CN1349962A - Fluorine-containing trifluorostyrene monomer and its synthesis and use - Google Patents
Fluorine-containing trifluorostyrene monomer and its synthesis and use Download PDFInfo
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Abstract
The invention relates to a novel trifluorostyrenes fluorinated monomer, synthesis method and its application. Said method is characterized by that it uses easily-available compound with fluorine-containing group, and makes it undergo the processes of nitration, diazotization and iodination, and then couple wtih trifluorobromethylene to obtain said fluorinated monomer. Said monomer can be copolymerized and sulfonated with styrene, trifluorostyrene or trifluorostyrene-like fluorine-contained derivative to prepare proton-exchange resin. Said resin can be used for preparing proton-exchange membrane for proton-exchange membrane fuel cell. Said invention also provides the structure formula of said fluorine-contained monomer.
Description
Technical Field
The invention relates to a novel trifluorostyrene fluorine-containing monomer, a synthesis method and application thereof.
Background
In recent decades, the pollution of flue gas discharged by coal-fired thermal power generation and tail gas of fuel-fired automobiles to the atmosphere has become a worldwide environmental problem, and the research on the optimized utilization of energy and the development of clean energy are important components of the strategy of 21 st century energy and environmental sustainable development and are also the foundation of the 21 st century world economic development.
Hydrogen energy has the advantage of being clean and inexhaustible and is known as the mainstream energy source in the 21 st century. Proton exchange membrane fuel cells are excellent devices for generating electricity from hydrogen energy. The novel portable power source has a series of advantages of low operating temperature, quick start, simple structure, good performance, long service life, no corrosiveness and the like, so that the novel portable power source has a huge potential application prospect in small-sized portable power sources, particularly electric vehicles, and is a hotspot of fuel cell research. It is expected that proton exchange membrane fuel cell electric vehicles will be commercialized in 2008.
Proton exchange membranes are one of the cores of proton exchange membrane fuel cells. The major use in the world is Nafion, which was successfully developed and commercialized by DuPont in 1966®Series perfluorinated proton exchange membranes (U.S. patent: 3,282,875[1966 ]]). Furthermore, the perfluorinated proton exchange membrane used is Flemion developed by Asahi glass company of Japan®Film and Aciplex developed by Asahi Kasei Co., Ltd®And (3) a membrane. The three perfluorinated proton exchange membranes are all prepared from perfluorinated proton exchange resins containing side chains with different lengths. The perfluorinated proton exchange resin has complex monomer synthesis and high cost. Dow chemical company developed Dow with shorter functional side chain in the 80 s®Perfluorinated proton exchange membranes (U.S. patent: 4,358,412[1982 ]]). Although the performance is better than that of Nafion®、Flemion®And Aciplex®The film is good, but the resin monomer synthesis is more complex, the cost is higher, and the service life is shorter than that of a long side chain film, so that the application prospect is limited.
The perfluorinated proton exchange resin has complex monomer synthesis, and although the performance is quite good, the cost is too high to limit the application of the perfluorinated proton exchange resin in fuel cells,for example, the price of Nafion 115 reaches 800US $/cm2Which accounts for about one third of the cost of proton exchange membrane fuel cells. Therefore, many companies and research units are currently around the world to develop new monomers and methods for synthesizing the same, and to use proton exchange membranes prepared from resins polymerized from such monomers in fuel cells. The Canadian Ballard company developed a partially fluorinated proton exchange resin andthus, a proton exchange membrane was prepared, and the resin main component was a copolymer of trifluorostyrene and its derivatives (U.S. P.5,422,411[ 1995)]；5,498,639[1996]；5,602,185[1997]；5,684,192[1997]；5,773,480[1998]). The proton exchange membrane made of the resin has the advantages of higher sulfonation degree and water content, and better performance shown by assembled fuel cells, but the poor mechanical strength and brittleness of the membrane during dehydration limit the long-term use of the proton exchange membrane, and most importantly, the synthesis cost of the resin monomer is still high.
The research on suitable monomers and synthesis methods is an effective way to reduce the cost of the proton exchange membrane fuel cell.
Object of the Invention
The invention aims to provide a novel trifluorostyrene fluorine-containing monomer.
