CN1282686C - Sulfonated polyether compound, its synthesis and use thereof - Google Patents

Sulfonated polyether compound, its synthesis and use thereof Download PDF

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CN1282686C
CN1282686C CNB2005100675313A CN200510067531A CN1282686C CN 1282686 C CN1282686 C CN 1282686C CN B2005100675313 A CNB2005100675313 A CN B2005100675313A CN 200510067531 A CN200510067531 A CN 200510067531A CN 1282686 C CN1282686 C CN 1282686C
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ether compounds
aryl ether
polyether compound
proton exchange
exchange membrane
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CN1680461A (en
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孟跃中
王雷
王栓紧
肖敏
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Guangzhou Institute of Chemistry of CAS
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Guangzhou Institute of Chemistry of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The present invention belongs to the technical field of fuel batteries, in particular to proton exchange membrane materials, which relates to a series of novel sulfonated aryl ether compounds and intermediates thereof, and the synthesis method and the application of the novel sulfonated aryl ether compounds and intermediates thereof. The present invention provides the sulfonated aryl ether compounds whose structure is disclosed in (I); the synthesis method of the present invention comprises the following steps: 1, 1-dichloro-diphenyl methane, 2, 6-dimethylphenol and phenol are synthesized into a bisphenol monomer whose structure is disclosed in (I); in a polar aprotic solvent, the prepared bisphenol monomer, a bisphenol monomer HO-B-OH and difluoro monomer F-Ar-F anhydrous potassium carbonate are mixed to react to prepare aryl ether compounds whose structure is disclosed in (III); the aryl ether compounds are sulfonated by chlorosulfonic acid to obtain novel sulfonated aryl ether compounds whose structure is disclosed in (I). The comprehensive performance of the membrane materials which are prepared by the novel sulfonated aryl ether compounds is good, and the novel sulfonated aryl ether compounds can be used for proton exchange membrane materials for fuel batteries.

