METHODS OF MAKING A POLYFLUORINATED ALLYL ETHER AND COMPOUNDS RELATING TO THE METHODS

Abstract

A method includes combining first components including at least one of CF.sub.2═CF—CF.sub.2—OSO.sub.2Cl or CF.sub.2═CF—CF.sub.2—OSO.sub.2CF.sub.3, a polyfluorinated compound having at least one ketone or carboxylic acid halide, and fluoride ion to provide a compound comprising at least one perfluorinated allyl ether group. A method includes combining second components including B(OSO.sub.2Cl).sub.3 and hexafluoropropylene to provide CF.sub.2═CF—CF.sub.2—OSO.sub.2Cl. Another method includes combining second components including M(OSO.sub.2CF.sub.3).sub.3 and hexafluoropropylene at a temperature above 0° C. to provide CF.sub.2═CF—CF.sub.2—OSO.sub.2CF.sub.3, wherein M is Al or B. The compound CF.sub.2═CF—CF.sub.2—OSO.sub.2Cl is also provided.

Claims

1. A method of making a compound comprising at least one perfluorinated allyl ether group, the method comprising: combining first components comprising: the compound of claim 11 a polyfluorinated compound comprising at least one ketone, carboxylic acid halide, or a combination thereof, and fluoride ion to provide the compound comprising at least one perfluorinated allyl ether group.

2. The method of claim 1, wherein the compound comprising at least one perfluorinated allyl ether group is represented by formula CF.sub.2═CFCF.sub.2(OC.sub.nF.sub.2n).sub.zORf, wherein each n is independently from 2 to 6, z is 0, 1, or 2, and Rf is a linear or branched perfluoroalkyl group having from 1 to 8 carbon atoms and optionally interrupted by one or more —O— groups.

3. The method of claim 1, wherein the compound comprising at least one perfluorinated allyl ether group is represented by formula CF.sub.2═CF—CF.sub.2—O—R.sub.F—O—CF.sub.2—CF═CF.sub.2, wherein R.sub.F represents linear or branched perfluoroalkylene or perfluoropolyoxyalkylene or arylene, which may be non-fluorinated or fluorinated.

4. The method of claim 3, wherein R.sub.F represents linear or branched perfluoroalkylene or perfluoropolyoxyalkylene.

5. The method of claim 1, wherein the polyfluorinated compound comprising at least one ketone, carboxylic acid halide, or combination thereof is O═CR.sup.3R.sup.3, wherein each R.sup.3 is independently a linear or branched perfluoroalkyl group having from 1 to 12 carbon atoms that is optionally terminated by —SO.sub.2F, —OCF.sub.2CF═CF.sub.2, —COF, —CF(CF.sub.3).sub.2, —CF.sub.2CO.sub.2H, —F, —Cl, —Br, —I, —CN, or —CO.sub.2-alkyl, and optionally interrupted by one or more —O— groups.

6. The method of claim 1, wherein the polyfluorinated compound comprising at least one ketone, carboxylic acid halide, or combination thereof is FC(O)(R.sup.1) or FC(O)(R.sup.2), wherein R.sup.1 is a linear or branched perfluoroalkyl group having from 2 to 12 carbon atoms that is optionally terminated by —SO.sub.2F, —OCF.sub.2CF═CF.sub.2, —COF, —Cl, —Br, —I, or —CO.sub.2-alkyl, and wherein R.sup.2 is a linear or branched perfluoroalkyl group having from 2 to 14 carbon atoms that is interrupted by one or more —O— groups and optionally terminated by —SO.sub.2F, —OCF.sub.2CF═CF.sub.2, —COF, —Cl, —Br, —I, or —CO.sub.2-alkyl.

7. The method claim 1, wherein the components comprise at least one of sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, or (R).sub.4NF, wherein is each R is independently alkyl having from 1 to 6 carbon atoms.

