CN102140074A - Sulfonated aromatic dicarboxylic acid for synthesizing sulfonated polymer and preparation method of sulfonated aromatic carboxylic acid - Google Patents
Sulfonated aromatic dicarboxylic acid for synthesizing sulfonated polymer and preparation method of sulfonated aromatic carboxylic acid Download PDFInfo
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Abstract
The invention relates to sulfonated aromatic dicarboxylic acid for synthesizing a sulfonated polymer and a preparation method of the sulfonated aromatic carboxylic acid, belonging to the technical field of fuel cells. The preparation method comprises the following steps: adding aromatic dipenol, 4-halogen benzonitrile, 3-halogen cyanobenzene and potassium carbonate in a reactor for stirring, and then adding an organic solvent and heating to react; after hydrolysis reaction, neutralizing so as to obtain 1,4-di(4-carboxyl phenoxy) benzene, 1,4-di(3-carboxyl phenoxy) benzene, 1,3-di(4-carboxyl phenoxy) benzene or 1,3-di(4-carboxyl phenoxy) benzene; and finally, salting out, filtering, drying and purifying so as to obtain the sodium salt of the sulfonated aromatic dicarboxylic acid.
Description
Technical field
What the present invention relates to is the polymkeric substance in a kind of fuel cell technology field and preparation method thereof, specifically is a kind of sulfonated aromatic dicarboxilic acid that is used for synthetic sulfonated polymer 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, on main polymer chain, directly insert sulfonic group, promptly directly carry out sulfonation with sulphonating agent, though this method is simple to operate, but weak point is easily to cause the degraded of the low and polymer chain of sulfonation degree, and the sulfonation degree of polymkeric substance is not easy control, makes the low and bad mechanical property of resulting sulfonated polymer electric conductivity; The 2nd, earlier monomer is carried out sulfonation, polymerization under certain condition then, this method building-up process is relatively a bit 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.
Find through retrieval prior art, Journal of Polymer Science, Part A:PolymerChemistry 2002,40,37033710 have 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, and 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 present invention is directed to the prior art above shortcomings, a kind of sulfonated aromatic dicarboxilic acid that is used for synthetic sulfonated polymer 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.
The present invention is achieved by the following technical solutions:
The present invention relates to be used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer, its structure is as follows:
Wherein: R is
The present invention relates to the above-mentioned preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer, may further comprise the steps:
The first step, will fragrant diphenol, 4-halogen benzonitrile or 3-halogen benzonitrile and salt of wormwood add in the reactor and carry out stir process, add organic solvent then and the reaction of heating, obtain 1,4-two (4-itrile group phenoxy group) benzene, 1,4-two (3-itrile group phenoxy group) benzene, 1,3-two (4-itrile group phenoxy group) benzene, 1,3-two (3-itrile group phenoxy group) benzene;
The consumption mol ratio of described fragrant diphenol, 4-halogen benzonitrile or 3-halogen benzonitrile and salt of wormwood is 1: 2: 1.5～10;
Described fragrant diphenol is a kind of in Resorcinol or the Resorcinol;
Described 4-halogen benzonitrile is a kind of in 4-fluorobenzonitrile, 4-chlorobenzonitrile or the 4-bromobenzylcyanide;
Described 3-halogen benzonitrile is a kind of in 3-fluorobenzonitrile, 3-chlorobenzonitrile or the 3-bromobenzylcyanide;
Described stir process is meant: the mechanical stirring under protection of inert gas;
Described organic solvent is meant: N-Methyl pyrrolidone, N, a kind of or its combination in dinethylformamide, N,N-dimethylacetamide or the dimethyl sulfoxide (DMSO);
The described reaction of heating is meant: reaction is 10-48 hour under 120-190 ℃ of condition;
The range of solid content of the reactant of the described reaction of heating is 5%～50%;
Second the step, with 1,4-two (4-itrile group phenoxy group) benzene, 1,4-two (3-itrile group phenoxy group) benzene, 1,3-two (4-itrile group phenoxy group) benzene or 1,3-two (3-itrile group phenoxy group) benzene obtain 1 through neutralizing treatment after being added to the reaction that is hydrolyzed in the strong base solution, 4-two (4-carboxyl phenoxy group) benzene, 1,4-two (3-carboxyl phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene or 1,3-two (3-carboxyl phenoxy group) benzene;
Described strong base solution is meant: potassium hydroxide ethylene glycol solution or sodium hydroxide ethylene glycol solution, wherein potassium hydroxide or sodium hydroxide and 1,4-two (4-itrile group phenoxy group) benzene, 1,4-two (3-itrile group phenoxy group) benzene, 1,3-two (4-itrile group phenoxy group) benzene or 1, the mol ratio of 3-two (3-itrile group phenoxy group) benzene is 1: 3～30;
Described hydrolysis reaction was meant: at 150-190 ℃ of hydrolysis reaction 10-48 hour;
The solid content of the reactant of described hydrolysis reaction is 1%～30%;
Described neutralizing treatment is meant: the reaction solution behind the hydrolysis reaction is poured in the deionized water, progressively added hydrochloric acid or sulfuric acid then until pH=0～5;
The 3rd the step, with 1,4-two (4-carboxyl phenoxy group) benzene, 1,4-two (3-carboxyl phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene or 1,3-two (3-carboxyl phenoxy group) benzene is added in the sulfuric acid, obtains the sodium salt of sulfonated aromatic diacid successively after the processing of saltouing, filtration drying and purification processes.
