CN1148338C - Fluorine-containing trifluorostyrene monomer and its synthesis and use - Google Patents

Fluorine-containing trifluorostyrene monomer and its synthesis and use Download PDF

Info

Publication number
CN1148338C
CN1148338C CNB011320990A CN01132099A CN1148338C CN 1148338 C CN1148338 C CN 1148338C CN B011320990 A CNB011320990 A CN B011320990A CN 01132099 A CN01132099 A CN 01132099A CN 1148338 C CN1148338 C CN 1148338C
Authority
CN
China
Prior art keywords
reaction
fluorine
fluoroalkyl benzene
proton exchange
fluoroalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB011320990A
Other languages
Chinese (zh)
Other versions
CN1349962A (en
Inventor
龙 吕
吕龙
胡里清
张卫星
王毅
李伟
何妍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Organic Chemistry of CAS
Original Assignee
Shanghai Institute of Organic Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Organic Chemistry of CAS filed Critical Shanghai Institute of Organic Chemistry of CAS
Priority to CNB011320990A priority Critical patent/CN1148338C/en
Publication of CN1349962A publication Critical patent/CN1349962A/en
Application granted granted Critical
Publication of CN1148338C publication Critical patent/CN1148338C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • 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
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Fuel Cell (AREA)

Abstract

The present invention relates to a fluorine-comprising trifluoro phenylethylene monomer, a synthesis method thereof and an application thereof. In the synthesis method of the fluorine-comprising trifluoro phenylethylene monomer, an easily obtained compound with a fluorine-comprising base group is used as a raw material, and after the processes of the nitration, the diazotization and the iodination of the compound are carried out, the easily obtained compound with a fluorine-comprising base group is coupled to trifluoro vinyl bromide. The fluorine-comprising trifluoro phenylethylene monomer can prepare proton exchange resin by copolymerization with phenylethylene and trifluoro phenylethylene or fluorine-comprising trifluoro phenylethylene derivatives, etc. and sulfonation, and the resin can be used for preparing a proton exchange film for a proton exchange film fuel cell. The constitutional formula of the fluorine-comprising trifluoro phenylethylene monomer is disclosed in the specification, wherein R<f>=C<m>F<2m+1> or (CF2CF2)<n>OCF2CF2SO2F, m=2, 3, 4, 5 or 6, and n=1, 2, 3 or 4.