8. The method of claim 1, further comprising combining second components comprising B(OSO.sub.2Cl).sub.3 and hexafluoropropylene to provide CF.sub.2═CF—CF.sub.2—OSO.sub.2Cl.

9. A method of making the compound of claim 11, the method comprising: combining second components comprising B(OSO.sub.2Cl).sub.3 and hexafluoropropylene to provide CF.sub.2═CF—CF.sub.2—OSO.sub.2Cl.

10. The method of claim 9, further comprising: combining third components comprising BCl.sub.3 and ClSO.sub.3H to provide B(OSO.sub.2Cl).sub.3.

11. A compound represented by formula CF.sub.2═CF—CF.sub.2—OSO.sub.2Cl.

12. The method of claim 2, wherein z is 0, and wherein Rf is a linear or branched perfluoroalkyl group having from 1 to 4 carbon atoms.

13. A method of making CF.sub.2═CF—CF.sub.2—OSO.sub.2CF.sub.3, the method comprising combining second components comprising M(OSO.sub.2CF.sub.3).sub.3 and hexafluoropropylene at a temperature above 0° C. to provide CF.sub.2═CF—CF.sub.2—OSO.sub.2CF.sub.3, wherein M is Al or B.

14. The method of claim 13, wherein the second components are combined at a temperature between 2° C. and 10° C., and wherein M is B.

15. The method of claim 1, further comprising combining the compound comprising at least one perfluorinated allyl ether group with at least one partially fluorinated or perfluorinated ethylenically unsaturated monomer represented by formula R.sup.aCF═CR.sup.a.sub.2, wherein each R.sup.a is independently fluoro, chloro, bromo, hydrogen, a fluoroalkyl group, alkyl having up to 10 carbon atoms, alkoxy having up to 8 carbon atoms, or aryl having up to 8 carbon atoms.

16. A method of making a compound comprising at least one perfluorinated allyl ether group, the method comprising: combining first components comprising: CF.sub.2═CF—CF.sub.2—OSO.sub.2CF.sub.3, a polyfluorinated compound comprising at least one carboxylic acid halide, and fluoride ion to provide the compound comprising at least one perfluorinated allyl ether group.

17. The method of claim 16, wherein the compound comprising at least one perfluorinated allyl ether group is represented by formula CF.sub.2═CFCF.sub.2(OC.sub.nF.sub.2n).sub.zORf, wherein each n is independently from 2 to 6, z is 0, 1, or 2, and Rf is a linear or branched perfluoroalkyl group having from 1 to 8 carbon atoms and optionally interrupted by one or more —O— groups.

18. The method of claim 17, wherein z is 0, and wherein Rf is a linear or branched perfluoroalkyl group having from 1 to 4 carbon atoms.

19. The method of claim 16, wherein the compound comprising at least one perfluorinated allyl ether group is represented by formula CF.sub.2═CF—CF.sub.2—O—RF—O—CF.sub.2—CF═CF.sub.2, wherein RF represents linear or branched perfluoroalkylene or perfluoropolyoxyalkylene or arylene, which may be non-fluorinated or fluorinated.

20. The method of claim 16, wherein the polyfluorinated compound comprising at least one carboxylic acid halide is FC(O)(R.sup.1) or FC(O)(R.sup.2), wherein R.sup.1 is a linear or branched perfluoroalkyl group having from 2 to 12 carbon atoms that is optionally terminated by —SO.sub.2F, —OCF.sub.2CF═CF.sub.2, —COF, —Cl, —Br, —I, or —CO.sub.2-alkyl, and wherein R.sup.2 is a linear or branched perfluoroalkyl group having from 2 to 14 carbon atoms that is interrupted by one or more —O— groups and optionally terminated by —SO.sub.2F, —OCF.sub.2CF═CF.sub.2, —COF, —Cl, —Br, —I, or —CO.sub.2-alkyl.

Description

DESCRIPTION OF EMBODIMENTS

[0134] The invention will be explained in more detail with reference to the following examples, of which the purpose is merely illustrative and not limiting the scope of the invention.

