CN101381329B - Sulfonated aromatic dicarboxilic acid and preparation method thereof - Google Patents
Sulfonated aromatic dicarboxilic acid and preparation method thereof Download PDFInfo
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- CN101381329B CN101381329B CN2008102016314A CN200810201631A CN101381329B CN 101381329 B CN101381329 B CN 101381329B CN 2008102016314 A CN2008102016314 A CN 2008102016314A CN 200810201631 A CN200810201631 A CN 200810201631A CN 101381329 B CN101381329 B CN 101381329B
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- AQOABKGETJLQRO-UHFFFAOYSA-N OC(c(cc1)ccc1Oc(c(-c(cc(cc1)S(O)(=O)=O)c1Oc(cc1)ccc1C(O)=O)c1)ccc1S(O)(=O)=O)=O Chemical compound OC(c(cc1)ccc1Oc(c(-c(cc(cc1)S(O)(=O)=O)c1Oc(cc1)ccc1C(O)=O)c1)ccc1S(O)(=O)=O)=O AQOABKGETJLQRO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses sulfonated aromatic dicarboxylic acid and a preparation method thereof. The sulfonated aromatic dicarboxylic acid is prepared by the following steps: 2, 2'-biphenol or 4, 4'-biphenol and 4-halogen benzonitrile are taken as raw materials to synthesize dicyanoarylene first, the dicyanoarylene is hydrolyzed to produce aromatic diacid, and then the aromatic diacid is sulfonated to obtain the sulfonated aromatic dicarboxylic acid. The sulfonated aromatic dicarboxylic acid can prepare sulfonated polyamide by reacting with diamine, and can prepare sulfonated polybenzimidazole by reacting with tetraarylamine or hexamine. Sulfonated polyamide and sulfonated polybenzimidazole crosslinking membranes have excellent mechanical properties, heat resistance, and solvent resistance, and are widely applied to aspects such as proton conducting membranes and separation membranes for fuel cells, ion exchange membranes for chlor-alkali industry and so on.
Description
Technical field
The present invention relates to class organic compound and preparation method thereof, particularly a kind of sulfonated aromatic dicarboxilic acid 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.Usually sulfonated polymer can obtain by two kinds of approach: the one, polymkeric substance is directly carried out sulfonation with sulphonating agent, though this method is simple to operate, but cause the degraded of the low and polymer chain of sulfonation degree easily, and the sulfonation degree of polymkeric substance is not easy control thereby resulting sulfonated polymer bad mechanical property; The 2nd, with sulfonated monomers polymerization under certain condition, this method is relatively complicated, but can control sulfonation degree by selecting monomer, and obtains having high molecular weight polymers.The sulfonation dicarboxylic acid is the basic raw material of synthetic sulfonated polyamide and sulfonated polyphenyl and imidazoles, can obtain over-all properties by the sulfonation dicarboxylic acid that designs different structure and meet practical sulfonated polyamide and sulfonated polyphenyl and the imidazoles that requires.Document Journal of Polymer Science, Part A:Polymer Chemistry2002,40,3703-3710 has reported that with a kind of commercialization aromatic diacid (m-phthalic acid) be the method for raw material by a kind of sulfonated aromatic diacid of Direct Sulfonation prepared in reaction, but the kind of commercialization aromatic diacid raw material seldom, the kind of the sulfonated aromatic diacid that can be made by these raw materials is very limited, is difficult to satisfy growing application requiring.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of sulfonated aromatic dicarboxilic acid and preparation method thereof is provided, the sulfonated aromatic dicarboxilic acid of preparation gained can be used for synthetic sulfonated polyamide and sulfonated polyphenyl and imidazoles, and then obtain the sulfonated polymer of high comprehensive performance, satisfy practical application request.
For achieving the above object, the present invention is from Molecular Structure Design and practical application angle, a synthetic class sulfonated aromatic dicarboxilic acid, this class sulfonated aromatic dicarboxilic acid is with 2,2 '-'-biphenyl diphenol or 4,4 '-'-biphenyl diphenol and 4-halogen benzonitrile are raw material, at first the synthetic aroma dintrile, the fragrance dintrile makes aromatic diacid through hydrolysis, and aromatic diacid prepares through oversulfonate again.With these sulfonated aromatic dicarboxilic acids is that raw material monomer can prepare sulfonated polymers such as novel sulfonated polybenzimidazole, sulfonated polyphenyl and oxazole and sulfonated polyamide.