Description

Fluorine-containing trifluorostyrene monomer, preparation method and use
Technical field
The present invention relates to a kind of novel fluorine-containing trifluorostyrene monomer, and this monomeric preparation method and use.
Background technology
In recent decades, coal-fired thermal power generation discharged flue gas and fuel-engined vehicle tail gas have become worldwide environmental problem to the pollution that atmosphere causes, research energy source optimization utilization and clear energy sources exploitation are the important component parts of the 21 century energy and environment strategy of sustainable development, also are the bases of 21 century development of world economy.
Hydrogen Energy has cleaning and inexhaustible advantage and is called as the main flow energy of 21 century.Proton Exchange Membrane Fuel Cells is the splendid device that utilizes hydrogen power generation.It has that service temperature is low, startup is fast, simple in structure, performance is good, the life-span is long and series of advantages such as non-corrosiveness thereby at small-sized portable power source, and huge potential application foreground is particularly arranged in power truck, is the focus of fuel cell studies.The power truck of external expectation Proton Exchange Membrane Fuel Cells will be in commercialization in 2008.
Proton exchange membrane is one of core of Proton Exchange Membrane Fuel Cells.That mainly adopt in the world at present is succeeded in developing in 1966 and the business-like Nafion of du pont company The series full fluorin proton exchange film (U.S.Patent:3,282,875[1966]).The full fluorin proton exchange film of Shi Yonging has the Flemion of Japan AGC company development in addition The Aciplex of film and the development of company of Japanese Asahi Chemical Industry Film.More than three kinds of full fluorin proton exchange films all be to make by the perfluor proton exchange resins that contain different long function side chains.This type of perfluor proton exchange resins monomer whose is synthetic complicated, and cost is very high.Dow chemical company is developed into the Dow that contains shorter function side chain at the beginning of the eighties Full fluorin proton exchange film (U.S.Patent:4,358,412[1982]).Though its performance compares Nafion , Flemion And Aciplex Film is good, but its resin monomer is synthetic more complicated, and cost is higher, and too late long side chain film of life-span, and this limits its application prospect.
The perfluor proton exchange resins is all synthetic complicated because of monomer whose, although its performance is pretty good, cost is too high and limit its application on fuel cell, reaches 800US$/cm as the price of Nafion 115 2, it accounts for 1/3rd of Proton Exchange Membrane Fuel Cells cost.Therefore many companies and research unit are arranged at present in development of new monomer and synthetic method thereof in the world, and by the application of proton exchange membrane in fuel cell of the resins of this class monomer polymerization.Canada Ballard company is developed into the fluorine-containing proton exchange resins of part and makes proton exchange membrane thus, the resin main component be trifluorostyrene and its derivative multipolymer (U.S.P.5,422,411[1995]; 5,498,639[1996]; 5,602,185[1997]; 5,684,192[1997]; 5,773,480[1998]).Its advantage of proton exchange membrane of making of resinoid is to have higher sulfonation degree and water-content thus, be assembled into fuel cell test and show its better performances, but physical strength that it is relatively poor and film embrittlement when dehydration all limits its long-time use, the most important thing is that the synthetic cost of its resin monomer is still very high.
Research suitable monomers and synthetic method are to reduce an effective way of Proton Exchange Membrane Fuel Cells cost.
Goal of the invention
The purpose of this invention is to provide a kind of novel fluorine-containing trifluorostyrene monomer.
Another object of the present invention provides a kind of fluorine-containing raw material IR from simply being easy to get fWith iodobenzene set out simple, the easy synthetic method of row of synthetic fluorine-containing trifluorostyrene monomer.R wherein f=C mF 2m+1Or (CF 2CF 2) nOCF 2CF 2SO 2F, m=1,2,3,4,5 or 6, n=1,2,3 or 4.