Description

Sulfonated polyether compound and synthetic and application thereof
The application is to be on October 24th, 2003 applying date, and application number is dividing an application of 200310111886.9 application for a patent for invention " sulfonated polyether compound and intermediate thereof and they synthetic and use ".
Technical field the invention belongs to fuel cell field, and especially proton exchange membrane material relates to a series of novel sulfonated polyether compounds and intermediate thereof and their synthetic and application.
The technical background fuel cell has effciency of energy transfer height (40-60%), environmental friendliness, and cleaning, pollution-free, the advantage that noiselessness etc. are outstanding is considered to the cleaning of 21 century first-selection, the energy efficiently.Proton Exchange Membrane Fuel Cells (PEMFC) be called as the 5th generation fuel cell, it starts but also have room temperature fast except possessing the advantage part of general fuel cell, no electrolyte loss, water is easily discharged, the life-span is long, outstanding features such as specific power and specific energy height.Proton exchange membrane is one of critical material of PEMFC, and the performance of proton exchange membrane is directly connected to whole fuel cell overall performance.General in the world proton exchange membrane is a perfluorinated sulfonic acid type proton exchange membrane at present, and wherein the most representative is the Nafion series perfluorinated sulfonic acid type proton exchange membrane that du pont company is produced, and the chemical structural formula of this macromolecular material is as follows:
Figure C20051006753100041
X=6-10 wherein; Y, z=1
This perfluorinated sulfonic acid type proton exchange membrane has the good proton performance of leading, and its proton conductivity can reach 10 under aqueous conditions -2-10 -1Scm -1, and have good thermostability and chemical stability, it can be under the environment of the Proton Exchange Membrane Fuel Cells under 80 ℃ (PEMFC) non-stop run up to ten thousand hours, also have good mechanical property simultaneously.But perfluorinated sulfonic acid type proton exchange membrane can sharply descend by its proton conductivity because moisture content runs off in a large number when temperature is higher than 100 ℃, thereby influences the high-temperature behavior of PEMFC.Its cost exceeds market requirement standard far away than higher in addition.At present the price of Nafion series proton exchange membrane be the 600-800 dollar/square metre.Market survey shows, if PEMFC will obtain business-like application on electromobile, wherein the cost of proton exchange membrane material must be controlled at the 50-150 dollar/square metre.So researching and developing cheaply proton exchange membrane has become the PEM fuel cell and has moved towards business-like key.Because fluorine-containing raw-material price is generally than higher, groundwork concentrates on the proton exchange membrane of development research free-floride and half fluorine.Wherein Canadian Ba Lade utility companies (BAM) has been developed BAM1G, BAM2G, and the BAM3G three generations is proton exchange membrane cheaply, and has obtained certain progress.But the leading performances such as proton and all can not compare of present free-floride and half fluorine proton exchange membrane with full fluorin proton exchange film.So the research and development of the proton exchange membrane of low-cost and high-performance have become the development that influences PEMFC, move towards one of commercialization gordian technique.
Summary of the invention the object of the present invention is to provide intermediate of preparation sulfonated polyether compound and preparation method thereof.
Another object of the present invention provides a series of sulfonated polyether compounds, and this sulfonated polyether compound is with low cost, and has good performance.
A further object of the present invention provides the product yield height, the synthetic method of this series sulfonated polyether compound that process is simple and economic.
Also purpose of the present invention provides the application of battery with proton exchange membrane material that act as a fuel of this compound.
The invention provides the following biphenol monomer of structure:
Figure C20051006753100051
The synthetic method of this biphenol monomer is with 1,1-dichloro diphenyl methane, 2, and 6-xylenol and phenol are by after 10: 21～30: 0.5～1.5 the mixed in molar ratio, at N 2Being stirred under the protection does not have gas to emit, and is warmed up to 50～60 ℃ and stirs 4～6 hours, slowly is warmed up to 120～160 ℃ then, reacts 30～50 minutes, again through separation, curing, purifying, gets lurid solid.
The invention provides the following polyether compound of structure:
Figure C20051006753100052
Wherein n is 40～140, preferred 80～120;
Be selected from
Preferably:
Be selected from:
Preferably:
Figure C20051006753100066
In the formula, m is 4～10.
The synthetic method of this polyether compound is in polar aprotic solvent, with above-mentioned biphenol monomer that makes and biphenol monomer
Figure C20051006753100067
Two fluorine monomers
Figure C20051006753100068
Anhydrous potassium carbonate is pressed 10: 0～20: 10～30: 15～45 mixed in molar ratio; and in the monomeric ratio adding of 4～8 milliliters of toluene/gram difluoro toluene; under the nitrogen protection, be warmed up to 135～145 ℃ (optimum temps is 140 ℃), stir reaction down 3～4 hours; steam toluene wherein; take the water of generation out of, be warmed up to 160～180 ℃ (optimum temps is 170 ℃) then, reacted 2～6 hours; the separated and collected product gets white cotton-shaped solid then.
Wherein polar aprotic solvent can be selected from N,N-dimethylacetamide (DMAC), N, dinethylformamide (DMF), 1-Methyl-2-Pyrrolidone (NMP) etc.
The invention provides the following sulfonated polyether compound of structure:
Figure C20051006753100071
Wherein n is 40～140;
Figure C20051006753100072
Be selected from
Figure C20051006753100073
Preferably:
Be selected from:
Figure C20051006753100076
Preferably:
In the formula, m is 4～10.
The synthetic method of this sulfonated polyether compound is that the above-mentioned polyether compound that makes is dissolved in the polar solvent, drip again with polar solvent dissolved chlorsulfonic acid, wherein the mol ratio of polyether compound and chlorsulfonic acid is 1: 6～10 (the best is 1: 7～8), stirring reaction 4～6 hours, the separated and collected product.
Wherein polar solvent comprises methylene dichloride, trichloromethane, 1,2-ethylene dichloride etc.
This sulfonated polyether compound can be used as the ionic exchange film for fuel cell material.