One class sulfonated aromatic dicarboxilic acid of the present invention's preparation, its structure is as shown in the formula shown in (1) and (2):
Institute of the present invention synthetic sulfonated aromatic dicarboxilic acid is with halogeno-benzene formonitrile HCN and 4,4 '-'-biphenyl diphenol or 2,2 '-'-biphenyl diphenol are basic raw material, prepares by three-step reaction, and its chemical equation can be expressed as follows:
The concrete preparation method of institute of the present invention synthetic sulfonated aromatic dicarboxilic acid is as follows:
Fs: under protection of inert gas, mechanical stirring condition; 1:2:1.5～10 in molar ratio; with 2; 2 '-'-biphenyl diphenol or 4; 4 '-'-biphenyl diphenol; 4-halogen benzonitrile; and in the salt of wormwood adding reactor, with N-methyl-2-pyrrolidone or N, N-dimethyl formamide or N; N-N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO) are solvent; the range of solid content of reactant is 5%～50%, reacts 10-40 hours under 120-190 ℃ of conditions, obtains 2; 2 '-two (4-itrile group phenoxy group) biphenyl or 4,4 '-two (4-itrile group phenoxy group) biphenyl.
Subordinate phase: with 2,2 '-two (4-itrile group phenoxy group) biphenyl or 4,4 '-two (4-itrile group phenoxy group) biphenyl is added to and contains in the alkaline ethylene glycol solution, wherein 2,2 '-two (4-itrile group phenoxy group) biphenyl or 4,4 '-two (4-itrile group phenoxy group) biphenyl and alkaline mol ratio are 1:3～30, solid content in the reaction solution is 1%～30%, in 150-190 ℃ of hydrolysis reaction after 10-40 hours, reaction solution is poured in the water, be neutralized to PH=0～5 with mineral acid then, obtain 2,2 '-two (4-carboxyl phenoxy group) biphenyl or 4,4 '-two (4-carboxyl phenoxy group) biphenyl.
Phase III: with 2,2 '-two (4-carboxyl phenoxy group) biphenyl or 4,4 '-two (4-carboxyl phenoxy group) biphenyl is added in the vitriol oil, and wherein 2,2 '-two (4-carboxyl phenoxy group) biphenyl or 4, the mol ratio of 4 '-two (the 4-carboxyl phenoxy group) biphenyl and the vitriol oil is 1:2～200, reacts 1～30 hour down in 30～100 ℃, after reaction finishes, reaction solution is poured in the trash ice, and saltout gained sedimentation and filtration, drying with sodium-chlor, obtain crude product, crude product is dissolved in dimethyl sulfoxide (DMSO), filters, the filtrate that obtains is through concentrating, and use washing with acetone, solid part filters, and obtains 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5 after the drying, 5 '-sodium disulfonate or 4,4 '-two (4-carboxyl phenoxy group) biphenyl-3,3 '-disulfonic acid promptly gets purified sulfonated aromatic dicarboxilic acid sodium.
4 used-halogen benzonitrile of the present invention is selected from 4-fluorobenzonitrile or 4-chlorobenzonitrile or 4-bromobenzylcyanide.
The used highly basic of the present invention is potassium hydroxide or sodium hydroxide.
The used mineral acid of the present invention is hydrochloric acid or sulfuric acid.
The sulfonated aromatic dicarboxilic acid of gained of the present invention is the basic raw material of synthetic sulfonated polyamide and sulfonated polyphenyl and imidazoles, can obtain over-all properties by the sulfonation dicarboxylic acid that designs different structure and meet practical sulfonated polyphenyl and the sulfonated polymers such as imidazoles, sulfonated polyphenyl and oxazole and sulfonated polyamide that require.Sulfonated polyphenyl and imidazoles cross linking membrane have excellent mechanical property, resistance toheat and solvent resistance, have widely with fields such as ion-exchange membranees with proton conductive membrane, separatory membrane and chlorine industry at fuel cell and use.
