CN1556100A - Sulfonated monomer, polymer and its synthesis method - Google Patents
Sulfonated monomer, polymer and its synthesis method Download PDFInfo
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- CN1556100A CN1556100A CNA2003101160090A CN200310116009A CN1556100A CN 1556100 A CN1556100 A CN 1556100A CN A2003101160090 A CNA2003101160090 A CN A2003101160090A CN 200310116009 A CN200310116009 A CN 200310116009A CN 1556100 A CN1556100 A CN 1556100A
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Abstract
A process for synthesizing a novel sulfonated monomer and its polymer includes sulfonating 4,4'-bis(4-fluoro-benzyl) benzene to obtain 1,4-bis (3-sodium sulfonate-yl-4-fluoro-benzoyl) benzene, regulating the ratio of sulfonated monomer to unsulfonated monomer, copolymerizing with biphenol, forming salt, distilling for removing toluene, reacting at 150-190 deg.C for 4-8 hr, adding resultant to water or acetone to obtain coarse product, pulverizing, boiling in acetone-reflux-filtering 5-6 times, boiling in distilled water-filtering 5-6 times, and baking to obtain a series of copolymers.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of sulfonated monomers, polymkeric substance and synthetic technology thereof that contains the sulfonic acid base class.
Background technology
Proton exchange model fuel cell (PEMFC) is a kind of efficient, oligosaprobic power generation assembly.Compare advantage such as PEMFC has the specific power height, service temperature is low, corrodibility is low and the life-span is long with the fuel cell of other type.As the heart of PEMFC, the performance of proton exchange membrane (PEM) plays a crucial role to fuel cell performance.At present the maximum of usefulness are perfluoro sulfonic acid membrane (Nafion), though this film has shown stability preferably, exist the cost height, and the proton-conducting when low humidity or high temperature is low, shortcomings such as methanol permeability height.Therefore develop new proton exchange membrane material is the focus that people pay close attention to always.The polyaryletherketone base polymer is known as special engineering plastics because of it has the excellent comprehensive performance.Its good thermotolerance and mechanical property have been subjected to people and have paid close attention to widely.Sulfonic group is incorporated in the main chain of polyaryletherketone, promptly can keeps the excellent properties of polyaryletherketone, can bring into play the characteristics of sulfonic group base polymer good film-forming property again.The sulfonated polyaryletherketone can be as the material of proton exchange membrane.In general, the preparation of sulfonated poly aryl ether ketone has polymkeric substance Direct Sulfonation and two approach of polymerization by sulfonated monomers.Carry out the sulfonated poly aryl ether ketone of polymerization preparation by sulfonated monomers and can effectively control sulfonation degree, deficiencies such as crosslinked, the degraded that has also overcome that sulfonation modifying causes simultaneously.The present invention is based on second kind of approach design and synthesized temperature classification height, good mechanical property, the controlled low-cost proton exchange membrane material of sulfonation degree.We have designed and synthesized a kind of new sulfonic monomer that contains.By nucleophilic condensation polymerization, obtained the different sulfonated polyether ketone of a series of sulfonation degree.
Summary of the invention
The objective of the invention is by 4; 4 '-two (4-fluoro-benzoyl) benzene and oleum reaction have obtained 1; 4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene; utilize nucleophilic condensation polymerization then; by adjusting the ratio of sulfonated monomers and non-sulfonated monomers, carry out the polyether ether ketone ketone that copolymerization goes out a series of different sulfonation degree with bis-phenol.This base polymer has good film-forming properties, in the fuel cell membranes field good application prospects is arranged.