Purpose of the present invention also provides a kind of purposes of above-mentioned fluorine-containing trifluorostyrene monomer, it can make proton exchange resins with vinylbenzene, trifluorostyrene or the copolymerization of fluorine-containing trifluorostyrene derivative and sulfonation, and this resin can be used for the low but used in proton exchange membrane fuel cell proton exchange membrane of excellent property of preparation cost.
Summary of the invention
The present invention is a kind of novel fluorine-containing trifluorostyrene monomer, and its structural formula is as follows:
R wherein f=C mF 2m+1Or (CF 2CF 2) nOCF 2CF 2SO 2F, m=2,3,4,5 or 6, n=1,2,3 or 4.
The monomeric building-up reactions formula of trifluorostyrene of the present invention can be exemplified below:
Figure C0113209900052
Figure C0113209900061
Linked reaction is at first trifluoro bromine conversion of ethylene to be become trifluoro bromo vinyl zincon, then under the catalysis of Primary Catalysts and promotor and-I-PhR fReaction obtains the trifluorostyrene monomer that corresponding fluoroalkyl replaces.Its process is as follows:
The synthetic novel fluorine-containing trifluorostyrene monomer that contains different substituents of the present invention, its structural formula is as follows:
Different substituent R fList in table 1.
Table 1
Numbering Rf
1-1 Between-C 2F 5
1-2 Between-C 3F 7
1-3 Between-C 4F 9
1-4 Between-C 5F 11
1-5 Between-C 6F 13
1-6 Between-CF 2CF 2OCF 2CF 2SO 2F
1-7 Between-(CF 2CF 2) 2OCF 2CF 2SO 2F
1-8 Between-(CF 2CF 2) 3OCF 2CF 2SO 2F
1-9 Between-(CF 2CF 2) 4OCF 2CF 2SO 2F
The present invention also provides a kind of method of synthesizing above fluorochemical monomer simple and effectively.From the fluorine-containing raw material IR that simply is easy to get fSet out with iodobenzene, in organic solvent and under the effect of copper powder, reaction obtains corresponding fluoroalkyl benzene.Iodobenzene, IR fWith the mol ratio of copper powder be 1.0: 0.8～1.5: 1.5～4.0, temperature of reaction is 60～120 ℃, reaction times is 15～40 hours, organic solvent used in the reaction can be N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) and N-Methyl pyrrolidone (DMP) etc.Above-mentioned R f=C mF 2m+1Or (CF 2CF 2) nOCF 2CF 2SO 2F, m=1,2,3,4,5 or 6, n=1,2,3 or 4.
Above-mentioned fluoroalkyl benzene is through the mixed acid nitrification of the nitrosonitric acid and the vitriol oil, obtain corresponding between the nitro fluoroalkyl benzene.Fluoroalkyl benzene, HNO 3And H 2SO 4Mol ratio be 1.0: 1.5～2.0: 1.5～2.0.The nitration reaction temperature is 30～60 ℃; Reaction times is 15～40 hours.
Between the nitro fluoroalkyl benzene at SnCl 22H 2Diazotization under the effect of O and dense HCl, obtain corresponding between amino fluoroalkyl benzene.Between nitro fluoroalkyl benzene, SnCl 22H 2The mol ratio of O and dense HCl is 1.0: 4.0～6.0: 8.0～12.0, and temperature of reaction is 30～80 ℃, and the reaction times is 0.5～2.0 hour.
Between amino fluoroalkyl benzene earlier and saturated NaNO 2Diazotization reaction takes place in solution and dense HCl, generates the diazonium chloride m-fluoroalkyl benzene, an amino fluoroalkyl benzene, NaNO 2With the mol ratio of HCl be 1.0: 1.0～1.3: 1.0～1.3, temperature of reaction is-5～5 ℃, the reaction times is 1.0～5.0 hours.
Iodination reaction takes place in diazonium chloride m-fluoroalkyl benzene and KI, between generation-and I-PhR f, the mol ratio of diazonium chloride m-fluoroalkyl benzene and KI is 1.0: 1.0～1.3, and temperature of reaction is 45～75 ℃, and the reaction times is 0.5～2.0 hour.Above-mentioned R f=C mF 2m+1Or (CF 2CF 2) nOCF 2CF 2SO 2F, m=1,2,3,4,5 or 6, n=1,2,3 or 4.
Between the iodo fluoroalkyl benzene under the effect under Primary Catalysts and the promotor with CF 2Linked reaction takes place in=CFZnBr.Between iodo fluoroalkyl benzene CF 2The mol ratio of=CFZnBr/ Primary Catalysts and promotor is 1.0: 1.0～1.3: 0.004～0.006: 0.012～0.05, and temperature of reaction is 40～70 ℃, and the reaction times is 5～20 hours.Wherein Primary Catalysts and promotor can be Pd (dba) 3/ Ph 3P, Pd (OAc) 2/ Ph 3P, PdCl 2/ Ph 3P, Pd (dba) 3/ POPh 3, Pd (OAc) 2/ POPh 3And PdCl 2/ POPh 3Deng, wherein dba=two inferior Bian benzylacetone bases, OAc=acetoxy group.The mol ratio of Primary Catalysts and promotor is 1: 3～10.