Described sulfuric acid is meant: concentration is 95～98% aqueous sulfuric acid.
Wherein: 1,4-two (4-carboxyl phenoxy group) benzene, 1,4-two (3-carboxyl phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene or 1,3-two (3-carboxyl phenoxy group) benzene and vitriolic mol ratio are 1: 2～200;
Described saltout to handle be meant: earlier 30～100 ℃ of reactions 1～48 hour down, after question response finishes, reaction mixture poured into lowers the temperature in the trash ice, saltout with sodium-chlor simultaneously;
Described purification processes is meant: the product that filtration drying is obtained is dissolved in dimethyl sulfoxide (DMSO), after the filtrate process that obtains after filtering concentrates and reaches washing with acetone, further filters the solid part that obtains and carries out drying, obtains sodium salt.
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 polyamide and sulfonated polyphenyl and the imidazoles that requires.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 is 1,3-two (4-itrile group phenoxy group) benzene (m-CN) and 1, the infrared spectra IR (KBr) of 3-two (4-carboxyl phenoxy group) benzene (m-COOH).
Fig. 2 is 1,3-two (4-itrile group phenoxy group) benzene
1H NMR (DMSO-d
6).
Fig. 3 is 1,3-two (4-carboxyl phenoxy group) benzene
1H NMR (DMSO-d
6).
Fig. 4 is 4,6-two (4-carboxyl phenoxy group) benzene-1, the infrared spectra IR (KBr) of 3-sodium disulfonate.
Fig. 5 is 4,6-two (4-carboxyl phenoxy group) benzene-1, the 3-sodium disulfonate
1H NMR (DMSO-d
6).
Embodiment
Below 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.
With 1.32g (12mmol) Resorcinol, 2.90g (24mmol) 4-fluorobenzonitrile and 3.31g (24mmol) salt of wormwood join mechanical stirring are housed, in the 250ml reactor of nitrogen inlet and reflux condensing tube, the N that adds 25ml, the N-N,N-DIMETHYLACETAMIDE, 155 ℃ of down reactions 24 hours, reduce to room temperature after, product is poured in the frozen water, filter, product vacuum-drying obtains 1,4-two (4-itrile group phenoxy group) benzene 3.45g, productive rate is 92%.
With 3.45g (11.05mmol) 1,4-two (4-itrile group phenoxy group) benzene, 3.09g potassium hydroxide (55.25mmol) and 86ml 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 1,4-two (4-carboxyl phenoxy group) benzene 3.52g, productive rate is 91%.
With 3.52g (10mmol) 1,4-two (the 4-carboxyl phenoxy group) benzene and the 40ml vitriol oil join in the reactor, react 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 decompression distillation that obtains, and use washing with acetone, and solid filtering, drying can obtain 1,4-two (4-carboxyl phenoxy group) benzene-2-benzene sulfonic acid sodium salt (structural formula is as follows) 4.36g, productive rate is 78.7%.
Embodiment 2
With 2.17g (19.7mmol) Resorcinol, 5.44g (39.4mmol) salt of wormwood joins mechanical stirring is housed, and in the 150ml reactor of nitrogen inlet and reflux condensing tube, adds the N,N-dimethylacetamide of 20ml, and normal temperature stirs down, reacts 1～2 hour.Oil bath is warming up to 110 ℃ then, divide by dropping funnel to drip 20ml toluene for three times, react treated that moisture content distilled out fully in 2 hours after, reduce to room temperature, add 4.77g (39.4mmol) 4-fluorobenzonitrile, reacted 24 hours down at 155 ℃, product is poured in the frozen water, filter, placed 70 ℃ of dryings of vacuum drying oven 20 hours, obtain 1,3-two (4-itrile group phenoxy group) benzene 5.72g, productive rate is 93%.
