CN1654454A - 1,3-di(3-sodium sulfonate group-4-fluoro-benzoyl) benzene and polymers and their synthesis method - Google Patents
1,3-di(3-sodium sulfonate group-4-fluoro-benzoyl) benzene and polymers and their synthesis method Download PDFInfo
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Abstract
The present invention relates to one kind of sulfo radical containing sulfonated monomer, its copolymers and their synthesis process. Compounds 3, 3'-di(4-fluorobeenzoyl) benzene and fuming sulfuric acid in the molar ratio of 1 to 2-4 are added into flask with stirrer, temperature and reflux condensation pipe, and heated to 100-120 deg.c for reaction of 4-8 hr; and the product is cooled to lower temperature, poured into ice water bath, neutralized with sodium hydroxide, salted out with sodium chloride, suction filtered, and re-crystallized in mixed solution of methanol and water to obtain 1, 3-di(3-sodium sulfonate-4-fluorobeenzoyl) benzene. Through further nucleophilic polycondensation, regulation of the ratio between sulfonated monomer and non-sulfonated monomer, and copolymerization with bisphenols, serial poly(ether-ether-ketone-ketone) products of different sulfonating degree are prepared. The polymers have excellent filming performance, and has excellent application foreground in the field of fuel cell film.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of multipolymer that contains the different sulfonation degree that sulfonic sulfonated monomers, sulfonated monomers obtain by nucleophilic condensation polymerization, and the synthetic method of this monomer, multipolymer.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) adopts the solid state electrolyte polymeric membrane as ionogen, therefore has advantages such as the energy transformation ratio high and low temperature starts, no electrolyzer leaks, the no burn into life-span is long.Therefore be acknowledged as the first-selected power supply that promises to be space flight, military affairs, electromobile and regional power station most.Proton exchange membrane is as the key part of Proton Exchange Membrane Fuel Cells, and it plays a part to isolate fuel and oxygenant and proton conducting, and its performance is determining fuel cell performance.What use morely at present is perfluoro sulfonic acid membrane (Nafion film), and it has shown satisfactory stability and some other high-performance.But because Nafion film cost height, the low proton conductivity when low humidity or high temperature, high methanol permeability have hindered its commercialization process.Therefore, world many countries has been carried out the development of the proton exchange membrane that new PE MFC uses in succession, and proton exchange membrane has been carried out various improvement, wishes that new proton exchange membrane can overcome the shortcoming of existing proton exchange membrane.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 good characteristics of sulfonic group base polymer solvability again.The sulfonated polyaryletherketone can be as the material of proton exchange membrane.In general, the preparation of sulfonated poly aryl ether ketone has the polymkeric substance Direct Sulfonation and carries out 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 the modification of polymkeric substance Direct Sulfonation causes simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of new sulfonic sulfonated monomers that contains, and synthesized temperature classification height, good mechanical property, controlled low-cost proton exchange membrane material---the sulfonated polyether ketone copolymer of sulfonation degree by polymerization, and the synthetic method of sulfonated monomers and sulfonated copolymer based on this monomer.
The present invention utilizes sulfonated reagent (as oleum) sulfonation 1; 3-two (4-fluoro benzoyl) benzene; obtain 1; 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene; again by adjusting the ratio of sulfonated monomers and non-sulfonated monomers; further carry out nucleophilic condensation polymerization,, prepare the sulfonated polyether ketone of a series of different sulfonation degree with the method for copolymerization with bis-phenol.This base polymer has good film-forming properties, in the fuel cell membranes field good application prospects is arranged.
One, 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene sulfonated monomers synthetic:
Containing of the present invention preparation is sulfonic 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene sulfonated monomers, its structural formula shown in (I),
Its synthetic method is as follows:
With 3; 3 '-two (4-fluoro benzoyl) benzene and the adding of sulfonated reagent oleum are equipped with in the there-necked flask of mechanical stirring, thermometer and reflux condensing tube; be heated to 100～120 ℃ of reaction 4～8h, the mol ratio of 3,3 '-two (4-fluoro benzoyl) benzene and oleum is 1: 2～1: 6.Cool and 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 methyl alcohol (ethanol or acetone) and water, obtain pure 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene.
The building-up reactions formula is as follows:
Two, the sulfonated polyether ketone random copolymers is synthetic:
Agitator is being housed; airway; in the there-necked flask of water trap and prolong; add m mole 3; 3 '-two (4-fluoro benzoyl) benzene; k mole 1; 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene; m+k mole biphenol monomer; with the salt of wormwood salt forming agent; its consumption is the m+k mole; with dimethyl sulfoxide (DMSO) (DMSO) (n-formyl sarcolysine base pyrrolidone (NMP); tetramethylene sulfone (TMS) also can) be solvent; solid content is 20-30% (ratio of solvent and monomeric total mass in monomer mass and the system) in the solvent; toluene (or dimethylbenzene) is the band aqua; at 130 ℃～150 ℃ band water 2～4h, steam toluene then, be warmed up to 170～220 ℃ of reaction 6～10h; reaction mixture is poured in water or the acetone then; pulverize with pulverizer; filter, solid is directly boiled with the acetone boiling method; filter, repeat 5～6 times; boil with distilled water again; filter; 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, sulfonation degree is 0 during as k=0, and sulfonation degree is 2 to the maximum when m=0.The structural formula of multipolymer is as follows, x 〉=0 wherein, and y 〉=0, m/k is ratio of integers arbitrarily, as m/k=1/9,2/8,3/7,4/6,5/5,6/4......