Novel fluorine-containing trifluorostyrene monomer of the present invention can be prepared into proton exchange resins with other styrenic fluorine-containing derivant copolymerization and sulfonation.The performance performance in fuel cell of the used in proton exchange membrane fuel cell proton exchange membrane of resins is good thus, and with low cost.
Description of drawings
Accompanying drawing 1 is the polarization curve of the monocell of single film assembling, and accompanying drawing 2 is polarization curves of the monocell of composite membrane assembling.Polarization curve can illustrate the chemical property of this type of resin.The ordinate zou of polarization curve is the voltage of monocell, and unit is a volt (V); X-coordinate is the current density of monocell, and unit is every square centimeter of (A/cm of ampere 2).The test condition of monocell is: battery temperature=75 ℃; Hydrogen inlet pressure=0.10MPa, gas inlet pressure=0.12MPa.
Specific implementation method
Following embodiment will the present invention is described in further detail, but the invention is not restricted to these specific exampless.Embodiment 1-14 has described R respectively f=C 6F 13, C 2F 5, (CF 2CF 2) 3OCF 2CF 2SO 2F or CF 2CF 2OCF 2CF 2SO 2The monomeric preparation process of F; Example 15-16 has described trifluorostyrene (TFS) ,-CF 3-TFS and-(CF 2CF 2) 3OCF 2CF 2SO 2F-PyCF=CF 2Binary polymerization and the sulfonation of resin; Example 17-18 has described the preparation process of fuel cell with single film and composite membrane; Example 19 has been described three-in-one electrode preparation and the test of fuel cell with single film and composite membrane.
Embodiment 1 PhC 6F 13Synthetic
In the three-necked bottle of 1L, logical nitrogen 1 hour.Add 1.1kgDMF under the mechanical stirring, 269g copper powder, 468g IC 6F 13, 214g C 6H 5I, 120 ℃ of reflux stirred 24 hours.Filtering reacting liquid, extracted with diethyl ether residual solids, merging filtrate.Take out DMF and other assorted liquid with the water pump decompression under 50 ℃.Collect product about 100 ℃, output 277g, productive rate 65%, purity 97.5%.
2-NO of embodiment 2-PhC 6F 13Synthetic
In the three-necked bottle of 1L, add 66.2g PhC 6F 13, ice-water bath adds the nitration mixture of the vitriol oil of the nitrosonitric acid of 10～15ml and 25～30ml under the mechanical stirring.Control reaction temperature is at 45～55 ℃.After reaction in second day finishes, reaction solution is poured in the frozen water, the extracted with diethyl ether organic layer is used NaHCO 3Solution is washed till neutrality, uses anhydrous MgSO again 4Drying, decompression at last steams product, output 64.5g, productive rate 87%.
3-NH of embodiment 2-PhC 6F 13Synthetic
In the three-necked bottle of 250ml, add 25～30g SnCl 22H 2The dense HCl of O and 20～30ml added in 15 minutes between 12.5g-NO 2-PhC 6F 13, 70 ℃ were reacted 1 hour down, then cool overnight.Filtering reacting liquid, filtrate neutralizes with NaOH or KOH solution, extracted with diethyl ether, decompression steams product, output 9.7g, productive rate 84%.
4-I-PhC of embodiment 6F 13Synthetic
Between adding 9.7 restrains in the three-necked bottle of 500ml-NH 2-PhC 6F 13With the dense HCl salify of 7ml, splash into 2g NaNO under the ice bath cooling mechanical stirring 2Saturated solution adds 4.6g KI saturated solution, vigorous stirring 1 hour after half an hour.Add ether and tell organic layer, use NaHCO 3The solution neutralization, dry back underpressure distillation goes out product, output 8.0, productive rate 93%.
5-C of embodiment 6F 13-PhCF=CF 2Synthetic
Logical nitrogen is 30 minutes in the reaction flask of 250mL, adds 56ml DMF then, continues logical nitrogen 30 minutes, under agitation adds 17.5g CF 2=CFZnBr, 0.23g Ph 3P and 0.15g Pd 2(dba) 3, be stirred and heated to 55 ℃, between adding 5.3g-I-PhC 6F 13, stirring is spent the night.Decompression steams monomer and part DMF, and the frozen water that adds equivalent shakes up layering to steaming liquid.Layer oily matter is the TFS monomer.Again between decompression steams-C 6F 13-PhCF=CF monomer, output 2.9g, productive rate 60%.
6-C of embodiment 6F 13-PhCF=CF 2Synthetic
