; be neutralized to acidity (PH=4) with concentrated hydrochloric acid, suction filtration is collected the throw out of being separated out; and be washed till neutrality with deionized water; oven dry obtains the 18.9g target product, and productive rate is 78%.Resulting product has been carried out structural characterization, comprised
1H nuclear-magnetism spectrum is seen Fig. 5; Infrared spectra is seen Fig. 6, proves that the synthetic product is 4,6-two (4-amino-benzene sulfydryl) benzene-1,3-disulfonic acid.
Concrete characterization result is as follows:
Fig. 5 is 4,6-two (4-amino-benzene sulfydryl) benzene-1, the infrared spectra of 3-disulfonic acid (KBr): 3448cm wherein
-1Be the absorption peak of water, 1628cm
-1, 1558cm
-1, 1530cm
-1Be on the phenyl ring-absorption peak of C=C-skeleton 1240cm
-1, 1214cm
-1, 1040cm
-1Be-SO
3 -Absorption peak; Fig. 6 is 4,6-two (4-amino-benzene sulfydryl) benzene-1, the 3-disulfonic acid
1H NMR is with DMSO-d
6Be solvent, wherein the ownership at each peak is indicated in collection of illustrative plates respectively.
Claims (9)
1. di sulfonated aromatic diamine is characterized in that general structure is shown below:
2. di sulfonated aromatic diamine according to claim 1 is characterized in that, said sulfonated aromatic diamine is: 4, and 6-two (4-amino-benzene oxygen) benzene-1,3-disulfonic acid or 4,6-two (4-amino-benzene sulfydryl) benzene-1,3-disulfonic acid.
3. the preparation method of the described di sulfonated aromatic diamine of claim 1 comprises the steps:
(1) with two halogeno-benzenes and oleum reaction, reaction is poured reaction system in the frozen water into after finishing, and to wherein adding carbonate, emits until no gas then, filters, and with the filtrate evaporate to dryness, the vacuum-drying of gained solid obtains the two halogeno-benzenes of two sulfonation;
(2) under nitrogen protection, with the two halogeno-benzenes of two above-mentioned sulfonation, equimolar amino phenol or amino thiophenol, anhydrous carbonate, the mixture heating up to 100 of organic solvent and aromatic hydrocarbons～200 ℃ steam aromatic hydrocarbons and water, reacted 5～40 hours, reaction is chilled to 10～30 ℃ with reaction system after finishing, and pours in the acetone then, suction filtration, resulting solid is soluble in water, add acidic substance and be acidified to pH=3～6, collect the target product di sulfonated aromatic diamine then;
Said pair of halogeno-benzene is m-difluorobenzene, Meta Dichlorobenzene or m-dibromobenzene;
The structure of said amino phenol and amino thiophenol is shown below:
4. method according to claim 3 is characterized in that, in the step (1), with two halogeno-benzenes and oleum reaction, 50～150 ℃ were reacted 5～20 hours.
5. method according to claim 3 is characterized in that, in the step (1), the mol ratio of the sulphur trioxide in two halogeno-benzenes and the oleum is 1: 2～1: 8, and the weight concentration of sulphur trioxide is 10%～60% in the oleum
6. method according to claim 3 is characterized in that, in the step (1), carbonate is selected from lime carbonate or barium carbonate.
7. method according to claim 3, it is characterized in that amino phenol or amino thiophenol be p-aminophenol, to amino thiophenol, Metha Amino Phenon, 4-amino-1-naphthols, 5-amino-1-naphthols, 6-amino-1-naphthols, 5-amino-beta naphthal or 8-amino-beta naphthal.
8. method according to claim 3 is characterized in that, in the step (2), said anhydrous carbonate comprises Carbon Dioxide clock or anhydrous sodium carbonate, and its consumption is 1～5 times of mole number of amino phenol or amino thiophenol;
Said organic solvent comprises N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Used aromatic hydrocarbons comprises benzene, toluene or dimethylbenzene; Said acidic substance are selected from hydrochloric acid or sulfuric acid.
9. method according to claim 3 is characterized in that, in the reaction system, the total concentration by weight of the two halogeno-benzenes of two sulfonation and amino phenol or amino thiophenol is 5～60%.
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|---|---|---|---|---|
| CN1634880A (en) * | 2004-11-18 | 2005-07-06 | 上海交通大学 | Sulfonated alkyl aromatic diamine and its hydrochloride and method for preparing same |
| CN1753860A (en) * | 2003-02-10 | 2006-03-29 | 出光兴产株式会社 | Process for producing aromatic diamine derivative |
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| CN1753860A (en) * | 2003-02-10 | 2006-03-29 | 出光兴产株式会社 | Process for producing aromatic diamine derivative |
| CN1634880A (en) * | 2004-11-18 | 2005-07-06 | 上海交通大学 | Sulfonated alkyl aromatic diamine and its hydrochloride and method for preparing same |
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