Its structural formula of synthetic sulfonated polyether ketone random copolymers of the present invention shown in (II),
Wherein
The building-up reactions formula is as follows:
Description of drawings
Fig. 1: 1, the nuclear-magnetism figure of 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene sulfonated monomers;
The infrared spectrum of Fig. 2: embodiment 2 polymkeric substance c.
As shown in Figure 1, provided the ownership of hydrogen in the monomer, confirmed that we have obtained the sulfonated monomers of expected structure.
As shown in Figure 2,1018cm wherein
-1Be the stretching vibration peak of S=O in the sodium group, 1082cm
-1, 1201cm
-1The absorption peak at place is respectively the asymmetric of O=S=O in the sodium group and symmetrical stretching vibration peak.Polymkeric substance is at 1140-1110cm
-1The charateristic avsorption band that does not have appearance to produce in the scope by crosslinking side reaction.This explanation: the introducing that we are successful in polymkeric substance sulfonic group, and, adopt the sulfonated monomers copolymerization mode, the degraded and the crosslinking reaction that have taken place when having eliminated the Direct Sulfonation polymkeric substance.
Embodiment
Embodiment 1:1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene synthetic:
With 32.2g (0.1mol) 1,3-two (4-fluoro benzoyl) benzene and 40ml oleum (about 0.4mmol) mixture heating up to 110 ℃ reaction 6h stops heating.When liquid temp to be mixed is reduced to below 50 ℃, mixture is poured in the 500ml frozen water.Add sodium hydroxide to solution then and be neutral; drop to and add sodium-chlor (150 gram) after the room temperature and saltout; suction filtration; dry 12h under 80 ℃; the mixing solutions (ratio 5 of volume: 1-7: 1) recrystallization with methyl alcohol (ethanol also can) and water; obtain pure 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene.
Embodiment 2:
Synthesizing of multipolymer, with mmol 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1,3-two (4-fluoro benzoyl) benzene, the dihydroxyphenyl propane of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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 water or the acetone, pulverized, filter, solid is directly boiled, filters with the acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer.(m/k＝1/9、2/8、3/7、4/6、5/5、6/4......)
Table 1: the performance perameter of present embodiment gained copolymer product:
| Numbering | m(mmol) | k(mmol) | ??m/k | Yield(％) | ?η sp/c |
| ????a ????b ????c ????d | ????10 ????20 ????30 ????40 | ????90 ????80 ????70 ????60 | ??1∶9 ??2∶8 ??3∶7 ??4∶6 | ????95 ????93 ????94 ????92 | ?0.44 ?0.52 ?0.58 ?0.63 |
Annotate: m is 1, and 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene content, k are 3,3 '-two (4-fluoro benzoyl) benzene content, Yield: productive rate, η
Sp/ c: reduced viscosity.
Embodiment 3:
With mmol 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1,3-two (4-fluoro benzoyl) benzene, the tetramethyl biphenyl diphenol of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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, pulverized, filter, solid is directly boiled, filters with the acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer.(m/k＝1/9、2/8、3/7、4/6、5/5、6/4......)
Embodiment 4:
With mmol 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1,3-two (4-fluoro benzoyl) benzene, the bisphenol S of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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, pulverized, filter, solid is directly boiled, filters with the acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer.(m/k＝1/9、2/8、3/7、4/6、5/5、6/4......)
Embodiment 5:
With mmol 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1,3-two (4-fluoro benzoyl) benzene, the phenolphthalein of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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, pulverized, filter, solid is directly boiled, filters with the acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer.(m/k＝1/9、2/8、3/7、4/6、5/5、6/4......)
Embodiment 6:
With mmol 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1,3-two (4-fluoro benzoyl) benzene, the adjacent methyl hydroquinone of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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, pulverized, filter, solid is directly boiled, filters with the acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer.(m/k＝1/9、2/8、3/7、4/6、5/5、6/4......)
Embodiment 7:
With mmol 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1,3-two (4-fluoro benzoyl) benzene, the o-tert-butyl Resorcinol of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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, pulverized, filter, solid is directly boiled, filters with the acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer with pulverizer.(m/k＝1/9、2/8、3/7、4/6、5/5、6/4......)
