CN104725175B - A kind of purification process of many sulfoacid compounds of aromatics - Google Patents
A kind of purification process of many sulfoacid compounds of aromatics Download PDFInfo
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Abstract
The present invention relates to a kind of purification process of many sulfoacid compounds of aromatics.The mixture of many sulfoacid compounds of aromatics prepared via sulfuric acid or oleum sulfonating reaction is reacted by neutralization and the displacement of oxalate compound, the inorganic acid and inorganic salts present in the mixture of many sulfoacid compounds of aromatics beyond many sulfoacid compounds of aromatics is removed.Residual quantity of the inorganic salts in polysulfonate substituted compound effectively can be controlled and significantly reduced, the purity of sulfonated monomer is improved.It is polymerize by high-purity multi-sulfonic substituted compound with diphenols compound and successfully obtains HMW sulfonated polyether-ether-ketone and birds of the same feather flock together compound.Such heavy polymer has a wide range of applications in the research of proton membrane fuel battery dielectric film.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of purification process of many sulfoacid compounds of aromatics.
Background technology
The aromatic compounds of sulfonic group substitution have a wide range of applications in medicine, agricultural chemicals, material and environmental area.And
New proton exchange Replacing fuel battery（PEMFC）Field, is polymerize by sulfonic compound monomer and obtaining high polymer material has
And be widely applied.Many sulfonic compounds are generally prepared by sulfuric acid or oleum sulfonation, normal basis in post processing
Its dissolubility in different solvents is different, using dimethyl sulfoxide（DMSO）Dissolution method（CN101717354）；NaCl salting-out method
（1,3- bis-（3- sodium sulfonate groups）- 4- fluoro benzoyls benzene, copolymer and synthetic method, CN1654454 and containing two sulfonic group sodium
The 4 of salt structure, 4 '-disubstituted diphenyl sulphone (DPS) and preparation method thereof, CN1470505）By many sulfonic compounds and inorganic sulfuric acid
Salt is separated.In actual production process, because dimethyl sulfoxide belongs to the labile organic solvent of higher boiling, high temperature, have to equipment
Very high requirement.In addition, the price of dimethyl sulfoxide is of a relatively high, the cost of production is added to a certain extent.Summary
Reason considers that separated sulfonic compound with inorganic salts using dimethyl sulfoxide dissolution method is still restricted in large-scale production.
The not foot point for the salting out method being of relatively low cost is that operation is cumbersome, and the universality for separating substrate is not high.Examined according to pertinent literature
The sulfonic acid group number contained in Suo Faxian, the structure that the sulfonic compound that can be separated is reported at present is no more than 2.Research
It was found that with the increase of sulfonic acid group, the enhancing of dissolubility in aqueous of many sulfoacid compounds of aromatics, to a certain extent
When sulfonic compound will not be separated out from salting liquid.It is known to neutralize many sulfoacid compounds of aromatics and calcium hydroxide and carbon
Sour sodium be converted separation inorganic acid or inorganic salts method, side reaction can occur in conversion process.
The content of the invention
In view of drawbacks described above of the prior art, the invention provides a kind of purifying side of many sulfoacid compounds of aromatics
Method, neutralization and grass are passed through by the mixture that many sulfoacid compounds of aromatics are prepared via sulfuric acid or oleum sulfonating reaction
The displacement reaction of phosphate compounds, finally gives many sulfoacid compounds of aromatics without inorganic salts.
The features such as many sulfoacid compounds of aromatics have easy deliquescence, polarity is big.Except in water and DMSO (dimethyl sulfoxide (DMSO)) tools
Have outside certain dissolubility, in most conventional organic solvents（Such as methanol, ethanol, acetone, dichloromethane, chloroform or ethyl acetate
Deng）Middle dissolubility is poor.Therefore, in last handling process, using extraction-many sulfoacid compounds of cleaning solution liquid two-phase laminated flow aromatics
Method with inorganic salts is infeasible.According to sulfonic acid calcium salt and calcium sulfate salt deliquescent difference in water, select in hydrogen-oxygen
Change calcium to neutralize, then the calcium sulfate removing produced will be reacted.Further, selection sodium carbonate is used as calcium in many sulfoacid compounds of aromatics
Ion exchange reagent, nmr analysis find there is new accessory substance generation in many sulfoacid compounds of aromatics.Studied by inventor
It was found that, many sulfoacid compounds of aromatics are unstable under the higher carbonate effect of basicity.