Another object of the present invention is to provide an IR-containing starting material which is easily obtainable from a simple substancefAnd iodobenzene are used for synthesizing the trifluorostyrene fluorine-containing monomer. Wherein R isf＝CmF2m+1Or (CF)2CF2)nOCF2SO2F, m is 2, 3, 4, 5 or 6, and n is 1, 2, 3 or 4.
The invention also aims to provide the application of the trifluorostyrene fluorine-containing monomer, which can be copolymerized with styrene, trifluorostyrene or trifluorostyrene fluorine-containing derivatives and sulfonated to prepare proton exchange resin, and the resin can be used for preparing a proton exchange membrane for a proton exchange membrane fuel cell with low cost and excellent performance.
Disclosure of Invention
The invention relates to a novel trifluorostyreneThe fluorine-containing monomer has the following structural formula:
wherein R isf＝CmF2m+1Or (CF)2CF2)nOCF2CF2SO2F, m is 2, 3, 4, 5 or 6, and n is 1, 2, 3 or 4.
The synthesis reaction formula of the trifluorostyrene monomer of the present invention can be exemplified as follows:
the coupling reaction is that firstly the trifluorobromoethylene is converted into trifluorobromovinyl zinc reagent, and then the trifluorobromoethylene is catalyzed by a main catalyst and a cocatalyst to react with m-I-PhRfReacting to obtain the corresponding fluoroalkyl-substituted trifluorostyrene monomer. The process is as follows:
the invention synthesizes novel trifluorostyrene fluorine-containing monomers containing different substituents, and the structural formula is as follows:
different substituents RfAre shown in Table 1. TABLE 1
| Numbering | Rf |
| 1-1 | meta-C2F5 |
| 1-2 | meta-C3F7 |
| 1-3 | meta-C4F9 |
| 1-4 | meta-C5F11 |
| 1-5 | meta-C6F13 |
| 1-6 | meta-CF2CF2OCF2CF2SO2F |
| 1-7 | Meta- (CF)2CF2)2OCF2CF2SO2F |
| 1-8 | Meta- (CF)2CF2)3OCF2CF2SO2F |
| 1-9 | Meta- (CF)2CF2)4OCF2CF2SO2F |
The invention also provides a method for simply, conveniently and effectively synthesizing the fluorine-containing monomer. From simple readily available fluorine-containing starting materials IRfReacting with iodobenzene under the action of neutralizing copper powder in organic solvent to obtain corresponding fluoroalkylBenzene. Iodobenzene, IRfThe molar ratio of the copper powder to the copper powder is 1.0: 0.8-1.5: 1.5-4.0; the reaction temperature is 60-120 ℃; the reaction time is 15-40 hours; the organic solvent used in the reaction may be N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (DMP), or the like.
The fluoroalkyl benzene is nitrified by mixed acid of fuming nitric acid and concentrated sulfuric acid to obtain the corresponding m-nitrofluoroalkyl benzene. Fluoroalkyl benzene, HNO3And HSO4The molar ratio of (A) to (B) is 1.0: 1.5-2.0. The nitration reaction temperature is 30-60 ℃; the reaction time is 15-40 hours.
M-nitrofluoroalkylbenzenes in SnCl2·2H2And diazotizing under the action of O and concentrated HCl to obtain the corresponding m-amino fluoroalkyl benzene. M-nitrofluoroalkylbenzenes, SnCl2·2H2The molar ratio of O to concentrated HCl is 1.0: 4.0-6.0: 8.0-12.0; the reaction temperature is 30-80 ℃; the reaction time is 0.5 to 2.0 hours.