EXAMPLES

Characterization

Equivalent Weight Determination

[0135] A weighted aliquot of the polymer (I) is compression moulded to yield a film, which is first completely hydrolyzed with a KOH solution in water and then treated with nitric acid. Polymer (I) is in this way converted from the precursor (—SO.sub.2F) form to the acid (—SO.sub.3H) form. Equivalent weight is thus determined by titration with a base.

Heat of Fusion Determination

[0136] Heat of fusion of a polymer is determined by DSC following the procedure of ASTM D3418-08. As specifically provided by this standard, heat of fusion is determined from the second heating curve at a heating rate of 10° C./min, after having suppressed effects of thermal history of the sample in a first heating cycle and subsequent cooling in well-defined conditions

Fluoride Emission Rate Determination

[0137] A polymer sample (0.4 g) is added in a polyethylene vessel previously filled with a solution containing Fe(NH.sub.4).sub.2(SO.sub.4).sub.2 (0.05 g) and H.sub.2SO.sub.4 (0.025 g) dissolved in a 15 w/w % solution of H.sub.2O/H.sub.2O.sub.2 (200 g). The mixture thus obtained is heated at 75° C. for 4 hours, and the polymer sample is then removed, the remaining liquid collected. Fluoride concentration in the aqueous medium is assessed via Ion-exchange Chromatography (IC) using a DIONEX ICS3000 chromatography system equipped with a DIONEX IONPACK AS14A anion-exchange column and an eluent generator providing a gradient elution from KOH/H.sub.2O 10 mM to KOH/H.sub.2O 70 mM.

Preparative Example 1: Synthesis of an Allyl-Bearing Fluorinated Polyfunctional Compound of Formula CF.SUB.2.═CFCF.SUB.2.OCF.SUB.2.CF.SUB.2.O-PFPE-OCF.SUB.2.CF.SUB.2.OCF.SUB.2.CF═CF.SUB.2

[0138] 8.81 g Anhydrous KF (151.6 mmol) and 65 mL anhydrous diglyme were charged in a 250 mL glass reactor equipped with two dropping funnels, a reflux condenser, an internal thermometer and a magnetic stirring bar therein. Air in the reactor was removed by nitrogen flux in order to create an inert reaction atmosphere. The reaction mixture was then stirred by the magnetic stirring bar at 1000 rpm and subsequently cooled in an ice-water bath until an internal temperature of 4° C. was reached. 25 g (64.1 mmol) of a perfluoropolyether diacylfluoride FOC-PFPE-COF (C2/C1 ratio in PFPE unit=3.72; EW=198 g/eq) [prepared according to D. SIANESI, G. MARCHIONNI, et al. ORGANOFLUORINE CHEMISTRY: PRINCIPLES AND COMMERCIAL APPLICATIONS. Edited by R.E. BANKS. NEW YORK: PLENUM PRESS, 1994. p. 431. and references therein] was slowly added in 10 minutes, the addition rate being carefully controlled to avoid the internal temperature exceeding 8° C. Once the FOC-PFPE-COF addition was completed, the reaction mixture was stirred for 60 minutes while the internal temperature being kept at 4° C. Then to the resulted mixture was added 34.7 g fluoroallylfluorosulfate (FAFS), CF.sub.2═CFCF.sub.2 OSO.sub.2F (150.9 mmol) prepared by reacting hexafluoropropene and sulfur trioxide (SO.sub.3) in the presence of a boron (BF.sub.3) catalyst [according to I. WLASSICS, et al. Perfluoro Allyl Fluorosulfate (FAFS): A Versatile Building Block for New Fluoroallylic Compounds. Molecules. 2011, vol. 16, p. 6512-6540.], in 15 minutes, the addition speed being carefully controlled to prevent the internal temperature from exceeding 10° C. Once the FAFS addition was completed, the mixture was again stirred at 4° C. for 60 minutes. Subsequently, the mixture was heated to room temperature and stirred for another 3 hours. The crude mixture thus obtained was washed in a separatory funnel with 300 ml distilled water, and the lower organic phase was diluted with an inert, low-boiling fluorinated solvent (CF.sub.3 OCFCIOCF.sub.2Cl; methyl adduct) [according to W. NAVARRINI, V. Tortelli, et al. Organic hypofluorites and their new role in industrial fluorine chemistry. Journal of Fluorine Chemistry. 1999, vol. 95, p. 27-39.] The thus obtained organic layer was then dried over MgSO.sub.4, filtered, and the solvent was evaporated under a reduced pressure. Afterwards, the dried crude organic compound was distilled keeping the PFPE distributions distilling between 76° /76 mm Hg and 98° C./38 mmHg.