Therefore, the present invention proposes a kind of purification process of many sulfoacid compounds of aromatics.Will be via sulfuric acid or oleum
The mixture for many sulfoacid compounds of aromatics that sulfonating reaction is prepared is reacted by neutralization and the displacement of oxalate compound,
Remove inorganic acid present in the mixture of many sulfoacid compounds of aromatics beyond many sulfoacid compounds of aromatics and inorganic
Salt.The many sulfoacid compounds of aromatics, its structure is such as（M1）It is shown：
In formula（M1）In, X is ketone group, sulfuryl, Direct Bonding ,-PO（R1）-、-（CF2）f-（F is 1~5 integer）Or-
C（CF3）2- in one kind；Wherein, R1For C1-6Alkyl, aryl, C1-6Oxyl or aryl substitution alkylidene at least
It is a kind of；Y is at least one of F, Cl, Br or I；M is 1 or 2；N is 1 or 2；M is Na+、K+、Li+、Mg2+Ion or ammonium
One or more in cation.
The structure of many sulfoacid compounds of aromatics, the knot mainly replaced containing multiple sulfonic groups being applicable from the present invention
Structure feature considers that many sulfoacid compounds of aromatics are preferably to have such as having structure formula（M2）：
In formula（M2）In, X is ketone group, sulfuryl, Direct Bonding ,-PO（R1）-、-（CF2）f-（fFor 1~5 integer）Or-
C（CF3）2- in one kind；Wherein, R1For C1-6Alkyl, aryl, C1-6Oxyl or aryl substitution alkylidene at least
It is a kind of；Y is at least one of F, Cl, Br or I；M is Na+、K+、Li+、Mg2+One kind or several in ion or ammonium cation
Kind.
Described N-process includes adding Ca (OH)2Or CaCO3Neutralize and filter the process for removing calcium sulfate precipitation.
Consider the uniformity of real reaction system, preferably Ca (OH)2Or CaCO3Suspension（The mass ratio of solid and water is 1:
1-1:3）；Due to CaCO3There are a large amount of CO in neutralization2Bubble is produced, and may be unfavorable for the control of reaction rate, further preferred Ca
(OH)2Neutralize.Neutralization operation in the step is an exothermic process, is further preferably controlled in the present invention in whole process
The maximum temperature of reaction solution is not higher than 45 DEG C.The pH value in reaction solution with terminal is controlled under the detection of pH meter in 7.05-8.50
Between, to avoid the alkali that processing residual is excessive, the pH value of terminal is further preferably neutralized between 7.05-7.25.
Displacement course of reaction in described purification process includes adding oxalate conversion and two parts are filtered in heat of solution.
First, a certain amount of oxalates is added into the solution after neutralization, it is contemplated that the speed of reaction, preferably controlling reaction temperature exist
50-80 DEG C, react 1.0-5.0 hours.Described oxalates can be selected from：Sodium oxalate, potassium oxalate, potassium binoxalate, potassium tetroxalate,
One or more in lithium oxalate, ammonium oxalate or magnesium oxalate；Consider the practicality of many sulfoacid compounds of aromatics, preferably
One or more in sodium oxalate, potassium oxalate, potassium binoxalate or potassium tetroxalate.Secondly, insoluble solids are filtered out, are concentrated
Be dried to obtain crude product.Finally, by crude product with etc. the aqueous solution of quality flowed back 1-2 hours at 100 DEG C, filter while hot, it is dry
To lurid solid powder.It is not particularly limited in the present invention for concentration and drying, for example：Above-mentioned concentration can use rotation
Turn evaporimeter removing eluant, eluent.Drying can select vacuum drying oven, normal pressure convection oven or infrared drying oven.
Many sulfonic acid substitution calcium salt that the present invention is obtained after being neutralized using calcium hydroxide or calcium carbonate is with calcium sulfate in water
Sex differernce is dissolved, separation of solid and liquid is the calcium salt that can obtain many sulfoacid compounds of aromatics.Further, calcium salt and oxalates are replaced
Reaction is converted into corresponding aromatics polysulfonate compound, realize many sulfoacid compounds of aromatics and inorganic salts effective point
From.