Process of the present invention is: (1) synthesizes a kind of novel biphenol monomer; (2) based on this biphenol monomer by copolymerization with all aggregated into a series of polyether compounds; (3) amount of control chlorsulfonic acid is to carrying out the polyether compound sulfonation.Outstanding advantages such as the mould material that this series sulfonated polyether compound is made has that cost is low, stability height, good water absorption, proton exchange capacity are big are the potential substitute of present fuel cell with expensive Nafion film.
The synthetic route of sulfonated polyether compound provided by the invention is as follows:
(1) biphenol monomer is synthetic
Figure C20051006753100082
(2) polyether compound is synthetic
Figure C20051006753100083
Be selected from
Figure C20051006753100093
Be selected from
Figure C20051006753100094
(3) polyether compound sulfonation
Figure C20051006753100095
The present invention has synthesized a series of polyarylether of sulfonic acid type cheaply proton exchange membrane from the angle of molecular designing.This series is from the synthetic a kind of novel biphenol monomer of simple industrial chemicals, copolymerization or homopolymerization take place with other bis-phenol and different activation dihalo-monomer in this monomer again under polar aprotic solvent, reaction total time is 5-10 hour, the polyarylether family macromolecule material of synthetic a series of excellent combination property.Handle (polymkeric substance: chlorsulfonic acid=1: 6-10, the best is 1: 7～8) through the chlorsulfonic acid sulfonation, introduce the proton exchange membrane that the sulfonic group of leading proton makes a series of novel high performance free-florides.This proton exchange film conductivity is 10 -4～10 1S/cm, water-absorbent 10%～90% has following characteristics:
1. the raw material that is adopted is a common chemical raw materials, and is cheap and easy to get, simple by the conventional synthetic route of synthetic polyarylether, at first solved the cost problem of material.
2. polyarylether resin has excellent chemical physics performance and mechanical property such as high temperature resistant, creep resistance, high strength, obdurability, is widely used at aspects such as polymeric membrane, aerospace and electronic industries.This invention synthetic macromolecular material polyarylether skeleton can satisfy PEMFC to the physical chemistry of proton exchange membrane and the requirement of mechanical property.
3. this invention is protected introducing substituting group on the phenyl ring on the macromolecular scaffold from molecular level, makes and only introduce the sulfonate functional base on side-chain benzene ring, thereby guarantee the chemical stability of high polymer main chain, and can not influence its excellent physical and mechanical performance.And traditional sulfonated polyether resin only carries out simple sulfonation processing, after phenyl ring is sulfonated on the macromolecular scaffold, ehter bond on the high polymer main chain is owing to sulfonic existence on the phenyl ring becomes unstable, it is unstable that made polymeric membrane becomes under the PEMFC Working environment, easily cracking has a strong impact on life-span of proton exchange membrane.
4. owing to having on two phenyl ring, institute synthetic polymer unit can introduce the sulfonate functional base, so its equivalent weight (EW, film weight mg/ sulfonic acid base unit weight meq) lower, between 300-600, suitable with the BAM3G third generation proton exchange membrane of Canadian Ba Lade company.The water-intake rate of equivalent weight and resin and to lead the proton performance closely related.The equivalent weight of institute's synthetic macromolecular material can be regulated by the consumption and the sulfonation condition of regulating sulphonating agent.Make it to have higher water-intake rate and higher proton conductivity.
Embodiment:
Embodiment
(1) biphenol monomer is synthetic:
2.37g (0.01mol) raw material 1 (1, the 1-dichloro diphenyl methane) and 2.44g (0.022mol) raw material 2 (2, the 6-xylenol) are added in the there-necked flask of a 100ml, and add the phenol (0.2g) of trace, N 2Protection stirring at normal temperature down is warmed up to 55 ℃ and stirred 4 hours to there not being gas to emit, and slowly is warmed up to 150 ℃ then, keeps 30 minutes, extracts lower boiling impurity out with vacuum pump, and cool to room temperature solidifies.Use dehydrated alcohol: sherwood oil (volume ratio)=3: 1 recrystallizations twice, get lurid solid, be biphenol monomer 3.
(2) polyether compound is synthetic:
With biphenol monomer 3; two fluorine monomers 4; biphenol monomer 5; Anhydrous potassium carbonate; toluene and polar solvent add in the there-necked flask, under the nitrogen protection; be warmed up to 135-145 ℃, optimum temps is 140 ℃, keeps 3-4 hour under the magnetic agitation; steam toluene wherein, take the water of generation out of, be warmed up to 160-180 ℃ then; optimum temps is 170 ℃; reacted 2-6 hour, and, it was splashed in the methyl alcohol that adds small amount of hydrochloric acid with solvent DMAC dilution; filter; drying with the chloroform dissolving, was placed 5-8 hour; filter; concentrate, splash in the methyl alcohol, filter; drying gets white cotton-shaped solid.Reaction conditions and productive rate see Table 1:
(3) sulfonation of polyether compound:
To add in the flask of 100mL through (2) synthetic polyether compound, add solvent and make its dissolving, dropwise splash into chlorosulfonic acid solution, stirring reaction 5 hours, there is brown precipitate to generate, inclining solvent, with 5mL normal hexane washed twice, adds 5mL methyl-sulphoxide (DMSO), stir and made its dissolving in 1-2 hour, add the sodium hydroxide solution of 10mL3wt%, stirred 6 hours, residual chlorsulfonic acid neutralizes; And then the aqueous hydrochloric acid of adding 100mL5vt%, react more than 5 hours dialysis, evaporate to dryness.Reaction conditions sees Table 1.
(4) sulfonated polyether compound is dissolved in DMSO, does film.
Table 1: reaction (2), (3) step reaction conditions and productive rate etc.
Embodiment Step (2) raw material and consumption (mmol) Step (2) solvent and consumption (ml) Step (2) temperature of reaction (℃) Polyether compound productive rate (%) Step (3) sulfonation condition
Biphenol monomer (3) Biphenol monomer (5) Two fluorine monomers (4) Solvent Polyether compound/chlorsulfonic acid mol ratio
1 1mmol - 4-a，1mmol 2.1ml DMAC 170 89.92 Methylene dichloride 1∶8
2 1mmol - 4-b，1mmol 2.4ml DMAC 180 95.10 Trichloromethane 1∶6
3 1mmol - 4-d，1mmol 2.4ml DMF 175 90.03 Methylene dichloride 1∶10
4 1mmol - 4-g，1mmol 2.4ml NMP 170 89.26 1, the 2-ethylene dichloride 1∶7
5 1mmol - 4-k，1mmol 2.5ml DMAC 165 92.45 Trichloromethane 1∶7.5
6 0.5mmol 5-IV，0.5mmol 4-d，1mmol 2.3ml DMAC 160 75.25 Methylene dichloride 1∶10
7 0.5mmol 5-I，0.5mmol 4-f，1mmol 2.1ml DMAC 170 87.64 Trichloromethane 1∶9
8 0.6mmol 5-III，0.4mmol 4-e，1mmol 2.0ml DMAC 175 84.37 Methylene dichloride 1∶8
9 0.8mmol 5-IV，0.2mmol 4-c，1mmol 2.3ml DMAC 160 79.83 1, the 2-ethylene dichloride 1∶8