Description of drawings
Fig. 1: the infrared spectra IR (KBr) of 2,2 '-two (4-itrile group phenoxy group) biphenyl (B-CN) and 2,2 '-two (4-carboxyl phenoxy group) biphenyl (B-COOH)
Fig. 2: 2,2 '-two (4-itrile group phenoxy group) biphenyl
1H NMR (DMSO-d
6)
Fig. 3: 2,2 '-two (4-carboxyl phenoxy group) biphenyl
1H NMR (DMSO-d
6)
Fig. 4: 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5, the infrared spectra IR (KBr) of 5 '-sodium disulfonate
Fig. 5: 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5,5 '-sodium disulfonate
1H NMR (DMSO-d
6)
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
With 5.59g (30mmol) 2,2 '-'-biphenyl diphenol, 7.27g (60mmol) 4-fluorobenzonitrile and 16.6g (120mmol) salt of wormwood join mechanical stirring are housed, in the 100ml reactor of nitrogen inlet and reflux condensing tube, N-the methyl-2-pyrrolidone that adds 30ml, 180 ℃ of reactions 20 hours down, reduce to room temperature after, product is poured in the water, filter, product vacuum-drying obtains 2,2 '-two (4-itrile group phenoxy group) biphenyl 10.48g, productive rate is 90%.
With 10.48g (27mmol) 2,2 '-two (4-itrile group phenoxy group) biphenyl, 7.84g potassium hydroxide (140mmol) and 190ml ethylene glycol join in the reactor, 180 ℃ of down reactions 20 hours, reaction solution are poured in the water after reducing to room temperature, add hydrochloric acid to acid (PH=1), filter, product vacuum-drying obtains 2,2 '-two (4-carboxyl phenoxy group) biphenyl 9.77g, productive rate is 85%.
9.77g (23mmol) 2,2 '-two (the 4-carboxyl phenoxy group) biphenyl and the 135ml vitriol oil are joined in the reactor, reacted 20 hours down at 50 ℃, after reducing to room temperature reaction solution is poured in the trash ice of 100g, and carried out " saltouing ", the gained sedimentation and filtration with sodium-chlor, drying obtains crude product.Crude product is dissolved in the dimethyl sulfoxide (DMSO), filters, the filtrate that obtains concentrates, and uses washing with acetone, and solid part filters, and drying can obtain 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5, and 5 '-sodium disulfonate 11.45g, productive rate are 79%.
With 7.45g (40mmol) 2,2 '-'-biphenyl diphenol, 9.69g (80mmol) 4-fluorobenzonitrile and 16.6g (120mmol) salt of wormwood join mechanical stirring are housed, in the 100ml reactor of nitrogen inlet and reflux condensing tube, N-the methyl-2-pyrrolidone that adds 60ml, 180 ℃ of reactions 24 hours down, reduce to room temperature after, product is poured in the water, filter, product vacuum-drying obtains 2,2 '-two (4-itrile group phenoxy group) biphenyl 13.6g, productive rate is 88%.
With 13.6g (35mmol) 2,2 '-two (4-itrile group phenoxy group) biphenyl, 9.8g potassium hydroxide (175mmol) and 200ml ethylene glycol join in the reactor, 180 ℃ of down reactions 20 hours, reaction solution are poured in the water after reducing to room temperature, add hydrochloric acid to acid (PH=1), filter, product vacuum-drying obtains 2,2 '-two (4-carboxyl phenoxy group) biphenyl 12.7g, productive rate is 85%.
12.7g (29.8mmol) 2,2 '-two (the 4-carboxyl phenoxy group) biphenyl and the 100ml vitriol oil are joined in the reactor, reacted 20 hours down at 60 ℃, after reducing to room temperature reaction solution is poured in the trash ice of 80g, and carried out " saltouing ", the gained sedimentation and filtration with sodium-chlor, drying obtains crude product.Crude product is dissolved in the dimethyl sulfoxide (DMSO), filters, the filtrate that obtains concentrates, and uses washing with acetone, and solid part filters, and drying can obtain 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5, and 5 '-sodium disulfonate 14.1g, productive rate are 75%.
With 5.59g (30mmol) 4,4 '-'-biphenyl diphenol, 7.27g (60mmol) 4-fluorobenzonitrile and 16.6g (120mmol) salt of wormwood join mechanical stirring are housed, in the 100ml reactor of nitrogen inlet and reflux condensing tube, N-the methyl-2-pyrrolidone that adds 30ml, 180 ℃ of reactions 20 hours down, reduce to room temperature after, product is poured in the water, filter, product vacuum-drying obtains 4,4 '-two (4-itrile group phenoxy group) biphenyl 9.9g, productive rate is 85%.
