CN1939900A - 2,7-disulfonic acid 9,9-2(4-hydroxy-phenyl) fluorene and its production - Google Patents
2,7-disulfonic acid 9,9-2(4-hydroxy-phenyl) fluorene and its production Download PDFInfo
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- CN1939900A CN1939900A CN 200510037440 CN200510037440A CN1939900A CN 1939900 A CN1939900 A CN 1939900A CN 200510037440 CN200510037440 CN 200510037440 CN 200510037440 A CN200510037440 A CN 200510037440A CN 1939900 A CN1939900 A CN 1939900A
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Abstract
2,7-disulfonic acid-9,9-2(4-hydroxy-phenyl)fluorine and its production are disclosed. The process is carried out by diazo-reacting 2,7-disulfonic acid-9,9-2(4-hydroxy-phenyl)fluorine with nitrite and hydrolyzing at a certain acidity and temperature. It's simple and efficient, has gentle reactive condition and short synthetic circuit. It can be used to prepare polyether compound and high-molecular materials.
Description
Technical field
The present invention relates to a kind of biphenol monomer of sulfonic groupization, relate to specifically a kind of 2,7-disulfonic acid base-9,9-two (4-hydroxy phenyl) fluorenes also relates to the preparation method of this compound in addition.
Background technology
The polyarylether compounds normally makes by bisphenols monomer and the reaction of activatory dihalo (mainly being two fluoro) compound monomer.Present some functional high molecule material, the proton exchange membrane of using as fuel cell, the preparation of ultra-filtration membrane etc., the polyarylether family macromolecule material that usually needs sulfonic groupization, and sulfonic number in these polyarylether high molecule material molecules and position play crucial effects (reference: 1. Miyatake K to the character of material, Oyaizu K, Tsuchida E, Hay A.Synthesis and properties of novel sulfonated arylene ether/fluorinated alkane copolymers.Macromolecules, 2001,34:2065; 2. Miyatake K, Chikashige Y, Watanabe M.Novel sulfonatedpoly (arylene ether): a proton conductive polymer electrolyte designed for fuel cell.Macromolecules, 2003,36:9691.).The sulfonic groupization of present polyarylether family macromolecule material, normally utilize polyarylether compounds and sulfonated reagent to react and realize (sulfonation after the first polymerization), the sulfonation degree of the functional high molecule material of Huo Deing and sulfonated position are difficult to control like this, thereby its performance also just is difficult to control (reference: Xueya Shang, Shuanghong Tian, Linghuan Kong, Yuezhong Meng.Synthesis and characterization of sulfonated fluorene-containing poly (aryleneether ketone) for proton exchange membrane.Journal of Membrane Science, 2005, wait to deliver .).If utilize the biphenol monomer of sulfonic groupization and the polyarylether material (earlier sulfonation post polymerization) that the reaction of activatory dihalo compound monomer directly makes sulfonic groupization, just can control its sulfonation degree, can control the sulfonated position again, thereby control the performance (reference: WEISSE HILMAR (DE) of prepared material, KEUL HELMUT (DE), US Patent 2001021764,2001).So the preparation that is necessary for the polyarylether family macromolecule material of sulfonic groupization provides the monomer of sulfonic groupization.
Summary of the invention
The object of the present invention is to provide a kind of biphenol monomer of sulfonic groupization of the polyarylether compounds that is used to prepare sulfonic groupization, make the polyarylether compounds before polymerization, carry out sulfonation, sulfonic number in like this can the controlled function macromolecular material can be controlled sulfonic position again; Another purpose of the present invention provides this monomeric preparation method.
The present invention utilizes nitrite to make 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes diazotization makes diazonium salt, and the diazonium salt that makes is hydrolyzed the biphenol monomer 2 of the sulfonic groupization that obtains, 7-disulfonic acid base-9 under certain acidity and temperature, 9-two (4-hydroxy phenyl) fluorenes, be used to prepare the polyarylether compounds of sulfonic groupization, sulfonic number and position in this compound of the fine control of energy, thus realized purpose of the present invention.