One, 1,4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene synthetic:
With 4; 4 '-two (4-fluoro-benzoyl) benzene (Gu) (prolonging Dragon Well tea chemical plant, limit) and oleum (Beijing chemical reagent factory) mixing (mol ratio 1: 3-1: 10); add and be equipped with in the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to 70-140 ℃ of reaction 4-8 hour.After cooling, pour in the ice-water bath, be neutralized to neutrality with sodium hydroxide earlier.Add sodium-chlor then and saltout, suction filtration, drying, with the mixing solutions recrystallization of 1: 1 methyl alcohol (ethanol or acetone also can) and water, obtain pure 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene, its structural formula is as follows:
1, the building-up reactions formula of 4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene:
Two, the sulfonated polyether ketone random copolymers is synthetic:
In the there-necked flask that agitator, airway, water trap and prolong are housed; add kmol4; 4 '-two (4-fluoro-benzoyl) benzene, mmol1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene, (m+k) mol bis-phenol (bis-phenol can be the structure in the following reaction formula).With salt of wormwood salt forming agent (m+kmol), DMSO (NMP, TMS, DMAC also can) is solvent (solid content 20-40%), and toluene is the band aqua.At 140 ℃ of band water 2-4h.Steam toluene then, at 150-190 ℃ of reaction 4h-8h, then reaction mixture is poured in water or the acetone, obtained thick product, thick product is pulverized, filtered with pulverizer, and boil, reflux, filter with acetone, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain polymer samples.Can adjust the sulfonation degree of polymkeric substance by adjusting the ratio of m and k, sulfonation degree is 0 during as m=0, and sulfonation degree is 2 to the maximum when k=0.The structural formula of multipolymer is as follows, x 〉=0 wherein, and y 〉=0:
The bis-phenol of above-mentioned copolymer structure (AR-) can be following structure:
The building-up reactions formula of sulfonated polyether ketone copolymer:
Illustrate: 1, salify: biphenol monomer and Carbon Dioxide nak response, slough two hydrogen ions, become the form of organic salt; 2, solid content: the reaction monomers that adds in the system shared mass percent in solvent.For example: adding the monomeric content of solid is 20g, and establishing the amount that needs DMSO is xml, if solid content is 20%, and 20%=20/ ρ x (ρ is the density of solvent).
Description of drawings
Fig. 1: sulfonated monomers nuclear-magnetism figure
The nuclear-magnetism figure of Fig. 1 has provided the ownership of each hydrogen in the sulfonated monomers, has confirmed the structure of the sulfonated monomers of our gained.
Specific implementation method
One, 1,4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene synthetic:
Embodiment one,
With 32.2g (0.1mol) 4,4 '-two (4-fluoro-benzoyl) benzene and 40ml oleum mixture heating up to 100 ℃ reaction 6h, stop heating.Liquid temp to be mixed will hang down to below 50 ℃ the time, and mixture is poured in the 500ml frozen water.Add sodium hydroxide to solution then and be neutral, drop to and add 200g sodium-chlor after the room temperature and saltout, suction filtration is at 80 ℃ of dry 12h down, with the mixing solutions recrystallization of 1: 1 methyl alcohol (ethanol, acetone and other organic solvent also can) and water.Obtain pure 1,4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene (the 42.1g productive rate is 80%).
Embodiment two,
64.4g (0.2mol) 4,4 '-two (4-fluoro-benzoyl) benzene and 90ml oleum are heated to 110 ℃ of reaction 4h, stop heating.Liquid temp to be mixed will hang down to below 50 ℃ the time, and mixture is poured in the 1000ml frozen water.Add sodium hydroxide to solution then and be neutral, drop to and add 200g sodium-chlor after the room temperature and saltout, suction filtration is at 80 ℃ of dry 12h down, with the mixing solutions recrystallization of 1: 1 methyl alcohol (ethanol, acetone and other organic solvent also can) and water.Obtain pure 1,4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene (the 89.2g productive rate is 82%).
Two, multipolymer is synthetic:
Embodiment one,
With mmol 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene, kmol 4,4 '-two (4-fluoro-benzoyl) benzene, the dihydroxyphenyl propane of m+kmol and the Anhydrous potassium carbonate of m+kmol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 30%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4 hours down, steams toluene then and is warming up to 180 ℃ of reactions 6 hours.Mixture is poured in water or the acetone, with pulverizer in 50% aqueous solution, pulverize, filtration under diminished pressure, solid is directly boiled, refluxes, filters with acetone, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, dry in baking oven, obtain multipolymer, productive rate is about 95%, (can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
The performance perameter of present embodiment gained copolymer product:
polymer m(mmol) k(mmol) m/k Yield(％) η
sp/c T
10％loss(℃) Ds
a 8 32 2∶8 94 1.29 517 0.4
b 16 24 4∶6 93 2.04 476 0.8
c 20 20 5∶5 95 4.24 472 1.0
d 24 16 6∶4 93 1.12 455 1.2
e 40 0 10∶0 94 1.10 379 2.0
A) η
SpRecord in the DMF solution of the tangible 5g/L of/c reduced viscosity
B) T