The purification process of the present invention not only greatly reduces the content of inorganic salts in many sulfoacid compounds of aromatics, Er Qiecao
Without using organic solvent in work, purifying cost is effectively reduced.
By many sulfoacid compounds of aromatics of the present invention height is obtained through being further purified to polymerize with diphenols compound
Molecular weight sulfonated polyether-ether-ketone is birdsed of the same feather flock together compound.Sulfonated polyether-ether-ketone compound of birdsing of the same feather flock together can further prepare excellent performance
Proton membrane fuel battery dielectric film.It is widely used in novel energy battery investigation of materials development field.
Embodiment
The present invention can be obtained by the embodiment of preferred embodiments below, but these embodiments are merely to illustrate,
The scope of the present invention is not made and defining.
The raw material used in embodiment：
Oxalates, the hydrate of oxalic acid two, calcium hydroxide, sodium hydroxide, the potassium hydroxide used in embodiment is point
Analyse pure reagent（AR）, purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Deionized water is made by oneself by ion exchange resin resin.
PH meter uses plum Teller, model：FE20（Correct）.4,4 '-two fluoro- 3,3 ', 5,5 '-tetrasulfonic acid sodium benzophenone
Method of the synthesis with reference to described in PCT/CN2012/081062.4,4 '-two fluoro- 3, the synthesis ginseng of 3 '-sodium disulfonate benzophenone
According to the method described in CN101717354.
Used detection method in embodiment：
（1）The many sulfoacid compounds of aromatics are converted into the detection method of sodium salt or sylvite
Whether many sulfoacid compounds of aromatics are fully converted to the detection of corresponding sodium, sylvite for displacement reaction, mainly
Use the residual for whether having calcium ion in the solution that titration identification reaction is obtained.The fragrance for taking displacement resulting after reacting
The many sulfoacid compound aqueous solution 15mL of class, through centrifugation and suction filtration, obtain concentration in 0.1-0.12g mL-1Between clear liquid 10mL.To
Sodium carbonate liquor is added dropwise in the solution（0.2g mL-1）, it is stirred at room temperature 10 minutes, observation, which whether there is precipitation, to be produced.According to calcium carbonate
Solubility product constant is KspCaCO3=0.87×10-8mol L-1, can confirm that displacement reaction is complete without deposition condition.
（2）The method for detecting residue of mineral sulfates
The many sulfoacid compound 1.0g of aromatics obtained by removing after inorganic salts are dissolved in 5mL deionized waters, using saturation
Barium chloride is titrated, and does not observe muddy appearance.According to solubility product constant KspBaSO4=1.08 × 10 of barium sulfate-10mol L-1,
BaCl2Saturated concentration is 1.8mol L under normal temperature-1, sulfate concentration is can obtain less than 1.5 × 10-10mol L-1.Illustrate fragrance
Mineral sulfates content is less than 50ppm in many sulfoacid compounds of class.
Embodiment 1
Take the dilution 2.0L after sulfonating reaction（4,4 '-two fluoro- 3,3 ' 5, the matter of 5 '-tetrasulfonic acid benzophenone cpd
Amount is about 180g, the aqueous solution that sulfuric acid is about 139g）, Ca (OH) is gradually added under the conditions of being sufficiently stirred for2Suspension（185.0g hydrogen
The mixture of calcium oxide and 150mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, through filtering, washing, merge and filter
Liquid obtains pink supernatant liquid.Under pH meter indicated condition, the aqueous solution of the calcium hydroxide containing 14.0g is added to pH=7.14, is taken out
Filter, washing, merging obtain light yellow liquid about 2.5L.Solid oxalic acid sodium 92.0g is added into solution, temperature 50 C is controlled, instead
2h is answered, suction filtration, washing merge, are dried to obtain crude product 162.0g.This crude product is placed in 180mL deionized waters, under counterflow condition
Dissolving, heat filtering, filtrate precipitation are dried and CaCl described above2Detection, obtains 4,4 '-two fluoro- 3 without mineral sulfates,
3 ' 5,5 '-tetrasulfonic acid benzophenone cpd 128.0g.