Of the present invention a kind of 2,7-disulfonic acid base-9,9-two (4-hydroxy phenyl) fluorenes, feature is that its structure is represented by formula (1):
Formula (1)
Of the present invention a kind of 2,7-disulfonic acid base-9, the preparation method of 9-two (4-hydroxy phenyl) fluorenes is characterized in that may further comprise the steps:
(1) 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes dissolves with alkaline solution, and is described 2,7-disulfonic acid base-9, the structure of 9-two (4-aminophenyl) fluorenes is with formula (2) expression;
(2) step (1) is obtained 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes solution mixes with the solution of nitrite compounds, then under 0～12 ℃ temperature, mixing solutions is added drop-wise in the sulfuric acid reaction obtains diazonium salt, the structure of described diazonium salt is with formula (3) expression;
(3) diazonium salt that step (2) is obtained is added drop-wise to hydrolysis in 60 ℃～100 ℃ the sulfuric acid, through extract, purifying, obtain the compound of formula (1).
Formula (2) formula (3)
The described alkaline solution of step (1) can be NaOH solution or KOH solution or Na
2CO
3Solution or K
2CO
3Solution etc., the massfraction of alkaline solution preferably 5%～15%.
Step (2) described 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes can be 1: 2～2.2 with the amount of substance ratio of nitrite compounds, and described nitrite compounds can be Sodium Nitrite or potassium nitrite etc., and preferably is made into saturated solution earlier.
Step (2) described 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes can be 1: 4～10 with vitriolic amount of substance ratio, preferably 1: 9, sulfuric acid can be made into massfraction and be 10%～30% solution, preferably be made into 25% solution, described temperature of reaction can be 0～12 ℃, preferably 9 ℃.
The described vitriolic massfraction of step (3) can be 5%～30%, preferably 10%, described hydrolysis temperature can be 60～100 ℃, preferably 80 ℃, to be the product solution that will make separate out from solution with solid sodium chloride or Repone K or sodium sulfate or the saturated product that makes of vitriolate of tartar described extraction purifying, filter, solid is thick product, is 4: 1～1: 4 the methyl alcohol and the mixing solutions recrystallization of dehydrated alcohol again with thick product volume ratio.
Of the present invention 2,7-disulfonic acid base-9,9-two (4-hydroxy phenyl) fluorenes can be used in preparation polyarylether compounds, and make its on certain position with on the sulfonic group of some amount.Preparation method of the present invention has raw material and is easy to get, and synthetic thread is short out, the reaction conditions gentleness, and the yield advantages of higher is for functional high molecule material provides a kind of very useful monomer.
Embodiment
Following examples are to further specify of the present invention, are not limitations of the present invention.
Embodiment 1
Take by weighing 2,7-disulfonic acid base-9, (it is synthetic to press literature method for 9-two (4-aminophenyl) fluorenes, reference: Guo X, FangJ, Watari T, Tanaka K, kita H, Okamoto K I.Novel sulfonated polyimides as polyelectrolytes forfuel cell application.2.Synthesis and proton conductivity of polyimides from9,9-bis (4-aminopheny) fluorine-2,7-disulfonic acid.Macromolecules, 2002,35:6707) 5.08 grams (10mmol) just dissolve it with the dropping of the KOH solution of massfraction 10%; Take by weighing NaNO again
21.50 gram (21.0mmol) is configured to saturated solution; Above-mentioned two kinds of solution mixing solutions that is configured to admixed together is cooled to 0 ℃, be added drop-wise in cooling, under stirring and fill in sulfuric acid (90mmol) solution of massfraction 30% that 30mL is cooled to 5 ℃, the temperature of control reactant is no more than 9 ℃ in the dropping process.After dropwising, continue with the check of starch-kalium iodide test paper, to become blue, add a small amount of urea and disappear to blue being no more than under 9 ℃ the temperature reaction 2 hours, diazonium salt solution.At last the diazonium salt solution that makes is added drop-wise to the 40mL massfraction and is hydrolysis in 80 ℃ of sulphuric acid solns of 10% under vigorous stirring, the control rate of addition, continues to react stopped reaction 30 minutes after dropwising for maintaining the temperature at about 80 ℃.