10%lossThe heat decomposition temperature of polymkeric substance 10%
C) Ds: the sulfonation degree of polymkeric substance
Embodiment two,
With mmol 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene, kmol 4,4 '-two (4-fluoro-benzoyl) benzene, the bisphenol S of m+kmol and the Anhydrous potassium carbonate of m+kmol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 30%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4 hours down, steams toluene then and is warming up to 180 ℃ of reactions 6 hours.Mixture is poured in the water,, solid is directly boiled, refluxes, filters with acetone, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain polymkeric substance with pulverizer pulverizing, filtration under diminished pressure in 50% aqueous solution.(can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
Embodiment three,
With mmol 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene, kmol 4,4 '-two (4-fluoro-benzoyl) benzene, the phenolphthalein of m+kmol and the Anhydrous potassium carbonate of m+kmol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 30%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4 hours down, steams toluene then and is warming up to 180 ℃ of reactions 6 hours.Mixture is poured in the water,, solid is directly boiled, refluxes, filters with acetone, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer pulverizing, filtration under diminished pressure in 50% aqueous solution.(can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
Embodiment four,
With mmol1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene, kmol 4,4 '-two (4-fluoro-benzoyl) benzene, the tetramethyl biphenyl diphenol of m+kmol and the Anhydrous potassium carbonate of m+kmol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 30%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4 hours down, steams toluene then and is warming up to 180 ℃ of reactions 6 hours.Mixture is poured in the water, in 50% aqueous solution, is pulverized, filters, solid is directly boiled, refluxes, filters with acetone with pulverizer,, repeat 5～6 times, boil, filter with the distilled water decompression again, repeat 5～6 times, in baking oven, dry, obtain multipolymer.(can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
Embodiment five,
With mmol1,4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 4,4 '-two (4-fluoro benzoyl) benzene, the adjacent methyl hydroquinone of m+kmol and the Anhydrous potassium carbonate of m+kmol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 25%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4h down, steams toluene then and is warming up to 180 ℃ of reaction 6h.Mixture is poured in the water, and the usefulness pulverizer is pulverized in 50% aqueous solution, filtration under diminished pressure, and solid is directly boiled, filters with the acetone boiling method, repeats 5～6 times, boils, filters with distilled water again, repeats 5～6 times, dries in baking oven, obtains multipolymer.(can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
Embodiment six
With mmol1,4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 4,4 '-two (4-fluoro benzoyl) benzene, the o-tert-butyl Resorcinol of m+kmol and the Anhydrous potassium carbonate of m+kmol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 25%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4h down, steams toluene then and is warming up to 180 ℃ of reaction 6h.Mixture is poured in the water, and the usefulness pulverizer is pulverized in 50% aqueous solution, filtration under diminished pressure, and solid is directly boiled, filters with the acetone boiling method, repeats 5～6 times, boils, filters with distilled water again, repeats 5～6 times, dries in baking oven, obtains multipolymer.(can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
Embodiment seven
With mmol1; 4-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 4; 2 of 4 '-two (4-fluoro benzoyl) benzene, m+kmol, the Anhydrous potassium carbonate of 6-di-tert-butyl hydroquinone and m+kmol joins in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 25%) with DMSO (NMP, TMS, DMAC also can), and toluene is the band aqua, at 140 ℃ of band water 4h down, steams toluene then and is warming up to 180 ℃ of reaction 6h.Mixture is poured in the water, and the usefulness pulverizer is pulverized in 50% aqueous solution, filtration under diminished pressure, and solid is directly boiled, filters with the acetone boiling method, repeats 5～6 times, boils, filters with distilled water again, repeats 5～6 times, dries in baking oven, obtains multipolymer.(can adjust the sulfonation degree of polymkeric substance) by adjusting the ratio of m and k
Claims (6)
1, a kind of sulfonated monomers, its structural formula shown in (I),
2; the preparation method of the described sulfonated monomers of claim 1; the steps include: 4; 4 '-two (4-fluoro-benzoyl) benzene and oleum mix; mol ratio 1: 3-1: 10; add mechanical stirring is housed; in the there-necked flask of thermometer and reflux condensing tube; be heated to 70-140 ℃ of reaction 4-8 hour; after cooling; pour in the ice-water bath, be neutralized to neutrality with sodium hydroxide earlier, add sodium-chlor then and saltout; suction filtration; dry; with 1: 1 methyl alcohol; the mixing solutions recrystallization of ethanol or acetone and water, obtain pure 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene.