[0139] CF.sub.2═CFCF.sub.2OCF.sub.2CF.sub.2O-PFPE-OCF.sub.2CF.sub.2OCF.sub.2CF═CF.sub.2 (Avg. MW=709 g/mol; Functionality=1.80; density=1.69 g/ml; C2/C1 in PFPE unit ratio=3.72) was obtained in 40 mol % Yield vs. starting FOC-PFPE-COF.

[0140] .sup.19F-NMR(ppm): .sup.a,bCF.sub.2═.sup.cCF.sup.dCF.sub.2O.sup.C2CF.sub.2CF.sub.2O).sub.2-.sup.C1PFPE a:-82 (2F); dd; b: −104 (2F); dd; c: −190; (2F); ddt; d: −71 (4F); s C1: −53; s; C2: −90; m.

[0141] FT-IR (cm.sup.−1): 1792 (CF.sub.2═CFCF.sub.2-st); 1213 (CF st).

Preparative Example 2: Synthesis of a an Allyl-Bearing Fluorinated Polyfunctional Compound of Formula CF.SUB.2.═CFCF.SUB.2.OCF.SUB.2.CF.SUB.2.O-PFPE-OCF═CF.SUB.2

[0142] 2.11 g anhydrous KF (36.4 mmol) were suspended in 25 ml anhydrous diglyme in a 250 mL glass reactor equipped with two dropping funnels, a reflux condenser, an internal thermometer and a magnetic stirring bar. Air in the reactor was removed by nitrogen flux in order to create an inert atmosphere. The suspension was stirred at 850 rpm and cooled to 0° C. in a water/ice bath. To the cooled suspension was slowly added 26 g ClCF.sub.2 CFClO-PFPE-OCF.sub.2COF prepared using a mixture of perfluoropolyether diacylfluoride according to U.S. Pat. No. 7,208,638 B (SOLVAY SOLEXIS) 24.04.2007 , in 15 minutes, while the addition speed being carefully controlled to avoid the mixture temperature exceeding 4°-5° C. Upon the addition completion, the mixture was then stirred for 60 minutes at 0° C. 8.3 g FAFS (36.4 mmol) obtained in the same way as described in Preparative Example 1 was then slowly added in 10 minutes, and the additional speed being controlled to avoid the mixture temperature exceeding 10° C. Following the FAFS addition, the mixture was first stirred for 2 hours at 0° C. and then another hour at an increased temperature of 15° C. Afterwards, the crude mixture was poured in a separatory funnel and two separate phases were obtained immediately: a clear, colourless lower phase and a yellow top phase. The lower phase was separated, discarding the top phase which is mainly diglyme. FAFS conversion=100%. Crude adduct yield=75%

[0143] Next, 45 ml DMF and 2.96 g powdery Zn (45.5 mmol) were suspended in a glass reactor identical to the one described above, and were heated to 85° C. with stirring (1000 rpm). Into the suspension the crude adduct was slowly added within 20 minutes, during which a maximum internal temperature of 8° C. was observed. The mixture was then heated to 85°-90° C. and stirred for additional two hours at the increased temperature. Following cooling, the crude dechlorinated organic mixture was poured in a separatory funnel containing 200 ml of distilled water. The organic/water mixture was extracted with 3 portions of 50 ml CH.sub.2Cl.sub.2. The organic layers were then pooled together, dried over MgSO.sub.4, filtered, and the solvent was evaporated under a reduced pressure. The crude oil thus obtained was distilled and the fractions distilling at 160° C./13-21 mm Hg were collected.