Embodiment 2
Take the dilution 1.0L after sulfonating reaction（4,4 '-two fluoro- 3, the quality of 3 '-disulfonic acid benzophenone compound is about
For 125g, the aqueous solution that sulfuric acid is about 70g）, Ca (OH) is gradually added under the conditions of being sufficiently stirred for2Suspension（78.0g calcium hydroxides
With the mixture of 100mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, powder is obtained through filtering, washing, merging filtrate
Red supernatant liquid.Under pH meter indicated condition, add the aqueous solution of the calcium hydroxide containing 5.0g to pH=7.28, suction filtration, washing,
Merging obtains light yellow liquid about 1.5L.Solid oxalic acid sodium 47.0g is added into solution, temperature 50 C is controlled, 1h is reacted, takes out
Filter, washing merge.A small amount of clear liquid is taken, is titrated using saturated solution of sodium carbonate described above, confirmation has been replaced completely.Slough solvent
Water, is dried to obtain crude product 110.0g.This crude product is placed in 120mL deionized waters, dissolved under counterflow condition, heat filtering, filtrate
Precipitation is dried and CaCl described above2Detection, obtains white is free of mineral sulfates 4,4 '-two fluoro- 3,3 '-tetrasulfonic acid hexichol
Methanone compounds 102.0g.
Embodiment 3
Take the dilution 2.0L after sulfonating reaction（4,4 '-two fluoro- 3,3 ' 5, the matter of 5 '-tetrasulfonic acid benzophenone cpd
Amount is about 180g, the aqueous solution that sulfuric acid is about 139g）, Ca (OH) is gradually added under the conditions of being sufficiently stirred for2Suspension（165.0g hydrogen
The mixture of calcium oxide and 150mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, through filtering, washing, merge and filter
Liquid obtains pink supernatant liquid.Under pH meter indicated condition, the aqueous solution of the calcium hydroxide containing 24.0g is added to pH=7.05, is taken out
Filter, washing, merging obtain light yellow liquid about 2.3L.Potassium Oxalate Solution is added into solution（115.0g containing potassium oxalate）, control
30 DEG C of temperature, reacts 5h, and suction filtration, washing merge, are dried to obtain crude product 135.0g.This crude product is placed in 150mL deionized waters,
Dissolved under counterflow condition, heat filtering, filtrate precipitation are dried and CaCl described above2Detection, obtains light yellow without inorganic sulfuric acid
The 4 of salt, 4 '-two fluoro- 3,3 ' 5,5 '-tetrasulfonic acid benzophenone cpd 130.0g.
Embodiment 4
Take the dilution 1.0L after sulfonating reaction（4,4 '-two fluoro- 3,3 ' 5, the matter of 5 '-tetrasulfonic acid benzophenone cpd
Amount is about 88.0g, the aqueous solution that sulfuric acid is about 63.0g）, Ca (OH) is gradually added under the conditions of being sufficiently stirred for2Suspension（78.0g
The mixture of calcium hydroxide and 75mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, through filtering, washing, merge
Filtrate obtains pink supernatant liquid.Under pH meter indicated condition, the aqueous solution of the calcium hydroxide containing 12.0g is added to pH=8.5, is taken out
Filter, washing, merging obtain light yellow liquid about 1.6L.Solid oxalic acid sodium 45.0g is added into solution, temperature 50 C is controlled, instead
1h is answered, suction filtration, washing merge.A small amount of clear liquid is taken, is titrated using saturated solution of sodium carbonate described above, confirmation has been replaced completely.
Aqueous solvent is sloughed, crude product 114.0g is dried to obtain, crude product is placed in 120mL deionized waters, is dissolved under counterflow condition, heat filtering,
Filtrate precipitation is dried and CaCl described above2Detection, obtain it is light yellow without mineral sulfates 4,4 '-two fluoro- 3,3 ' 5,5 '-
Tetrasulfonic acid benzophenone cpd 110.0g.