With 5.72g (18.3mmol) 1,3-two (4-itrile group phenoxy group) benzene, 5.12g (91.5mmol) potassium hydroxide and 140ml ethylene glycol join in the reactor, reacted 24 hours down at 170 ℃, reaction makes vacuum distillation apparatus into after finishing, and removes most of ethylene glycol, and product soaks with Virahol, filter, the solid that obtains is dissolved in deionized water, and adding dense HCl to pH is filtration in 1 o'clock, and oven dry obtains white solid 1,3-two (4-carboxyl phenoxy group) benzene 5.26g, productive rate is 82%.
With 5.26g (15mmol) 1,3-two (the 4-carboxyl phenoxy group) benzene and the 108ml vitriol oil join in the reactor, react 19 hours down at 80 ℃, after reducing to room temperature reaction solution is poured in the trash ice of 300g, 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 decompression distillation that obtains, and use washing with acetone, and solid filtering, drying can obtain 4,6-two (4-carboxyl phenoxy group) benzene-1,3-sodium disulfonate (structural formula is as follows) 6.98g, productive rate is 84%.
2.20g (20mmol) Resorcinol, 5.52g (40mmol) salt of wormwood joins mechanical stirring is housed, and in the 100ml reactor of nitrogen inlet and reflux condensing tube, adds the N,N-dimethylacetamide of 25ml, and normal temperature stirs down, reacts 1～2 hour.Oil bath is warming up to 110 ℃ then, divide by dropping funnel to drip 20ml toluene for three times, react treated that moisture content distilled out fully in 2 hours after, reduce to room temperature, add 4.84g (40mmol) 3-fluorobenzonitrile, reacted 24 hours down at 155 ℃, product is poured in the frozen water, filter, placed 70 ℃ of dryings of vacuum drying oven 20 hours, obtain 1,4-two (3-itrile group phenoxy group) benzene 4.68g, productive rate is 75%.
With 4.68g (15mmol) 1,4-two (3-itrile group phenoxy group) benzene, potassium hydroxide and the 90ml ethylene glycol of 4.20g (75mmol) join in the reactor, reacted 24 hours down at 180 ℃, reaction makes vacuum distillation apparatus into after finishing, and removes most of ethylene glycol, and product soaks with Virahol, filter, the solid that obtains is dissolved in deionized water, and adding dense HCl to pH is filtration in 1 o'clock, and oven dry obtains white solid 1,4-two (3-carboxyl phenoxy group) benzene 4.47g, productive rate is 85%.
With 4.47g (12.77mmol) 1,4-two (the 3-carboxyl phenoxy group) benzene and the 51ml vitriol oil join in the reactor, react 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 decompression distillation that obtains, and use washing with acetone, and solid filtering, drying can obtain 1,4-two (3-carboxyl phenoxy group) benzene-2-benzene sulfonic acid sodium salt (structural formula is as follows) 5.59g, productive rate is 79%.
With 1.76g (16mmol) Resorcinol, 4.42g (32mmol) salt of wormwood joins mechanical stirring is housed, and in the 100ml reactor of nitrogen inlet and reflux condensing tube, adds the N,N-dimethylacetamide of 16ml, and normal temperature stirs down, reacts 1～2 hour.Oil bath is warming up to 110 ℃ then, divide by dropping funnel to drip 16ml toluene for three times, react treated that moisture content distilled out fully in 2 hours after, reduce to room temperature, add 3.87g (32mmol) 3-fluorobenzonitrile, reacted 24 hours down at 155 ℃, product is poured in the frozen water, filter, placed 70 ℃ of dryings of vacuum drying oven 20 hours, obtain 1,3-two (3--itrile group phenoxy group) benzene 4.15g, productive rate is 83%.
With 4.15g (13.3mmol) 1,3-two (3-itrile group phenoxy group) benzene, 3.72g (66.5mmol) potassium hydroxide and 104ml ethylene glycol join in the reactor, reacted 24 hours down at 175 ℃, reaction makes vacuum distillation apparatus into after finishing, and removes most of ethylene glycol, and product soaks with Virahol, filter, the solid that obtains is dissolved in deionized water, and adding dense HCl to pH is filtration in 1 o'clock, and oven dry obtains white solid 1,3-two (3-carboxyl phenoxy group) benzene 3.50g, productive rate is 75%.
With 3.50g (10mmol) 1,3-two (the 4-carboxyl phenoxy group) benzene and the 40ml vitriol oil join in the reactor, react 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 decompression distillation that obtains, and use washing with acetone, and solid filtering, drying can obtain 4,6-two (3-carboxyl phenoxy group) benzene-1,3-sodium disulfonate (structural formula is as follows) 3.55g, productive rate is 64%.