With 9.9g (25.5mmol) 4,4 '-two (4-itrile group phenoxy group) biphenyl, 7.28g potassium hydroxide (130mmol) and 180ml ethylene glycol join in the reactor, 180 ℃ of down reactions 20 hours, reaction solution are poured in the water after reducing to room temperature, add hydrochloric acid to acid (PH=1), filter, product vacuum-drying obtains 4,4 '-two (4-carboxyl phenoxy group) biphenyl 8.9g, productive rate is 82%.
8.9g (21mmol) 4,4 '-two (the 4-carboxyl phenoxy group) biphenyl and the 120ml vitriol oil are joined in the reactor, reacted 24 hours down at 50 ℃, after reducing to room temperature reaction solution is poured in the trash ice of 100g, and carried out " saltouing ", the gained sedimentation and filtration with sodium-chlor, drying obtains crude product.Crude product is dissolved in the dimethyl sulfoxide (DMSO), filters, the filtrate that obtains concentrates, and uses washing with acetone, and solid part filters, and drying can obtain 4,4 '-two (4-carboxyl phenoxy group) biphenyl-3, and 3 '-sodium disulfonate 10.3g, productive rate are 78%.
To resulting 2,2 '-two (4-itrile group phenoxy group) biphenyl, 4,4 '-two (4-itrile group phenoxy group) biphenyl, 2,2 '-two (4-carboxyl phenoxy group) biphenyl, 4,4 '-two (4-carboxyl phenoxy group) biphenyl, 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5,5 '-sodium disulfonate and 4,4 '-two (4-carboxyl phenoxy group) biphenyl-3,3 '-disulfonic acid carries out structural characterization, comprise infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum (
1H nuclear-magnetism spectrum), prove that the synthetic product is a target product 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5,5 '-sodium disulfonate and 4,4 '-two (4-carboxyl phenoxy group) biphenyl-3,3 '-sodium disulfonate.
Characterization result is as follows:
Fig. 1 is 2, the infrared spectra (KBr) of 2 '-two (4-itrile group phenoxy group) biphenyl (B-CN) and 2,2 '-two (4-carboxyl phenoxy group) biphenyl (B-COOH): 2228cm wherein
-1Be-charateristic avsorption band of CN; 2228cm in the infrared spectra of 2,2 '-two (the 4-carboxyl phenoxy group) biphenyl (B-COOH) that obtains after 2,2 '-two (4-itrile group phenoxy group) biphenyl hydrolysis
-1The absorption peak of place-CN disappears, 1691cm
-1The absorption peak of place-C=O strengthens greatly.
Fig. 2 is 2,2 '-two (4-itrile group phenoxy group) biphenyl
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, wherein 7.64～7.72ppm place is the chemical shift of 1 hydrogen on the phenyl ring, 6.82～6.88ppm place is the chemical shift of 2 hydrogen on the phenyl ring, 7.04～7.12ppm place is the chemical shift of 3 hydrogen on the phenyl ring, 7.22～7.30ppm place is the chemical shift of 4 hydrogen on the phenyl ring, 7.36～7.44ppm place is the chemical shift of 5,6 hydrogen on the phenyl ring.
Fig. 3 is 2,2 '-two (4-carboxyl phenoxy group) biphenyl
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, wherein the 7.80ppm place is the chemical shift of 1 hydrogen on the phenyl ring, 6.80ppm locating is the chemical shift of 2 hydrogen on the phenyl ring, 7.02ppm locating is the chemical shift of 3 hydrogen on the phenyl ring, 7.22ppm locating is the chemical shift of 4 hydrogen on the phenyl ring, the 7.38ppm place is the chemical shift of 5,6 hydrogen on the phenyl ring, and the 12.75ppm place is the chemical shift of hydrogen on the carboxyl.Adopting differential heat scanning analysis method (DSC) to record 2,2 '-two (4-carboxyl phenoxy group) biphenyl fusing point is 277.9 ℃.
Fig. 4 is 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5, the infrared spectra of 5 '-sodium disulfonate (KBr): 1250～1150cm wherein
-1Be-SO
3 -Absorption peak.