Process and reaction conditions are all as embodiment 5.With PdCl 2/ POPh 3Replace Pd (dba) 3/ Ph 3Between P makes-C 6F 13-PhCF=CF 2, productive rate 45%.
7-C of embodiment 2F 5-PhCF=CF 2Synthetic
Process and reaction conditions are respectively as embodiment 1～5.Among the embodiment 1 with IC 2F 5Replace IC 6F 13Make PhC 2F 5, productive rate is 60%; Among the embodiment 2 with PhC 2F 5Replace PhC 6F 13Between making-NO 2-PhC 2F 5, productive rate is 86%; As among the embodiment 3 with-NO 2-PhC 2F 5Between replacement-NO 2-PhC 2F 5Between making-NH 2-PhC 2F 5, productive rate is 79%; Among the embodiment 4 with-NH 2-PhC 2F 5Between replacement-NH 2-PhC 6F 13Between making-I-PhC 2F 5, productive rate is 90%; Among the embodiment 5 with-I-PhC 2F 5Between replacement-I-PhC 6F 13, between making at last-C 2F 5-PhCF=CF 2, productive rate 65%.
Embodiment 8 Ph (CF 2CF 2) 3OCF 2CF 2SO 2F's is synthetic
In the three-necked bottle of 1L, logical nitrogen 1 hour.Add 1.5kg DMF, 384g copper powder, 939g I (CF under the mechanical stirring 2CF 2) 3OCF 2CF 2SO 2F, 306g C 6H 5I, 120 ℃ of reflux stirred 24 hours.Filtering reacting liquid, extracted with diethyl ether residual solids, merging filtrate.Take out DMF and other assorted liquid with the water pump decompression under 50 ℃.Collect product about 100 ℃, output 626g, productive rate 72%, purity 98%.
9-NO of embodiment 2-Ph (CF 2CF 2) 3OCF 2CF 2SO 2F's is synthetic
In the three-necked bottle of 1L, add 137.6g Ph (CF 2CF 2) 3OCF 2CF 2SO 2F, ice-water bath, the nitration mixture of the vitriol oil of the nitrosonitric acid of adding 19ml and 40ml under the mechanical stirring.Control reaction temperature is at 45 ℃.After reaction in second day finishes, reaction solution is poured in the frozen water, the extracted with diethyl ether organic layer is used NaHCO 3Solution is washed till neutrality, uses anhydrous MgSO again 4Drying, decompression at last steams product, output 134g, productive rate 90%.
10-NH of embodiment 2-Ph (CF 2CF 2) 3OCF 2CF 2SO 2F's is synthetic
In the three-necked bottle of 250ml, add 41g SnCl 22H 2The dense HCl of O and 37ml added in 15 minutes between 25g-NO 2-Ph (CF 2CF 2) 3OCF 2CF 2SO 2F, 70 ℃ were reacted 1 hour down, then cool overnight.Filtering reacting liquid, filtrate neutralizes with NaOH solution, extracted with diethyl ether, decompression steams product, output 19.8g, productive rate 84%.
11-I-Ph of embodiment (CF 2CF 2) 3OCF 2CF 2SO 2F's is synthetic
Between adding 19.8 restrains in the three-necked bottle of 500ml-NH 2-Ph (CF 2CF 2) 3OCF 2CF 2SO 2The dense HCl salify of F and 10ml splashes into 3g NaNO under the ice bath cooling mechanical stirring 2Saturated solution adds 6.6gKI saturated solution, vigorous stirring 1 hour after half an hour.Add ether and tell organic layer, use NaHCO 3The solution neutralization, dry back underpressure distillation goes out product, output 13g, productive rate 55%.
12-(CF of embodiment 2CF 2) 3OCF 2CF 2SO 2F-PhCF=CF 2Synthetic
Logical nitrogen is 30 minutes in the reaction flask of 250mL, adds 80ml DMF then, continues logical nitrogen 30 minutes, under agitation adds 25g CF 2=CFZnBr, 0.32g Ph 3P and 0.22g Pd 2(dba) 3, be stirred and heated to 55 ℃, between adding 10g-I-Ph (CF 2CF 2) 3OCF 2CF 2SO 2F, stirring is spent the night.Decompression steams monomer and part DMF, and the frozen water that adds equivalent shakes up layering to steaming liquid.Layer oily matter is the TFS monomer.Again between decompression steams-(CF 2CF 2) 3OCF 2CF 2SO 2The F-PhCF=CF monomer, output 4.2g, productive rate 45%.
13-(CF of embodiment 2CF 2) 3OCF 2CF 2SO 2F-PhCF=CF 2Synthetic
Process and reaction conditions are all as embodiment 12.With PdCl 2/ POPh 3Replace Pd (dba) 3/ Ph 3Between P makes-(CF 2CF 2) 3OCF 2CF 2SO 2F-PhCF=CF 2, productive rate 30%.
14-CF of embodiment 2CF 2OCF 2CF 2SO 2F-PhCF=CF 2Synthetic
Process and reaction conditions are respectively as embodiment 8～12.Among the embodiment 8 with ICF 2CF 2OCF 2CF 2SO 2F replaces I (CF 2CF 2) 3OCF 2CF 2SO 2F makes PhCF 2CF 2OCF 2CF 2SO 2F, productive rate are 69%; Among the embodiment 9 with PhCF 2CF 2OCF 2CF 2SO 2F replaces Ph (CF 2CF 2) 3OCF 2CF 2SO 2Between F makes-NO 2-PhCF 2CF 2OCF 2CF 2SO 2F, productive rate are 91%; Among the embodiment 10 with-NO 2-PhCF 2CF 2OCF 2CF 2SO 2Between F replaces-NO 2-Ph (CF 2CF 2) 3OCF 2CF 2SO 2Between F makes-NO 2-PhCF 2CF 2OCF 2CF 2SO 2F, productive rate are 88%; Among the embodiment 11 with-NH 2-PhCF 2CF 2OCF 2CF 2SO 2Between F replaces-NH 2-Ph (CF 2CF 2) 3OCF 2CF 2SO 2Between F makes-I-PhCF 2CF 2OCF 2CF 2SO 2F, productive rate are 60%; Among the embodiment 12 with-I-PhCF 2CF 2OCF 2CF 2SO 2Between between F replaces-I-Ph (CF 2CF 2) 3OCF 2CF 2SO 2F, between making at last-CF 2CF 2OCF 2CF 2SO 2F-PhCF=CF 2, productive rate 40%.