M-amino fluoroalkyl benzene first saturated NaNO2And concentrated HCl to generate diazotization reaction to generate diazonium monofluoroalkyl benzene, m-amino fluoroalkyl benzene and NaNO2The molar ratio of HCl to HCl is 1.0: 1.0-1.3, the reaction temperature is-5 ℃, and the reaction time is 1.0-5.0 hours;
iodinating diazo-m-fluoroalkyl benzene and KI to generate m-I-PhRfThe mol ratio of the diazo-m-fluoroalkyl chloride to KI is 1.0: 1.0-1.3, the reaction temperature is 45-75 ℃, and the reaction time is 0.5-2.0 hours;
the m-iodo-fluoroalkyl benzene reacts with CF under the action of a main catalyst and a cocatalyst2The coupling reaction occurs with CFZnBr. M-iodo radicalFluoroalkyl benzene, CF2The molar ratio of CFZnBr to the main catalyst to the cocatalyst is 1.0: 1.0-1.3: 0.004-0.006: 0.012-0.05; the reaction temperature is 40-70 ℃; the reaction time is 5-20 hours. Wherein the main catalyst and the cocatalyst can be Pd (dba)3/Ph3P、Pd(OAc)2/Ph3P、PdCl2/Ph3P、Pd(dba)3/POPh3、Pd(OAc)2/POPh3And PdCl2/POPh3And the like, wherein dba ═ dibenzylidene acetonyl and OAc ═ acetic acid. The molar ratio of the main catalyst to the cocatalyst is 1: 3-10.
The novel trifluorostyrene fluorine-containing monomer can be copolymerized with other styrene fluorine-containing derivatives and sulfonated to prepare the proton exchange resin. The proton exchange membrane for the proton exchange membrane fuel cell prepared by the resin has good performance in the fuel cell and low cost.
Drawings
Fig. 1 is a polarization curve of a single cell assembled from a single film, and fig. 2 is a polarization curve of a single cell assembled from a composite film. The polarization curve may illustrate the electrochemical performance of such resins. The ordinate of the polarization curve is the voltage of the single cell in volts (V); the abscissa is the current density of the single cell in amperes per square centimeter (A/cm)2). The test conditions for the single cells were: the temperature of the battery is 75 ℃; hydrogen inlet pressureThe force was 0.10MPa and the air inlet pressure was 0.12 MPa.
Detailed description of the invention
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these specific examples. Examples 1 to 14 respectively describe Rf＝C6F13，C2F5，(CF2CF2)3OCF2CF2SO2F or CF2CF2OCF2CF2SO2Preparation of F monomerA process; examples 15-16 describe Trifluorostyrenes (TFS), m-CF3-TFS and meta- (CF)2CF2)3OCF2CF2SO2F-PyCF＝CF2Terpolymerization of (a) and sulfonation of the resin; examples 17-18 describe the preparation of single and composite membranes for fuel cells; example 19 describes the preparation and testing of a three-in-one electrode for fuel cells using single and composite membranes.
Example 1 PhC6F13Synthesis of (2)
In a 1L three-necked flask, nitrogen gas was introduced for 1 hour. 1.1kg of DMF, 269g of copper powder, 468g of IC are added with mechanical stirring6F13，214g C6H5I, heating, refluxing and stirring at 120 ℃ for 24 hours. The reaction solution was filtered, the residual solid was extracted with ether, and the filtrates were combined. DMF and other impurities were removed under reduced pressure at 50 ℃ by means of a water pump. The product was collected at about 100 ℃ with a yield of 277g, 65% yield and 97.5% purity.
EXAMPLE 2 meta-NO2-PhC6F13Synthesis of (2)
A1L three-necked flask was charged with 66.2g of PhC6F13And (3) adding 10-15 ml of fuming nitric acid and 25-30 ml of concentrated sulfuric acid into the mixture under mechanical stirring in an ice-water bath. Controlling the reaction temperature to be 45-55 ℃. After the reaction was completed the next day, the reaction solution was poured into ice water, the organic layer was extracted with diethyl ether, and NaHCO was used3Washing the solution to neutrality, and then using anhydrous MgSO4Drying and finally distilling off the product under reduced pressure gave a yield of 64.5g, 87%.
Example 3 m-NH2-PhC6F13Synthesis of (2)
Adding 25-30 g SnCl into a 250ml three-necked bottle2·2H2O and 20-30 ml of concentrated HCl, 12.5g of m-NO is added within 15 minutes2-PhC6F13The reaction was carried out at 70 ℃ for 1 hour and then cooled overnight. The reaction solution was filtered, the filtrate was neutralized with NaOH or KOH solution, extracted with diethyl ether and the product was distilled off under reduced pressure at a yield of 9.7g and 84% yield.