After the reaction system cooling, saturated with solid sodium chloride, separate out a large amount of solids, filter, the solid that obtains is thick product.With solid vacuum-drying, with dehydrated alcohol and methyl alcohol volume ratio 1: 4 mixing solutions recrystallization.Recrystallization will carry out in dry environment, can not allow solution absorb water.Recrystallization obtains slightly khaki white solid, at 50 ℃ of vacuum dryings, weighs 4.13 grams, yield 80.98%.
Embodiment 2
Take by weighing 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes 5.08 restrains (10mmol), is 5% Na with massfraction
2CO
3Drips of solution adds to just dissolving; Take by weighing NaNO again
21.40 gram (20.0mmol) is configured to saturated solution; Above-mentioned two kinds of solution mixing solutions that is configured to admixed together is cooled to 0 ℃, be added drop-wise in cooling, under stirring and fill in sulfuric acid (40mmol) solution of massfraction 10% that 40mL is cooled to 5 ℃, the temperature of control reactant is no more than 12 ℃ in the dropping process.After dropwising, continue with the check of starch-kalium iodide test paper, to become blue, add a small amount of urea and disappear to blue being no more than under 12 ℃ the temperature reaction 2 hours, diazonium salt solution.The massfraction that at last diazonium salt solution that makes is added drop-wise to 30mL under vigorous stirring is hydrolysis in 60 ℃ of sulphuric acid solns of 15%, and the control rate of addition, continues to react stopped reaction 60 minutes after dropwising for maintaining the temperature at about 60 ℃.
After the reaction system cooling, saturated with solid Repone K, separate out a large amount of solids, filter, the solid that obtains is thick product.With solid vacuum-drying, with dehydrated alcohol and methyl alcohol volume ratio 4: 1 mixing solutions recrystallization.Recrystallization will carry out in dry environment, can not allow solution absorb water.Recrystallization obtains slightly khaki white solid, at 50 ℃ of vacuum dryings, weighs 3.67 grams, yield 71.96%.
Embodiment 3
Take by weighing 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes 5.08 restrains (10mmol), is 15% K with massfraction
2CO
3Drips of solution adds to just dissolving; Take by weighing again
NaNO216.8 gram (22.0mmol) is configured to saturated solution; Above-mentioned two kinds of solution mixing solutions that is configured to admixed together is cooled to 0 ℃, be added drop-wise in cooling, under stirring and fill in sulfuric acid (80mmol) solution of massfraction 20% that 40mL is cooled to 5 ℃, the temperature of control reactant is no more than 10 ℃ in the dropping process.After dropwising, continue with the check of starch-kalium iodide test paper, to become blue, add a small amount of urea and disappear to blue being no more than under 10 ℃ the temperature reaction 2 hours, diazonium salt solution.At last the diazonium salt solution that makes is added drop-wise to the 40mL massfraction and is hydrolysis in 100 ℃ of sulphuric acid solns of 5% under vigorous stirring, the control rate of addition after dropwising, continues reaction 50 minutes, stopped reaction for keeping the solution boiling.
After the reaction system cooling, saturated with solid sodium sulfate, separate out a large amount of solids, filter, the solid that obtains is thick product.With solid vacuum-drying, with dehydrated alcohol and methyl alcohol volume ratio 2: 3 mixing solutions recrystallization.Recrystallization will more carry out at dry environment, can not allow solution absorb water.Recrystallization obtains slightly khaki white solid, at 50 ℃ of vacuum dryings, weighs 3.73 grams, yield 73.12%.
Embodiment 4
Take by weighing 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes 5.08 gram (10mmol) just adds to the NaOH drips of solution of massfraction 10% and to dissolve; Take by weighing KNO again
22.12 gram (21.0mmol) is configured to saturated solution; Above-mentioned two kinds of solution mixing solutions that is configured to admixed together is cooled to 0 ℃, being added drop-wise in cooling, under stirring and filling massfraction that 40mL is cooled to 5 ℃ is that the temperature of control reactant is no more than 6 ℃ in the dropping process in 25% sulfuric acid (100mmol) solution.After dropwising, continue with the check of starch-kalium iodide test paper, to become blue, add a small amount of urea and disappear to blue being no more than under 6 ℃ the temperature reaction 2 hours, diazonium salt solution.At last the diazonium salt solution that makes is added drop-wise to the 20mL massfraction and is hydrolysis in 90 ℃ of sulphuric acid solns of 30% under vigorous stirring, the control rate of addition, continues to react stopped reaction 40 minutes after dropwising for maintaining the temperature at about 90 ℃.