The polyreaction of embodiment 15 termonomer
The logical nitrogen of 3L there-necked flask 30 minutes adds 1050ml water and 19g n-C then 12H 25NH 2The Cl emulsifying agent continued logical nitrogen 1 hour; Be heated to 50 ℃, the constant temperature induction stirring; Take by weighing 119g TFS (trifluorostyrene) in proportion, 43g m-CF 3-TFS and a spot of m-(CF 2CF 2) 3OCF 2CF 2SO 2F-PhCF=CF 2(ratio of ternary system can be regulated) adds in the flask, adds the 1.45g initiator potassium persulfate at last, reacts 72 hours; Product after the polymerization is poured in the sodium hydroxide solution, and mechanical stirring is carried out breakdown of emulsion, approximately needs 10～15 minutes; The B filtering solution is washed till neutrality with distilled water with product earlier, uses residual water of washed with methanol and low molecular weight substance then, drains; 60 ℃ of bakings of vacuum drying oven 24 hours get final product.Polymerization yield rate is more than 90%.Limiting viscosity is 1.226.
The sulfonation of embodiment 16 polymkeric substance
At first the polymkeric substance that 75g embodiment 15 is made is dissolved in the 660ml methylene dichloride, joins stirring and dissolving in the sulfonation reactor; Under vigorous stirring, add 49g triethyl phosphate, the mixing solutions of 43.7ml sulphur trioxide and 110ml methylene dichloride; Added in about 5 minutes, reflux is 1 hour then; Filter,, wash to neutral with the deionization frozen water at last with the washing of 500ml chloroform; The sulfonated products kept dry, the sulfonation productive rate is greater than 90%.The resin sulfonation degree is 2.4mmolHSO 4 +/ g (resin), water ratio are 70%.
Embodiment 17 casting method prepare single film
The sulfonation degree that embodiment 16 is made is 2.2～2.4mmolHSO 4 +The novel proton exchange resins of/g (resin) is made into 20% DMF solution, and with this solution curtain coating on the casting film-forming platform, temperature is controlled at 50 ℃.After equal solvent is evaporated completely, water spray, skinning.About 30～50 microns of film thickness.
Embodiment 18 decompression completion methods prepare composite membrane
Sheng concentration is 5% novel proton exchange resins methanol solution in a sealed vessel, and resin is made by embodiment 16, and sulfonation degree is 2.2～2.4mmolHSO 4 +/ g (resin).With thickness is that 20～30 microns ptfe porous membrane is put in the solution.Vacuum pump maintains absolute pressure 50mmHg with the sealed vessel internal pressure, and it is transparent that film becomes soon.Return to normal pressure, soaked 1 hour, take out airing then.About 30～50 microns of film thickness.
Embodiment 19 electrode preparation and performance test
1. proton exchange membrane (single film and composite membrane) pre-treatment
Film is placed in 10% the HCl solution and soaks more than 4 hours, in deionized water, soaked 2 hours again, then at 60 ℃ 10% HNO 3Soak half an hour in the solution, extremely neutral with deionized water wash at last.
2. three-in-one electrode compacting
Pretreated proton exchange membrane is clipped in two carbon papers that scribble catalyzer, and (Shenli Science and Technology Co Ltd, Shanghai provides, and area is 44.9cm 2) in the middle of, at 110 ℃ and 1.4 * 10 3N/cm 2Under suppress and made three-in-one electrode in 2 minutes.It is added upper side frame and be assembled into monocell test.
3. battery testing
The test condition of monocell is: battery temperature=75 ℃; Hydrogen inlet pressure=0.10MPa, gas inlet pressure=0.12MPa.
Novel fluorine-containing trifluorostyrene monomer by the present invention's development can be prepared into proton exchange resins with other styrenic fluorine-containing derivant copolymerization and sulfonation.The proton fuel cell of resins is good with proton exchange membrane performance performance in fuel cell thus, and with low cost.