Example 4 m-I-PhC6F13Synthesis of (2)
9.7g of m-NH were added to a 500ml three-necked flask2-PhC6F13Salifying with 7ml of concentrated HCl and ice-cooling2g of NaNO is dripped into the mixture under the stirring of a cooling machine2Saturated solution, after half an hour 4.6g of saturated KI solution was added and stirred vigorously for 1 hour. The organic layer was separated by addition of diethyl ether and washed with NaHCO3The solution was neutralized, dried and the product was distilled off under reduced pressure, yield 8.0, 93%.
Example 5 m-C6F13-PhCF＝CF2Synthesis of (2)
A250 mL reaction flask was purged with nitrogen for 30 minutes, then 56mL of DMF was added, purging with nitrogen continued for 30 minutes, and 17.5g of CF was added with stirring2＝CFZnBr、0.23g Ph3P and 0.15g Pd2(dba)3Heating to 55 deg.C with stirring, adding 5.3g of m-I-PhC6F13And stirred overnight. The monomer and part of DMF were distilled off under reduced pressure, and an equal amount of ice water was added to the distillate, which was shaken up and the layers were separated. The lower oil is the TFS monomer. The m-C is distilled out under reduced pressure again6F13-PhCF ═ CF monomer, yield 2.9g, yield 60%.
Example 6 m-C6F13-PhCF＝CF2Synthesis of (2)
The procedure and reaction conditions were as in example 5. With PdCl2/POPh3In place of Pd (dba)3/Ph3P to form meta-C6F13-PhCF＝CF2The yield was 45%.
Example 7 m-C2F5-PhCF＝CF2Synthesis of (2)
The process and reaction conditions were as in examples 1 to 5, respectively. Example 1 with IC2F5Replacing IC6F13To obtain PhC2F5The yield is 60%; PhC in example 22F5Substitute for PhC6F13To obtain meta-NO2-PhC2F5Yield ofIs 86%; as in example 3 with meta-NO2-PhC2F5Substitution of meta-NO2-PhC2F5To obtain meta-NH2-PhC2F5The yield is 79%; example 4 with meta-NH2-PhC2F5Substitution of meta-NH2-PhC6F13To obtain m-I-PhC2F5The yield is 90%; example 5 with meta-I-PhC2F5In place of meta-I-PhC6F13Finally, m-C is prepared2F5-PhCF＝CF2The yield was 65%.
Example 8 Ph (CF)2CF2)3OCF2CF2SO2Synthesis of F
In a 1L three-necked flask, nitrogen gas was introduced for 1 hour. 1.5kg of DMF, 384g of copper powder, 939g I (CF) were added with mechanical stirring2CF2)3OCF2CF2SO2F，306g C6H5I, heating, refluxing and stirring at 120 ℃ for 24 hours. The reaction solution was filtered, the residual solid was extracted with ether, and the filtrates were combined. DMF and other impurities were removed under reduced pressure at 50 ℃ by means of a water pump. The product is collected at about 100 ℃, and the yield is 626g, the yield is 72 percent, and the purity is 98 percent.
Example 9 meta-NO2-Ph(CF2CF2)3OCF2CF2SO2Synthesis of F
A1L three-necked flask was charged with 137.6g of Ph (CF)2CF2)3OCF2CF2SO2F, adding mixed acid of 19ml of fuming nitric acid and 40ml of concentrated sulfuric acid into the ice-water bath under mechanical stirring. The reaction temperature was controlled at 45 ℃. After the reaction was completed the next day, the reaction solution was poured into ice water, the organic layer was extracted with diethyl ether, and NaHCO was used3Washing the solution to neutrality, and then using anhydrous MgSO4Drying and finally distilling off the product under reduced pressure, the yield is 134g and 90 percent.
Example 10 m-NH2-Ph(CF2CF2)3OCF2CF2SO2Synthesis of F
41g of SnCl were added to a 250ml three-necked flask2·2H2O and 37ml of concentrated HCl, 25g of m-NO being added over 15 minutes2-Ph(CF2CF2)3OCF2CF2SO2F, reaction at 70 ℃ for 1 hour, and then cooling overnight. The reaction solution was filtered, the filtrate was neutralized with NaOH solution, extracted with diethyl ether and the product was distilled off under reduced pressure, yield 19.8g, 84% yield.