Embodiment 5
Take the dilution 2.0L after sulfonating reaction（4,4 '-two fluoro- 3,3 ' 5, the matter of 5 '-tetrasulfonic acid benzophenone cpd
Amount is about 180g, the aqueous solution that sulfuric acid is about 139g）, CaCO is gradually added under the conditions of being sufficiently stirred for3Suspension（250.0g carbonic acid
The mixture of calcium and 255mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, obtained through filtering, washing, merging filtrate
Pink supernatant liquid.Under pH meter indicated condition, add the aqueous solution of the calcium carbonate containing 20.0g to pH=7.54, suction filtration, washing,
Merging obtains light yellow liquid about 2.5L.Solid oxalic acid sodium 92.0g is added into solution, temperature 50 C is controlled, 2h is reacted, takes out
Filter, washing merge, are dried to obtain crude product 162.0g.This crude product is placed in 180mL deionized waters, dissolved under counterflow condition, heat
Filtering, filtrate precipitation are dried and CaCl described above2Detection, obtain without mineral sulfates 4,4 '-two fluoro- 3,3 ' 5,5 '-
Tetrasulfonic acid benzophenone cpd 128.0g.
Embodiment 6
Take the dilution 2.0L after sulfonating reaction（4,4 '-two fluoro- 3,3 ' 5, the matter of 5 '-tetrasulfonic acid benzophenone cpd
Amount is about 180g, the aqueous solution that sulfuric acid is about 139g）, CaCO is gradually added under the conditions of being sufficiently stirred for3Suspension（215.0g carbonic acid
The mixture of calcium and 250mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, obtained through filtering, washing, merging filtrate
Pink supernatant liquid.Under pH meter indicated condition, add the aqueous solution of the calcium carbonate containing 40.0g to pH=7.25, suction filtration, washing,
Merging obtains light yellow liquid about 2.3L.Potassium Oxalate Solution is added into solution（117.0g containing potassium oxalate）, 30 DEG C of temperature is controlled,
5h is reacted, suction filtration, washing merge, are dried to obtain crude product 134.0g.This crude product is placed in 150mL deionized waters, counterflow condition
Lower dissolving, heat filtering, filtrate precipitation are dried and CaCl described above2Detection, obtain it is light yellow without mineral sulfates 4,4 '-
Two fluoro- 3,3 ' 5,5 '-tetrasulfonic acid benzophenone cpd 138.0g.
Comparative example 1
Take the dilution 2.0L after sulfonating reaction（4,4 '-two fluoro- 3,3 ' 5, the matter of 5 '-tetrasulfonic acid benzophenone cpd
Amount is about 180g, the aqueous solution that sulfuric acid is about 139g）, the suspensions of Ca (OH) 2 are gradually added under the conditions of being sufficiently stirred for（185.0g hydrogen
The mixture of calcium oxide and 150mL deionized waters）, control temperature is less than 45 DEG C.After the completion of addition, through filtering, washing, merge and filter
Liquid obtains pink supernatant liquid.Under pH meter indicated condition, the aqueous solution of the calcium hydroxide containing 14.0g is added to pH=7.14, is taken out
Filter, washing, merging obtain yellow liquid about 2.5L.Solid sodium carbonate 72.0g is added into solution, temperature 50 C, reaction is controlled
2h, suction filtration, washing merge, are dried to obtain crude product 162.0g.This crude product is placed in 180mL deionized waters, it is molten under counterflow condition
Solution, heat filtering, filtrate precipitation are dried and CaCl described above2Detection, obtains 4 without mineral sulfates of yellow, 4 '-two
Fluoro- 3,3 ' 5,5 '-tetrasulfonic acid benzophenone cpd 108.0g.Due to what is obtained, further nmr analysis are found, in reactant
There is new impurity component and cause the product finally obtained to be yellow powder.
Comparative example 2
To 1.2kg4,4 '-two fluoro- 3,3 ' 5,5 '-tetrasulfonic acid sodium benzophenone crude product（20~26%）Middle addition 3.0L
DMSO, 30 DEG C of ultrasound 2h of water-bath, centrifugation（Rotating speed 8000rpm, needs 2~3h of time altogether）.Upper clear supernate after centrifugation is taken out
Filter, the rotated evaporimeter removing major part DMSO of filtrate（High vacuum oil pump is depressurized）3~5h, obtains yellowish-brown sticky oil thing.Plus
Enter 1.0L absolute ethyl alcohols（AR）, 30min is stirred, solid is separated out, suction filtration is obtained light yellow solid, washed twice using absolute ethyl alcohol
（0.5L/ is each）, suction filtration, vacuum drying, obtain the light yellow solid 200g without mineral sulfates.