Claims (4)

1, a kind of fluorine-containing trifluorostyrene monomer, its structural formula is as follows:
R wherein f=C mF 2m+1Or (CF 2CF 2) nOCF 2CF 2SO 2F, m=2,3,4,5 or 6, n=1,2,3 or 4.
2, the synthetic method of fluorine-containing trifluorostyrene monomer as claimed in claim 1 is characterized in that by following prepared in reaction:
1) in organic solvent and under the copper powder effect, iodobenzene and IR fReacting makes fluoroalkyl benzene, iodobenzene, IR fWith the copper powder mol ratio be 1: 0.8～1.5: 1.5～4.0, temperature of reaction is 60～120 ℃, the reaction times is 15～40 hours;
2) fluoroalkyl benzene the nitration mixture effect of the nitrosonitric acid and the vitriol oil issue the caliche reaction make corresponding between the nitro fluoroalkyl benzene, fluoroalkyl benzene, HNO 3And H 2SO 4Mol ratio be 1.0: 1.5～2.0: 1.5～2.0, temperature of reaction is 30～60 ℃, the reaction times is 15～40 hours;
3) the nitro fluoroalkyl benzene is at SnCl between 22H 2Diazotization under the effect of O and dense HCl, obtain corresponding between amino fluoroalkyl benzene, a nitro fluoroalkyl benzene, SnCl 22H 2The mol ratio of O and dense HCl is 1.0: 4.0～6.0: 8.0～12.0, and temperature of reaction is 30～80 ℃, and the reaction times is 0.5～2.0 hour;
4) amino fluoroalkyl benzene elder generation and saturated NaNO between 2Diazotization reaction takes place in solution and dense HCl, generates the diazonium chloride m-fluoroalkyl benzene, an amino fluoroalkyl benzene, NaNO 2With the mol ratio of HCl be 1.0: 1.0～1.3: 1.0～1.3, temperature of reaction is-5～5 ℃, the reaction times is 1.0～5.0 hours;
5) iodination reaction takes place in diazonium chloride m-fluoroalkyl benzene and KI, between generation-and I-PhR f, the mol ratio of diazonium chloride m-fluoroalkyl benzene and KI is 1.0: 1.0～1.3, and temperature of reaction is 45～75 ℃, and the reaction times is 0.5～2.0 hour;
6) between the iodo fluoroalkyl benzene under the effect under Primary Catalysts and the promotor with CF 2Linked reaction takes place in=CFZnBr, an iodo fluoroalkyl benzene, CF 2The mol ratio of=CFZnBr, Primary Catalysts and promotor is 1.0: 1.0～1.3: 0.004～0.006: 0.012～0.05, and temperature of reaction is 40～70 ℃, and the reaction times is 5～20 hours, and described catalyzer and promotor are Pd (dba) 3/ Ph 3P, Pd (OAc) 2/ Ph 3P, PdCl 2/ Ph 3P, Pd (dba) 3/ POPh 3, Pd (OAc) 2/ POPh 3And PdCl 2/ POPh 3, wherein dba=two inferior Bian benzylacetone bases, OAc=acetoxy group;
Above-mentioned R f=C mF 2m+1Or (CF 2CF 2) nOCF 2CF 2SO 2F, m=1,2,3,4,5 or 6, n=1,2,3 or 4.
3, the synthetic method of fluorine-containing trifluorostyrene monomer as claimed in claim 2 is characterized in that wherein 1) described in the reaction organic solvent be N, dinethylformamide, N,N-dimethylacetamide and N-Methyl pyrrolidone.
4, a kind of fluorine-containing trifluorostyrene monomer purposes as claimed in claim 1 is characterized in that being used to preparing the proton exchange resins of the proton exchange membrane of used in proton exchange membrane fuel cell.
CNB011320990A 2001-11-02 2001-11-02 Fluorine-containing trifluorostyrene monomer and its synthesis and use Expired - Fee Related CN1148338C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB011320990A CN1148338C (en) 2001-11-02 2001-11-02 Fluorine-containing trifluorostyrene monomer and its synthesis and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB011320990A CN1148338C (en) 2001-11-02 2001-11-02 Fluorine-containing trifluorostyrene monomer and its synthesis and use