Fig. 5 is 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5,5 '-sodium disulfonate
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, wherein the 7.60ppm place is the chemical shift of 1,2 hydrogen on the phenyl ring, 6.80ppm locating is the chemical shift of 4 hydrogen on the phenyl ring, 6.90ppm locating is the chemical shift of 3 hydrogen on the phenyl ring, 7.80ppm locating is the chemical shift of 5 hydrogen on the phenyl ring, the 12.75ppm place is the chemical shift of hydrogen on the carboxyl.
Claims (3)
1. sulfonated aromatic dicarboxilic acid is characterized in that structural formula is:
2. the preparation method of sulfonated aromatic dicarboxilic acid according to claim 1 is characterized in that comprising the steps:
(1) under protection of inert gas, mechanical stirring condition, 1: 2: 1.5 in molar ratio～10, with 2,2 '-'-biphenyl diphenol or 4,4 '-'-biphenyl diphenol, the 4-halogen benzonitrile, and in the salt of wormwood adding reactor, with N-Methyl pyrrolidone or N, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO) are solvent, the range of solid content of reactant is 5%～50%, and reaction is 10-40 hour under 120-190 ℃ of condition, obtains 2,2 '-two (4-itrile group phenoxy group) biphenyl or 4,4 '-two (4-itrile group phenoxy group) biphenyl;
(2) with 2,2 '-two (4-itrile group phenoxy group) biphenyl or 4,4 '-two (4-itrile group phenoxy group) biphenyl is added to and contains in the alkaline ethylene glycol solution, wherein 2,2 '-two (4-itrile group phenoxy group) biphenyl or 4,4 '-two (4-itrile group phenoxy group) biphenyl and alkaline mol ratio are 1: 3～30, solid content in the reaction solution is 1%～30%, after 150-190 ℃ of hydrolysis reaction 10-40 hour, reaction solution is poured in the water, be neutralized to PH=0～5 with mineral acid then, obtain 2,2 '-two (4-carboxyl phenoxy group) biphenyl or 4,4 '-two (4-carboxyl phenoxy group) biphenyl;
(3) with 2,2 '-two (4-carboxyl phenoxy group) biphenyl or 4,4 '-two (4-carboxyl phenoxy group) biphenyl is added in the vitriol oil, and wherein 2,2 '-two (4-carboxyl phenoxy group) biphenyl or 4, the mol ratio of 4 '-two (the 4-carboxyl phenoxy group) biphenyl and the vitriol oil is 1: 2～200, reacts 1～20 hour down in 30～100 ℃, after reaction finishes, reaction solution is poured in the trash ice, and saltout gained sedimentation and filtration, drying with sodium-chlor, obtain crude product, crude product is dissolved in dimethyl sulfoxide (DMSO), filters, the filtrate that obtains is through concentrating, and use washing with acetone, solid part filters, and obtains 2,2 '-two (4-carboxyl phenoxy group) biphenyl-5 after the drying, 5 '-disulfonic acid or 4,4 '-two (4-carboxyl phenoxy group) biphenyl-3,3 '-disulfonic acid promptly gets purified sulfonated aromatic dicarboxilic acid;
The above highly basic is selected from potassium hydroxide or sodium hydroxide, and described mineral acid is hydrochloric acid or sulfuric acid.
3. method according to claim 2 is characterized in that described 4-halogen benzonitrile is selected from 4-fluorobenzonitrile, 4-chlorobenzonitrile or 4-bromobenzylcyanide.
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| CN102140074A (en) * | 2010-01-07 | 2011-08-03 | 上海交通大学 | Sulfonated aromatic dicarboxylic acid for synthesizing sulfonated polymer and preparation method of sulfonated aromatic carboxylic acid |
| CN102241610A (en) * | 2011-04-20 | 2011-11-16 | 上海交通大学 | Sulfonated aromatic dicarboxilic acid and preparation method thereof |
| CN105131289B (en) * | 2015-08-24 | 2018-07-17 | 上海交通大学 | A kind of novel sulfonated polybenzimidazoles copolymer, cross linking membrane, preparation method and applications |
| CN110204459A (en) * | 2019-04-30 | 2019-09-06 | 珠海派锐尔新材料有限公司 | A kind of aromatic series diether dioctyl phthalate and preparation method thereof |
| CN113801042B (en) * | 2021-08-25 | 2022-09-27 | 上海新阳半导体材料股份有限公司 | Multi-onium salt type photoacid generator for dry-process photoetching of ArF light source |
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