Example 11 m-I-Ph (CF)2CF2)3OCF2CF2SO2Synthesis of F
19.8g of m-NH were added to a 500ml three-necked flask2-Ph(CF2CF2)3OCF2CF2SO2F and 10ml of concentrated HCl for salifying, cooling in ice bath, and dripping 3g of NaNO under mechanical stirring2Saturated solution, 6.6gKI saturated solution was added half an hour later and stirred vigorously for 1 hour. The organic layer was separated by addition of diethyl ether and washed with NaHCO3The solution was neutralized, dried and the product was distilled off under reduced pressure, yield 13g, 55%.
EXAMPLE 12 meta- (CF)2CF2)3OCF2CF2SO2F-PhCF＝CF2Synthesis of (2)
A250 mL reaction flask was purged with nitrogen for 30 minutes, then 80mL of DMF was added, purged with nitrogen for 30 minutes, and 25g of CF was added with stirring2＝CFZnBr、0.32g Ph3P and 0.22g Pd2(dba)3Heated to 55 ℃ with stirring, 10g of m-I-Ph (CF) are added2CF2)3OCF2CF2SO2F, stirring overnight. The monomer and part of DMF were distilled off under reduced pressure, and an equal amount of ice water was added to the distillate, which was shaken up and the layers were separated. The lower oil is the TFS monomer. The m- (CF) is distilled out under reduced pressure again2CF2)3OCF2CF2SO2F-PhCF ═ CF monomer, yield 4.2g, yield 45%.
EXAMPLE 13 meta- (CF)2CF2)3OCF2CF2SO2F-PhCF＝CF2Synthesis of (2)
The procedure and reaction conditions were as in example 12. With PdCl2/POPh3In place of Pd (dba)3/Ph3P to m- (CF)2CF2)3OCF2CF2SO2F-PhCF＝CF2The yield was 30%.
Example 14 m-CF2CF2OCF2CF2SO2F-PhCF＝CF2Synthesis of (2)
The process and reaction conditions were as in examples 8 to 12, respectively. Example 8 uses ICF2CF2OCF2CF2SO2F instead of I (CF)2CF2)3OCF2CF2SO2F to obtain PhCF2CF2OCF2CF2SO2F, the yield is 69%; example 9 with PhCF2CF2OCF2CF2SO2F instead of Ph (CF)2CF2)3OCF2CF2SO2F to meta-NO2-PhCF2CF2OCF2CF2SO2F, the yield is 91%; example 10 with meta-NO2-PhCF2CF2OCF2CF2SO2F instead of meta-NO2-Ph(CF2CF2)3OCF2CF2SO2F to form m-NH2-PhCF2CF2OCF2CF2SO2F, the yield is 88%; example 11 with meta-NH2-PhCF2CF2OCF2CF2SO2F instead of m-NH2-Ph(CF2CF2)3OCF2CF2SO2F to obtain m-I-PhCF2CF2OCF2CF2SO2F, the yield is 60%; example 12 as meta-I-PhCF2CF2OCF2CF2SO2F instead of m-I-Ph (CF)2CF2)3OCF2CF2SO2F, finally obtaining m-CF2CF2OCF2CF2SO2F-PhCF＝CF2The yield was 40%.
EXAMPLE 15 polymerization of ternary monomers
A3L three-necked flask was purged with nitrogen for 30 minutes, and then 1050ml of water and 19g n-C were added12H25NH2Introducing nitrogen continuously for 1 hour by using a Cl emulsifier; heating to 50 ℃, and electromagnetically stirring at constant temperature; 119g of TFS (trifluorostyrene), 43g m-CF were weighed out in proportion3TFS and a small amount of m- (CF)2CF2)3OCF2CF2SO2F-PhCF＝CF2(the proportion of the ternary system can be adjusted) is added into a flask, and finally 1.45g of initiator potassium persulfate is added for reaction for 72 hours; pouring the polymerized product into a sodium hydroxide solution, mechanically stirring, and demulsifying for about 10-15 minutes; filtering the solution by a Buchner funnel, washing the product to be neutral by distilled water, washing residual water and low molecular weight substances by methanol, and pumping to dry; and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the final product. The polymerization yield is more than 90%. The intrinsic viscosity was 1.226.