Publications (2)

Publication Number Publication Date
CN1349962A CN1349962A (en) 2002-05-22
CN1148338C true CN1148338C (en) 2004-05-05

Family

ID=4671144

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB011320990A Expired - Fee Related CN1148338C (en) 2001-11-02 2001-11-02 Fluorine-containing trifluorostyrene monomer and its synthesis and use

Country Status (1)

Country Link
CN (1) CN1148338C (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060135715A1 (en) * 2003-06-27 2006-06-22 Zhen-Yu Yang Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes
JP4796055B2 (en) * 2004-05-07 2011-10-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Stable trifluorostyrene-containing compounds grafted to a base polymer
WO2006102671A1 (en) * 2005-03-24 2006-09-28 E. I. Du Pont De Nemours And Company Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture
CN1300240C (en) * 2005-04-21 2007-02-14 上海交通大学 Ion exchange resin of sulfonic perfluoroalkyl poly alpha methylstyrene and preparation method thereof
CN102241554A (en) * 2011-04-22 2011-11-16 中国科学院上海有机化学研究所 Method for synthesizing trifluorostyrene fluorine-containing monomer
EP3497137B1 (en) * 2016-08-12 2024-05-01 Akron Polymer Systems, Inc. Method for the preparation of nitrated styrenic fluoropolymers
CN106748635B (en) * 2016-12-05 2019-07-12 青岛昌泰和生物科技有限公司 A kind of preparation method of trifluoro ethyl phenylacetylene compound

Also Published As

Publication number Publication date
CN1349962A (en) 2002-05-22

Similar Documents

Publication Publication Date Title
CN1148338C (en) Fluorine-containing trifluorostyrene monomer and its synthesis and use
CN101029144A (en) Crosslinked fluoride proton exchange film, its production and use
CN101510615A (en) Semi-interpenetrating network type composite proton exchange film based on crosslinkable medlin and preparation method thereof
CN103981720A (en) Polyaniline (PANI)-modified aramid fiber (ARF) composite conductive fiber and preparation method thereof
CN106543439A (en) Fuel cell cross-linking type sulfonation containing amino polyfluorene ether sulfone nitrile proton exchange membrane material, preparation method and applications
CN1128679C (en) Fluoric proton exchange resins of polytrifluorostyrenes, synthesizing process and application thereof
CN106378189B (en) Catalyst and its preparation method and application for synthesizing polymethoxy dimethyl ether
CN110317356B (en) Multifunctional crosslinking type polyarylene butanedione anion exchange membrane and preparation method thereof
CN100336843C (en) Sulfonated high polymer containing bisphenol fluorine, synthesis and application thereof
CN108878740B (en) Non-ionic side chain modified polybenzimidazole membrane and preparation method thereof
CN1317783C (en) Graft olefin sulfonic acid proton exchange membrane containing hydrogen silicone oil and its preparing method
CN1235849C (en) Compound of sulfonation polyarylether, intermediate, and its synthesis and application
CN114716650B (en) Sulfonated indigo red aryl polymer structure with spiral structure, efficient preparation and application thereof
CN1166723C (en) Polystyrene sulfonate film for low-temp. direct methanol fuel cell and preparation process thereof
CN1282686C (en) Sulfonated polyether compound, its synthesis and use thereof
CN103346341A (en) Acid-base composite high-temperature proton exchange membrane and preparation method thereof
CN103113588A (en) Polysulfone with quaternary ammonium group at side chain and preparation method of polysulfone
JP4399746B2 (en) Sulphonic acid group-containing terphenyl dihalide monomer and process for producing the same
CN108043463B (en) High-performance catalyst for carbon dioxide recycling and preparation method thereof
CN102432765B (en) Poly(2-hydroxyethyl methacrylate) and anion exchange membrane for vanadium battery
CN1045966C (en) Trifluoro vinyl phosphonate diester monomer and its synthetic process
CN113600026B (en) Preparation method of anti-pollution cross-linking type anion exchange membrane based on polyvinyl alcohol
CN1290899C (en) Atactic sulfonated high polymer containing dual diaza naphthone and synthesis and application thereof
CN114716649B (en) Fluorine-containing sulfonated polyaryl high molecular structure, high-efficiency preparation and application thereof
CN102336924B (en) Method for preparing perfluorosulfonic acid ion exchange membrane

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20040505

Termination date: 20111102