After the reaction system cooling, saturated with solid sulphuric acid potassium, separate out a large amount of solids, filter, the solid that obtains is thick product.With solid vacuum-drying, with dehydrated alcohol and methyl alcohol volume ratio 1: 1 mixing solutions recrystallization.Recrystallization will carry out in dry environment, can not allow solution absorb water.Recrystallization obtains slightly khaki white solid, at 50 ℃ of vacuum dryings, weighs 3.81 grams, yield 74.71%.
Embodiment 5
The product that embodiment 1～4 obtains is analyzed, and confirmation is the compound of formula (1).Analytical data is as follows:
HNMR composes (DMSO-d
6Mark in the solvent, TMS, ppm): 6.652 (d); 6.838 (d); 7.536 (s); 7.596 (d); 7.832 (d), IR (cm
-1): 3444; 2364; 2096; 1624; 1510; 1452; 1385; 1128; 1034; 1005; 829; 712; 619; 561; Fusing point: survey fusing point with micro-fusing point instrument, 235 ℃ begin to decompose, do not find fusion up to 365 ℃.
Claims (7)
1. the compound of formula (1):
Formula (1)
2. the preparation method of the compound of formula (1) is characterized in that may further comprise the steps:
(1) 2 of formula (2) expression, 7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes
Formula (2)
Dissolve with alkaline solution;
(2) step (1) is obtained 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes solution mixes with the solution of nitrite compounds, then under 0～12 ℃ temperature, mixing solutions is added drop-wise to the diazonium salt of the formula that obtains in the sulfuric acid (3) expression
Formula (3)
(3) diazonium salt that step (2) is obtained is added drop-wise to hydrolysis in 60 ℃～100 ℃ the sulfuric acid, through extract, purifying, obtain the compound of above-mentioned formula (1).
3. the preparation method of the compound of formula according to claim 2 (1) is characterized in that the described alkaline solution of step (1) is NaOH solution or KOH solution or Na
2CO
3Solution or K
2CO
3Solution, the massfraction of alkaline solution is 5%～15%.
4. according to the preparation method of the compound of claim 2 or 3 described formulas (1), it is characterized in that the nitrite compounds described in the step (2) is Sodium Nitrite or potassium nitrite, and be made into saturated solution, described 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes is 1: 2～2.2 with the amount of substance ratio of nitrite compounds, described 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes is 1: 4～10 with vitriolic amount of substance ratio, and sulfuric acid is made into massfraction is 10%～30% solution.
5. the preparation method of the compound of formula according to claim 4 (1), it is characterized in that step (2) is described 2,7-disulfonic acid base-9,9-two (4-aminophenyl) fluorenes is 1: 9 with vitriolic amount of substance ratio, and being made into 25% solution, described temperature of reaction is 9 ℃.
6. according to the preparation method of the compound of claim 2 or 3 described formulas (1), it is characterized in that the described vitriolic massfraction of step (3) is 5%～30%, described hydrolysis temperature is 80 ℃, to be the product solution that will make separate out from solution with solid sodium chloride or Repone K or sodium sulfate or the saturated product that makes of vitriolate of tartar described extraction purifying, filter, solid is thick product, is 4: 1～1: 4 the methyl alcohol and the mixing solutions recrystallization of dehydrated alcohol again with thick product volume ratio.
7. the preparation method of the compound of formula according to claim 6 (1) is characterized in that the described vitriolic massfraction of step (3) is 10%.
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| JP2016069289A (en) * | 2014-09-26 | 2016-05-09 | 東京応化工業株式会社 | Production method of vinyl group-containing compound |
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