EXAMPLE 16 sulfonation of the Polymer
Firstly, 75g of the polymer prepared in example 15 is dissolved in 660ml of dichloromethane and added into a sulfonation reactor to be stirred and dissolved; a mixed solution of 49g of triethyl phosphate, 43.7ml of sulfur trioxide and 110ml of dichloromethane was added with vigorous stirring; after about 5 minutes, the addition was heated to reflux for 1 hour; filtering, washing with 500ml chloroform, and finally washing with deionized ice water to neutrality; the sulfonated product is stored in a dry way, and the sulfonation yield is more than90 percent. The sulfonation degree of the resin is 2.4mmolHSO4 +(resin) and a water content of 70%.
EXAMPLE 17 casting preparation of Single film
The sulfonation degree of the sulfonated polymer prepared in example 16 is 2.2-2.4 mmolHSO4 +Preparing 20% DMF solution with/g (resin) of novel proton exchange resin, and casting the solution on a film forming tableCasting, and controlling the temperature at 50 ℃. Spraying water to form film after the solvent is volatilized. The film thickness is about 30 to 50 microns.
Example 18 preparation of composite Membrane by vacuum filling
A novel 5% strength methanolic proton exchange resin prepared as described in example 16 and having a sulfonation degree of 2.2 to 2.4mmol of HSO was placed in a sealed container4 +(ii) in terms of/g (resin). And putting the porous polytetrafluoroethylene film with the thickness of 20-30 microns into the solution. The vacuum pump maintained the pressure in the sealed vessel at 50mmHg absolute and the film quickly became transparent. Recovering to normal pressure, soaking for 1 hr, taking out, and air drying. The film thickness is about 30 to 50 microns.
Example 19 electrode preparation and Performance testing
1. Pretreatment of proton exchange membranes (single and composite membranes)
Soaking the membrane in 10% HCl solution for more than 4 hr, soaking in deionized water for 2 hr, and adding 10% HNO at 60 deg.C3Soaking in the solution for half an hour, and washing with deionized water to neutrality.
2. Three-in-one electrode pressing
The pretreated proton exchange membrane was sandwiched between two catalyst coated carbon papers (supplied by Shanghai Shenli science and technology Co., Ltd., area 44.9 cm)2) Intermediate, at 110 ℃ and 1.4X 103N/cm2Pressing for 2 minutes to obtain the three-in-one electrode. The frame is added and assembled into a single cell for testing.
3. Battery testing
The test conditions for the single cells were: the temperature of the battery is 75 ℃; the hydrogen inlet pressure was 0.10MPa, and the air inlet pressure was 0.12 MPa.
The novel trifluorostyrene fluorine-containing monomer developed by the invention can be copolymerized and sulfonated with other styrene fluorine-containing derivatives to prepare the proton exchange resin. The proton exchange membrane for the proton fuel cell prepared by the resin has good performance in the fuel cell and low cost.
Claims (4)
1. A trifluorostyrene fluorine-containing monomer has the following structural formula:wherein R isf＝CmF2m+1Or (CF)2CF2)nOCF2CF2SO2F, m is 2, 3, 4, 5 or 6, and n is 1, 2, 3 or 4.