Embodiment 8:
With mmol 1; 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene, kmol 1; 3-two (4-fluoro benzoyl) benzene, the 2,5 di tert butyl hydroquinone of m+k mol and the Anhydrous potassium carbonate of m+k mol join in the there-necked flask that mechanical stirring, thermometer are housed.Nitrogen protection is solvent (solid content is 20%) 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, pulverized, filter, solid is directly boiled, filters with the acetone boiling method with pulverizer, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain multipolymer (m/k=1/9,2/8,3/7,4/6,5/5,6/4......)
Claims (6)
1,1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene sulfonated monomers, its structural formula shown in (I),
2, claim 1 described 1, the preparation method of 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene sulfonated monomers, the steps include: 3,3 '-two (4-fluoro benzoyl) benzene and the adding of sulfonated reagent oleum are equipped with in the there-necked flask of mechanical stirring, thermometer and reflux condensing tube, be heated to 100～120 ℃ of reaction 4～8h, the mol ratio of 3,3 '-two (4-fluoro benzoyl) benzene and oleum is 1: 2～1: 6; Cool and pour in the ice-water bath, earlier be neutralized to neutrality, add sodium-chlor then and saltout with sodium hydroxide, suction filtration, drying, with the mixing solutions recrystallization of methyl alcohol, ethanol or acetone and water, obtain pure 1,3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene.
3, a kind of sulfonated polyether ketone random copolymers, its structural formula shown in (II), x 〉=0, y 〉=0,
AR=wherein
4, the preparation method of the described sulfonated polyether ketone random copolymers of claim 3, its method is as follows:
Agitator is being housed; airway; in the there-necked flask of water trap and prolong; add m mole 3; 3 '-two (4-fluoro benzoyl) benzene; k mole 1; 3-two (3-sodium sulfonate group-4-fluoro benzoyl) benzene; m+k mole biphenol monomer; with the salt of wormwood salt forming agent; its consumption is the m+k mole, with dimethyl sulfoxide (DMSO) (DMSO); n-formyl sarcolysine base pyrrolidone (NMP) or tetramethylene sulfone (TMS) are solvent, and solid content is 20-30% in the solvent; toluene or dimethylbenzene are the band aqua; at 130 ℃～150 ℃ band water 2～4h, steam toluene then, be warmed up to 170～220 ℃ of reaction 6～10h; reaction mixture is poured in water or the acetone then; pulverize with pulverizer; filter, solid is directly boiled with the acetone boiling method; filter, repeat 5～6 times; boil with distilled water again; filter; repeat 5～6 times, in baking oven, dry, obtain multipolymer.
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, adjust the sulfonation degree of polymkeric substance, sulfonation degree is 0 when k=0, and sulfonation degree is 2 to the maximum when m=0.
6, the preparation method of claim 4 or 5 described sulfonated polyether ketone copolymers is characterized in that: bis-phenol is the described bis-phenol of following structural formula.
R=wherein
Or
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104803892A (en) * | 2014-01-26 | 2015-07-29 | 东丽先端材料研究开发（中国）有限公司 | Aryl sulfonic acid compound purifying method |
| CN109096485A (en) * | 2018-07-23 | 2018-12-28 | 大连理工大学 | The novel crystallizable polyether-ether-ketone keto-resin and preparation method that can dissolve the side group containing phthalein |
| CN109971013A (en) * | 2019-04-03 | 2019-07-05 | 山东星火科学技术研究院 | A kind of preparation method of cross-linked polyether-ether-ketone membrane material |
| CN110885411A (en) * | 2019-12-03 | 2020-03-17 | 九江天赐高新材料有限公司 | Preparation method of PBA-b-PEEK-b-PBA block copolymer and block copolymer prepared by same |
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2005
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803892A (en) * | 2014-01-26 | 2015-07-29 | 东丽先端材料研究开发（中国）有限公司 | Aryl sulfonic acid compound purifying method |
| CN104803892B (en) * | 2014-01-26 | 2018-01-23 | 东丽先端材料研究开发（中国）有限公司 | A kind of purification process of aryl sulfonic acid compound |
| CN109096485A (en) * | 2018-07-23 | 2018-12-28 | 大连理工大学 | The novel crystallizable polyether-ether-ketone keto-resin and preparation method that can dissolve the side group containing phthalein |
| CN109096485B (en) * | 2018-07-23 | 2020-09-25 | 大连理工大学 | Crystallizable and dissolvable polyether-ether-ketone resin containing phthalein side group and preparation method thereof |
| CN109971013A (en) * | 2019-04-03 | 2019-07-05 | 山东星火科学技术研究院 | A kind of preparation method of cross-linked polyether-ether-ketone membrane material |
| CN110885411A (en) * | 2019-12-03 | 2020-03-17 | 九江天赐高新材料有限公司 | Preparation method of PBA-b-PEEK-b-PBA block copolymer and block copolymer prepared by same |
| CN110885411B (en) * | 2019-12-03 | 2022-07-08 | 九江天赐高新材料有限公司 | Preparation method of PBA-b-PEEK-b-PBA block copolymer and block copolymer prepared by same |
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