To resulting 1,3-two (4-itrile group phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene and 4,6-two (4-carboxyl phenoxy group) benzene-1, the 3-sodium disulfonate carries out structural characterization, comprises infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum (1H nuclear-magnetism spectrum), proves that the synthetic product is a target product 4,6-two (4-carboxyl phenoxy group) benzene-1, the 3-sodium disulfonate.
Characterization result is as follows:
As shown in Figure 1,1,3-two (4-itrile group phenoxy group) benzene (m-CN) and 1, the infrared spectra (KBr) of 3-two (4-carboxyl phenoxy group) benzene (m-COOH): 2220cm wherein
-1Be-charateristic avsorption band of CN; 1, obtain after 3-two (4-itrile group phenoxy group) the benzene hydrolysis 1,2220cm in the infrared spectra of 3-two (4-carboxyl phenoxy group) benzene (m-COOH)
-1The absorption peak of place-CN disappears, 3000cm
-1～2440cm
-1The stretching vibration peak of the O-H of Shi Pi OOH, 1760cm
-1The absorption peak of place-C=O strengthens greatly.
As shown in Figure 2,1,3-two (4-itrile group phenoxy group) benzene
1HNMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, wherein 7.61～7.66ppm place is the chemical shift of 1 hydrogen on the phenyl ring, 7.03～7.08ppm place is the chemical shift of 2 hydrogen on the phenyl ring, 6.79ppm locating is the chemical shift of 3 hydrogen on the phenyl ring, 6.88～6.93ppm place is the chemical shift of 4 hydrogen on the phenyl ring, 7.39～7.45ppm place is the chemical shift of 5 hydrogen on the phenyl ring.
As shown in Figure 3,1,3-two (4-carboxyl phenoxy group) benzene
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, wherein～peak at 12.8ppm place belongs to carboxyl functional group and (COOH) goes up the chemical shift of H, 6.85ppm locating is the chemical shift of 1 hydrogen on the phenyl ring, 6.91～6.96ppm place is the chemical shift of 2 hydrogen on the phenyl ring, 7.44～7.51ppm place is the chemical shift of 3 hydrogen on the phenyl ring, 7.05～7.11ppm place is the chemical shift of 4 hydrogen on the phenyl ring, and 7.91～7.98ppm place is the chemical shift of 5 hydrogen on the phenyl ring.Adopt differential heat scanning analysis method (DSC) to record 1, the fusing point of 3-two (4-carboxyl phenoxy group) benzene is 301.4 ℃.
As shown in Figure 4,4,6-two (4-carboxyl phenoxy group) benzene-1, the infrared spectra IR (KBr) of 3-sodium disulfonate: 1250～1150cm wherein
-1Be-SO
3 -Absorption peak.
As shown in Figure 5,4,6-two (4-carboxyl phenoxy group) benzene-1, the 3-sodium disulfonate
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates that respectively the 12.65ppm place is the chemical shift of H on the carboxyl.Wherein 6.85～7.91ppm place is the chemical shift of 1 hydrogen on the phenyl ring, and the 6.33ppm place is the chemical shift of 2 hydrogen on the phenyl ring, and the 6.38ppm place is the chemical shift of 3 hydrogen on the phenyl ring, and 7.79～7.86ppm place is the chemical shift of 4 hydrogen on the phenyl ring.
Claims (10)
1. sulfonated aromatic dicarboxilic acid that is used for synthetic sulfonated polymer is characterized in that its structure is as follows:
Wherein: R is
2. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 1 is characterized in that, may further comprise the steps:
The first step, will fragrant diphenol, 4-halogen benzonitrile or 3-halogen benzonitrile and salt of wormwood add in the reactor and carry out stir process, add organic solvent then and the reaction of heating, obtain 1,4-two (4-itrile group phenoxy group) benzene, 1,4-two (3-itrile group phenoxy group) benzene, 1,3-two (4-itrile group phenoxy group) benzene or 1,3-two (3-itrile group phenoxy group) benzene;
Second the step, with 1,4-two (4-itrile group phenoxy group) benzene, 1,4-two (3-itrile group phenoxy group) benzene, 1,3-two (4-itrile group phenoxy group) benzene or 1,3-two (3-itrile group phenoxy group) benzene obtain 1 through neutralizing treatment after being added to the reaction that is hydrolyzed in the strong base solution, 4-two (4-carboxyl phenoxy group) benzene, 1,4-two (3-carboxyl phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene or 1,3-two (3-carboxyl phenoxy group) benzene;
The 3rd the step, with 1,4-two (4-carboxyl phenoxy group) benzene, 1,4-two (3-carboxyl phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene or 1,3-two (3-carboxyl phenoxy group) benzene is added in the sulfuric acid, obtains the sodium salt of sulfonated aromatic diacid successively after the processing of saltouing, filtration drying and purification processes.
3. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, the consumption mol ratio of described fragrant diphenol, 4-halogen benzonitrile or 3-halogen benzonitrile and salt of wormwood is 1: 2: 1.5～10, and wherein: fragrant diphenol is a kind of in Resorcinol or the Resorcinol; The 4-halogen benzonitrile is a kind of in 4-fluorobenzonitrile, 4-chlorobenzonitrile or the 4-bromobenzylcyanide; The 3-halogen benzonitrile is a kind of in 3-fluorobenzonitrile, 3-chlorobenzonitrile or the 3-bromobenzylcyanide.
4. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, described organic solvent is meant: N-Methyl pyrrolidone, N, a kind of or its combination in dinethylformamide, N,N-dimethylacetamide or the dimethyl sulfoxide (DMSO).
5. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, described strong base solution is meant: potassium hydroxide ethylene glycol solution or sodium hydroxide ethylene glycol solution, wherein potassium hydroxide or sodium hydroxide and 1,4-two (4-itrile group phenoxy group) benzene, 1,4-two (3-itrile group phenoxy group) benzene, 1,3-two (4-itrile group phenoxy group) benzene or 1, the mol ratio of 3-two (3-itrile group phenoxy group) benzene is 1: 3～30.
6. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, described hydrolysis reaction is meant: at 150-190 ℃ of hydrolysis reaction 10-48 hour, the solid content of the reactant of this hydrolysis reaction was 1%～30%.
7. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, described neutralizing treatment is meant: the reaction solution behind the hydrolysis reaction is poured in the deionized water, progressively added hydrochloric acid or sulfuric acid then until pH=0～5.
8. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that described sulfuric acid is meant: concentration is 95～98% aqueous sulfuric acid.Wherein: 1,4-two (4-carboxyl phenoxy group) benzene, 1,4-two (3-carboxyl phenoxy group) benzene, 1,3-two (4-carboxyl phenoxy group) benzene or 1,3-two (3-carboxyl phenoxy group) benzene and vitriolic mol ratio are 1: 2～200.
9. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, the described processing of saltouing is meant: reacted 1～48 hour down at 30～100 ℃ earlier, after question response finishes, reaction mixture poured in the trash ice lower the temperature, saltout with sodium-chlor simultaneously.
10. the preparation method who is used for the sulfonated aromatic dicarboxilic acid of synthetic sulfonated polymer according to claim 2, it is characterized in that, described purification processes is meant: the product that filtration drying is obtained is dissolved in dimethyl sulfoxide (DMSO), after the filtrate process that obtains after filtering concentrates and reaches washing with acetone, further filter the solid part that obtains and carry out drying, obtain sodium salt.
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Cited By (1)
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|---|---|---|---|---|
| CN113801042A (en) * | 2021-08-25 | 2021-12-17 | 上海新阳半导体材料股份有限公司 | Multi-onium salt type photoacid generator for dry-method ArF light source photoetching |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850767A (en) * | 2006-05-25 | 2006-10-25 | 上海交通大学 | 3,5-di (4-carboxy phenoxy) benzene carbonic acid-and its preparing method |
| CN101381329A (en) * | 2008-10-23 | 2009-03-11 | 上海交通大学 | Sulfonated aromatic dicarboxilic acid and preparation method thereof |
-
2010
- 2010-01-07 CN CN2010103000857A patent/CN102140074A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850767A (en) * | 2006-05-25 | 2006-10-25 | 上海交通大学 | 3,5-di (4-carboxy phenoxy) benzene carbonic acid-and its preparing method |
| CN101381329A (en) * | 2008-10-23 | 2009-03-11 | 上海交通大学 | Sulfonated aromatic dicarboxilic acid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| GEOFFREY C. EASTMOND，JERZY PAPROTNY: "Synthesis of bis(ether nitrile)s and bis(ether acid)s from simple aromatic diols by meta-fluoro displacement from 3-fluorobenzonitrile", 《JOURNAL OF MATERIAL CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801042A (en) * | 2021-08-25 | 2021-12-17 | 上海新阳半导体材料股份有限公司 | Multi-onium salt type photoacid generator for dry-method ArF light source photoetching |
| 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 |
| WO2023024231A1 (en) * | 2021-08-25 | 2023-03-02 | 上海新阳半导体材料股份有限公司 | Polyonium salt photoacid generator for arf light source dry lithography, preparation method therefor and application thereof |
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