2. The method for synthesizing trifluorostyrene type fluoromonomer according to claim 1, wherein the fluorostyrene type fluoromonomer is prepared by the following reaction:
1) under the action of organic solvent and copper powder, iodobenzene and IRfReacting to obtain the fluoroalkyl benzene. Iodobenzene, IRfThe molar ratio of the copper powder to the copper powder is 1: 0.8-1.5: 1.5-4.0, the reaction temperature is 60-120 ℃, and the reaction time is 15-40 hours;
2) the fluoroalkyl benzene is nitrated under the mixed acid action of fuming nitric acid and concentrated sulfuric acid to prepare corresponding m-nitrofluoroalkyl benzene, fluoroalkyl benzene and HNO3And HSO4The molar ratio of (A) to (B) is 1.0: 1.5-2.0; the reaction temperature is 30-60 ℃, and the reaction time is 15-40 hours;
3) m-nitrofluoroalkylbenzenes in SnCl2·2H2Diazotizing under the action of O and concentrated HCl to obtain corresponding m-amino fluoroalkyl benzene, m-nitro fluoroalkyl benzene and SnCl2·2H2The molar ratio of O to concentrated HCl is 1.0: 4.0-6.0: 8.0-12.0; the reaction temperature is 30-80 ℃, and the reaction time is 0.5-2.0 hours;
4) m-amino fluoroalkyl benzene and NaNO2Saturated concentrated HCl is subjected to diazotization reaction to generate diazonium metafluoroalkyl benzene, metaamino fluoroalkyl benzene and NaNO2The molar ratio of HCl to HCl is 1.0: 1.0-1.3, the reaction temperature is-5 ℃, and the reaction time is 1.0-5.0 hours;
5) iodinating diazo-m-fluoroalkyl benzene and KI to generate m-I-PhRfThe mol ratio of the diazo-m-fluoroalkyl chloride to KI is 1.0: 1.0-1.3, the reaction temperature is 45-75 ℃, and the reaction time is 0.5-2.0 hours;
6) the m-iodo-fluoroalkyl benzene reacts with CF under the action of a main catalyst and a cocatalyst2Coupling reaction between CFZnBr and m-iodofluoroalkylbenzene, CF2The molar ratio of CFZnBr to the main catalyst to the cocatalyst is 1.0: 1.0-1.3: 0.004-0.006: 0.012-0.05; the reaction temperature is 40-70 ℃; the reaction time is 5-20 hours, and the catalyst and the cocatalyst are Pd (dba)3/Ph3P、Pd(OAc)2/Ph3P、PdCl2/Ph3P、Pd(dba)3/POPh3、Pd(OAc)2/POPh3And PdCl2/POPh3Wherein dba is two benzyl subbaseLactone, OAc ═ acetate;
r is as defined abovef＝CmF2m+1Or (CF)2CF2)nOCF2CF2SO2F, m is 1, 2, 3, 4, 5 or 6, and n is 1, 2, 3 or 4.
3. The method for synthesizing trifluorostyrene type fluoromonomer according to claim 2, wherein the organic solvent used in the reaction of 1) is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
4. Use of a trifluorostyrene fluoromonomer according to claim 1, characterized by being used for the preparation of a proton exchange resin for a proton exchange membrane fuel cell.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005003083A1 (en) * | 2003-06-27 | 2005-01-13 | E.I. Dupont De Nemours And Company | Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes |
| 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 |
| US7737190B2 (en) * | 2005-03-24 | 2010-06-15 | E.I. Du Pont De Nemours And Company | Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture |
| US7829603B2 (en) * | 2004-05-07 | 2010-11-09 | E.I. Du Pont De Nemours And Company | Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes |
| 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 |
| CN106748635A (en) * | 2016-12-05 | 2017-05-31 | 青岛昌泰和生物科技有限公司 | A kind of preparation method of trifluoro ethyl phenylacetylene compound |
| CN109563197A (en) * | 2016-08-12 | 2019-04-02 | 阿克隆聚合物系统有限公司 | Prepare the fluoropolymer-containing method of nitrated styrenes class |
-
2001
- 2001-11-02 CN CNB011320990A patent/CN1148338C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005003083A1 (en) * | 2003-06-27 | 2005-01-13 | E.I. Dupont De Nemours And Company | Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes |
| US7829603B2 (en) * | 2004-05-07 | 2010-11-09 | E.I. Du Pont De Nemours And Company | Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes |
| US7737190B2 (en) * | 2005-03-24 | 2010-06-15 | 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 |
| WO2012142956A1 (en) * | 2011-04-22 | 2012-10-26 | 中国科学院上海有机化学研究所 | Preparation method of trifluorostyrene compound |
| CN109563197A (en) * | 2016-08-12 | 2019-04-02 | 阿克隆聚合物系统有限公司 | Prepare the fluoropolymer-containing method of nitrated styrenes class |
| CN109563197B (en) * | 2016-08-12 | 2022-09-09 | 阿克隆聚合物系统有限公司 | Method for preparing nitrated styrene type fluorine-containing polymer |
| CN106748635A (en) * | 2016-12-05 | 2017-05-31 | 青岛昌泰和生物科技有限公司 | A kind of preparation method of trifluoro ethyl phenylacetylene compound |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1148338C (en) | 2004-05-05 |
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