3, a kind of sulfonated polyether ketone copolymer, its structural formula shown in (II), x 〉=0 wherein, y 〉=0,
Bis-phenol (AR-) can be following structure:
4; the preparation method of the described sulfonated polyether ketone copolymer of claim 3; its method is as follows: agitator is being housed; airway; in the there-necked flask of water trap and prolong; add k mol 4; 4 '-two (4-fluoro-benzoyl) benzene; m mol 1; 4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene; m+k mol bis-phenol is with m+k mol salt of wormwood salt forming agent, DMSO or NMP; TMS; DMAC is a solvent; solid content 20-40%; toluene is the band aqua, at 140 ℃ of band water 2-4h, steams toluene then; at 150-190 ℃ of reaction 4h-8h; then reaction mixture is poured in water or the acetone, obtained thick product, thick product is pulverized with pulverizer; filter; and boil with acetone; reflux; filter; repeat 5～6 times, boil with distilled water again; filter, repeat 5～6 times; in baking oven, dry, obtain polymer samples.
5, the preparation method of sulfonated polyether ketone copolymer as claimed in claim 4 is characterized in that: by adjusting the ratio of m and k, can adjust the sulfonation degree of polymkeric substance, the multipolymer sulfonation degree is 0 during m=0, and the multipolymer sulfonation degree is 2 to the maximum during k=0.
6, the preparation method of claim 4 or 5 described sulfonated polyether ketone copolymers is characterized in that: bis-phenol can be the described bis-phenol of following structural formula.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100347222C (en) * | 2005-01-13 | 2007-11-07 | 上海交通大学 | Sulfonated polyaryl sulfoether containing triphenyl biketone structure unit and preparing process thereof |
| CN101463186B (en) * | 2008-12-30 | 2011-01-26 | 吉林大学 | Composite type proton conduction membrane material containing amino-sulfonic group and preparation thereof |
| CN102120874A (en) * | 2010-12-10 | 2011-07-13 | 中国科学院大连化学物理研究所 | Sulfonated polyarylether polymer ion exchange membrane containing crosslinking groups and application thereof |
| CN102945972A (en) * | 2012-09-07 | 2013-02-27 | 四川大学 | Preparation method of composite proton exchange membrane for all vanadium redox flow battery |
| CN103980465A (en) * | 2014-06-06 | 2014-08-13 | 中国科学院长春应用化学研究所 | Sulfonated polyphenylether ketone and preparation method thereof, and sulfonated polyphenylether ketone proton exchange membrane |
| CN105582819A (en) * | 2016-01-25 | 2016-05-18 | 吉林大学 | Solvent-resistant sulfonated PEAK (polyaryletherketone) ultrafiltration membrane and preparation method thereof |
| CN107394240A (en) * | 2017-06-02 | 2017-11-24 | 南京工业大学 | A kind of sulfonated poly aryl ether ketone amberplex preparation method and application |
| CN108258170A (en) * | 2017-12-05 | 2018-07-06 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm |
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2003
- 2003-12-30 CN CN 200310116009 patent/CN1233626C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347222C (en) * | 2005-01-13 | 2007-11-07 | 上海交通大学 | Sulfonated polyaryl sulfoether containing triphenyl biketone structure unit and preparing process thereof |
| CN101463186B (en) * | 2008-12-30 | 2011-01-26 | 吉林大学 | Composite type proton conduction membrane material containing amino-sulfonic group and preparation thereof |
| CN102120874A (en) * | 2010-12-10 | 2011-07-13 | 中国科学院大连化学物理研究所 | Sulfonated polyarylether polymer ion exchange membrane containing crosslinking groups and application thereof |
| CN102945972A (en) * | 2012-09-07 | 2013-02-27 | 四川大学 | Preparation method of composite proton exchange membrane for all vanadium redox flow battery |
| CN103980465A (en) * | 2014-06-06 | 2014-08-13 | 中国科学院长春应用化学研究所 | Sulfonated polyphenylether ketone and preparation method thereof, and sulfonated polyphenylether ketone proton exchange membrane |
| CN103980465B (en) * | 2014-06-06 | 2016-06-01 | 中国科学院长春应用化学研究所 | A kind of sulfonated poly (phenylene oxide) ketone and its preparation method, sulfonated poly (phenylene oxide) ketone class proton exchange membrane |
| CN105582819A (en) * | 2016-01-25 | 2016-05-18 | 吉林大学 | Solvent-resistant sulfonated PEAK (polyaryletherketone) ultrafiltration membrane and preparation method thereof |
| CN107394240A (en) * | 2017-06-02 | 2017-11-24 | 南京工业大学 | A kind of sulfonated poly aryl ether ketone amberplex preparation method and application |
| CN107394240B (en) * | 2017-06-02 | 2020-05-26 | 南京工业大学 | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane |
| CN108258170A (en) * | 2017-12-05 | 2018-07-06 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyether-ether-ketone base lithium battery diaphragm |
| CN108258170B (en) * | 2017-12-05 | 2021-07-16 | 宜宾天原集团股份有限公司 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
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