[0144] CF.sub.2═CFCF.sub.2OCF.sub.2CF.sub.2O-PFPE-OCF═CF.sub.2 (Avg. MW=903 g/mol; Functionality=1.94; density=1.7 g/ml, b.p.=240° C., C2/C1 PFPE unit=3.38, —CF═CF2/—OCF2CF═CF2=1.15/0.85) was obtained in 38 mol % Yield vs. starting ClCF.sub.2CFClO-PFPE-OCF.sub.2COF.

[0145] .sup.19F-NMR(ppm): .sup.a,bCF.sub.2═.sup.cCF.sup.dCF.sub.2O.sup.C2CF.sub.2CF.sub.2O—.sup.C1PFPE-O.sup.eCF═.sup.f,gCF.sub.2 a: −90 (1F); dd; b: −102.5 (1F); dd; c: −188; (1F); ddt; d: −69.5 (2F); s: Cl: −53; −49; s; C2: −85-−89; m; e: −133.5 (1 F); ddt; .sup.3J.sub.FF=65 Hz; 111 Hz; .sup.4J.sub.FF=6 Hz; f: −112.5; dd; .sup.2J.sub.FF=80 Hz; .sup.3J.sub.FF=65 Hz (1 F, cis); g: -120 (1F); ddt; .sup.2J.sub.FF=84 Hz; .sup.3J.sub.FF=110 Hz (1F, trans).

[0146] FT-IR (cm.sup.−1; KBr): 1792 (CF.sub.2═CFCF.sub.2O— st); 1828 (CF.sub.2═CFO— st); 1193 (CF st).

Preparative Example 3: Synthesis of a an Allyl-Bearing Fluorinated Polyfunctional Compound of Formula (CF.SUB.2.═CFCF.SUB.2.OCF.SUB.2.CF.SUB.2.SO.SUB.2.).SUB.2.NH

(a) Preparation of BrCF.SUB.2.CFBrCF.SUB.2.OCF.SUB.2.CF.SUB.2.SO.SUB.2.F

[0147] 35 ml anhydrous CH.sub.3CN was used to dilute 16.9 g FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF═CF.sub.2 (51.2 mmol) [prepared according to I. WLASSICS, et al. Perfluoro Ally! Fluorosulfate (FAFS): A Versatile Building Block for New Fluoroallylic Compounds. Molculs. 2011, vol. 16, p. 6512-6540.] in a 250 ml glass reactor equipped with a dropping funnel, a reflux condenser, an internal thermometer and a magnetic stirring bar. Air in the reactor was removed by nitrogen flux in order to create an inert atmosphere. The homogeneous solution was stirred at 750 rpm and heated to 80° C. in an oil bath, after which a homogeneous solution of CH.sub.3CN (20 ml) and Br.sub.2 (13.1 g; 81.94 mmol) was slowly added therein, in 25 minutes. The mixture was then stirred at 80° C. for 8 hours. The crude organic solution was washed with 30 ml of 10% (w/v) solution of Na.sub.2S.sub.2O.sub.3 in 150 ml H.sub.2O. A yellow-coloured oil phase separated at the bottom layer was collected, diluted in 50 ml CH.sub.2Cl.sub.2, dried over MgSO.sub.4 and filtered, and the solvent was evaporated under a reduced pressure.

[0148] BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F was obtained with 100% selectivity and 68 mol % yield vs. FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF═CF.sub.2, of which the conversion rate is 100%.