Comparative example 3
Referenced patent CN1470505 is purified using salting out method to sulfonating reaction liquid.By 250mL 4,4 '-two fluoro- 3,
3 ' 5,5 '-tetrasulfonic acid benzophenone sulfonating reaction liquid (prepares the method described in referenced patent PCT/CN2012/081062）Point
Do not proceed as follows：（A）Take 50mL to be added in 300mL sodium chloride saturated solutions, there are no solid precipitation.(B) 50mL is taken
It is added in 300mL ethanol solutions, there are no solid precipitation.(C) take after 50mL neutralizes through NaOH, be added to 300mL chlorine
Change in sodium saturated solution, there are no solid precipitation.Description of test, the compound 4 with 4 sulfonic group substitutions, 4 '-two fluoro- 3,
3 ', 5,5 '-tetrasulfonic acid benzophenone or its sodium salt have preferable dissolubility in aqueous, are saltoutd using conventional sodium chloride
Method is infeasible.
Claims (4)
1. a kind of purification process of many sulfoacid compounds of aromatics, it is characterised in that：Will be anti-via sulfuric acid or oleum sulfonation
The mixture for many sulfoacid compounds of aromatics that should be prepared passes through Ca (OH)2Or CaCO3Neutralization and oxalates displacement
Reaction, remove inorganic acid present in the mixture of many sulfoacid compounds of aromatics beyond many sulfoacid compounds of aromatics and
Inorganic salts；The many sulfoacid compounds of aromatics, its structure is such as shown in (M1)：
In formula (M1), X is ketone group, sulfuryl, Direct Bonding ,-PO (R1)-、-(CF2)f- or-C (CF3)2- in one kind；Its
In, R1For C1-6Alkyl, aryl, C1-6Oxyl or aryl substitution at least one of alkylidene, f for 1~5 it is whole
Number；Y is at least one of F, Cl, Br or I；M is 1 or 2；N is 1 or 2；M is Na+、K+、Li+Ion or ammonium cation
In one or more.
2. purification process according to claim 1, it is characterised in that：The many sulfoacid compounds of aromatics, its structure is as follows
Shown in row formula (M2)：
In formula (M2), X is ketone group, sulfuryl, Direct Bonding ,-PO (R1)-、-(CF2)f- or-C (CF3)2- in one kind；Its
In, R1For C1-6Alkyl, aryl, C1-6Oxyl or aryl substitution at least one of alkylidene, f for 1~5 it is whole
Number；Y is at least one of F, Cl, Br or I；M is Na+、K+、Li+One or more in ion or ammonium cation.
3. purification process according to claim 1, it is characterised in that：The pH value in reaction solution with terminal is controlled in 7.05-
8.50 between.
4. purification process according to claim 1, it is characterised in that：The oxalates used in the displacement course of reaction can
With selected from：One or more in sodium oxalate, potassium oxalate, potassium binoxalate, potassium tetroxalate, lithium oxalate or ammonium oxalate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470505A (en) * | 2003-06-26 | 2004-01-28 | 上海交通大学 | 4,4'-disubstituent diphenyl sulfon comprisnig di-sulfo group (salt) structure and its preparing method |
| CN101550094A (en) * | 2009-05-12 | 2009-10-07 | 天津师范大学 | Method for preparing important monomer dihalo-disulfonic acid benzophenone of sulfonated polyetheretherketone and salt thereof |
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| KR101965922B1 (en) * | 2011-09-20 | 2019-04-04 | 도레이 카부시키가이샤 | Sulfonic acid group-containing polymer, sulfonic acid group-containing aromatic compound and method of making the same, as well as polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470505A (en) * | 2003-06-26 | 2004-01-28 | 上海交通大学 | 4,4'-disubstituent diphenyl sulfon comprisnig di-sulfo group (salt) structure and its preparing method |
| CN101550094A (en) * | 2009-05-12 | 2009-10-07 | 天津师范大学 | Method for preparing important monomer dihalo-disulfonic acid benzophenone of sulfonated polyetheretherketone and salt thereof |
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