Claims (3)

1. the synthetic method of a sulfonated polyether compound, be that polyether compound is dissolved in the polar solvent, drip again with polar solvent dissolved chlorsulfonic acid, described polar solvent is methylene dichloride, trichloromethane or 1, the 2-ethylene dichloride, wherein the mol ratio of polyether compound and chlorsulfonic acid is 1: 6～10, stirring reaction 4～6 hours, separated and collected product; Wherein the polyether compound structure is
Or
Figure C2005100675310002C2
N is 40～140 in the formula,
Figure C2005100675310002C3
Be selected from
Figure C2005100675310002C4
Figure C2005100675310002C5
Be selected from:
Figure C2005100675310002C6
In the formula, m is 4～10.
2. the process of claim 1 wherein
Figure C2005100675310002C7
Be selected from
Figure C2005100675310003C1
Figure C2005100675310003C2
Be selected from
In the formula, m is 4～10.
3. claim 1 or 2 synthetic method, wherein the mol ratio of polyether compound and chlorsulfonic acid is 1: 7～8.
CNB2005100675313A 2003-10-24 2003-10-24 Sulfonated polyether compound, its synthesis and use thereof Expired - Fee Related CN1282686C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438696A (en) * 2018-11-07 2019-03-08 沈阳化工大学 A kind of sulfonation structure containing anthrone polyarylether and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101240063B (en) * 2008-01-18 2011-12-21 深圳大学 Sulfonated polyarylether with sulfonic group at side chain naphthalene ring and preparation method thereof
CN101381455B (en) * 2008-10-08 2011-04-06 吉林大学 Side base sulfonic acid type polyarylether material, and preparation method and application thereof
CN101434697B (en) * 2008-12-15 2010-08-11 吉林大学 Side chain type sulphonation polyarylether ketone based on naphthalene ring and preparation thereof
CN109546192B (en) * 2018-11-15 2021-10-15 先进储能材料国家工程研究中心有限责任公司 Hyperbranched sulfonated polyarylether doped composite proton exchange membrane and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438696A (en) * 2018-11-07 2019-03-08 沈阳化工大学 A kind of sulfonation structure containing anthrone polyarylether and preparation method thereof

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