[0149] .sup.19F-NMR(ppm): Br.sup.aCF.sub.2.sup.bCFBr.sup.cCF.sub.2O.sup.dCF.sub.2.sup.eCF.sub.2SO.sub.2.sup.fF a: −55; (2F); (AB); b: −131 (1 F); s; c: −72 (AB); (2F); d: −79.5 (2F); s; e: −109 (2F) s; f: 49.4 (1F); s.

(b) Preparation of BrCF.SUB.2.CFBrCF.SUB.2.OCF.SUB.2.CF.SUB.2.SO.SUB.2.NH.SUB.2

[0150] 1.7 g liquid NH.sub.3 (97.9 mmol) was obtained by condensing NH.sub.3 in a vessel at −78° C. by flowing in said vessel a gaseous stream obtained by heating NH.sub.4OH at 60° C. under a slight flux of N.sub.2. The −78° C. vessel containing NH.sub.3 (liq.) was connected by means of PTFE tubing to a reflux condenser, which was equipped with a latex balloon at its off-gas exit port and was also cooled to −78° C. Said reflux condenser was attached to the top of a 100 mL glass reactor equipped with a dropping funnel, an internal thermometer, and a magnetic stirring bar. Air in the reactor was removed by nitrogen flux in order to create an inert atmosphere. The reactor was at 20° C. and was loaded with 8.0 g (16.34 mmol) of BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F diluted in 50 ml CF.sub.3OCFClCF.sub.2Cl. The vessel with NH.sub.3 (liq.) was slowly warmed to room temperature, thereby condensing NH.sub.3 (liq.) inside the reactor. The internal reactor temperature dropped to −10° C. after condensation and was subsequently heated to room temperature by immersing it in an oil bath at 50° C. As the reaction proceeded, a yellow-orange solid (NH.sub.4F) formed along the sides of the reactor and the reflux rate on the reflux condenser was observed to slow down. The reactor was heated externally until the internal temperature approached the external temperature, which was an indicator that [NH.sub.3] was lowering and that the reaction was over. The reflux condenser was re-heated to room temperature, the oil bath was removed from under the reactor, and stirring was maintained until no refluxing was observed and all excess NH.sub.3 (gas) entered the latex balloon. The crude mixture was then diluted in another 50 ml CF.sub.3OCFClCF.sub.2Cl and the diluted mixture was then poured in 250 ml H.sub.2O, resulting separation of two homogeneous phases. The pH value of the top aqueous phase was measured to be 7.8. It was titrated to pH value of 1.8 with 20 ml of HCl (37% w/w). The lower organic phase was separated, dried over MgSO4, filtered and the solvent was evaporated under reduced pressure. The reddish, oily residue crystallized to give needle-shaped crystals at 20° C. in 2 hours.

[0151] BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2NH.sub.2 was obtained in 58 mol % Yield, with a respective conversion of 97.5%.

[0152] .sup.19F-NMR(ppm): Br.sup.aCF.sub.2.sup.bCFBr.sup.cCF.sub.2O.sup.dCF.sub.2.sup.eCF.sub.2SO.sub.2NH.sub.2 a: −55 (AB); (2F); b: −130.8 (1F); s; c: −72.5 (AB); (2F); d: −78.7 (m); (2F); e: −114.3 (s), (2F). FT-IR (cm.sup.−1; KBr): 1535 (—SO2—NH2 st); 3388.6, 3274.7 (—NH2 st); 1201 (CF st).

(c) Preparation of (BrCF.SUB.2.CFBrCF.SUB.2.OCF.SUB.2.CF.SUB.2.SO.SUB.2.).SUB.2.NH

[0153] 4.64 g of BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F (9.47 mmol) and 4.61 g BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2NH.sub.2 (9.47 mmol) were placed in a 100 ml glass reactor equipped with a dropping funnel, an internal thermometer and a magnetic stirring bar, and the reactor was connected to a reflux condenser having a latex balloon connected to its top off-gas exit port. Air in the reactor was removed by nitrogen flux in order to create an inert atmosphere. Into the reactor was added 35 ml of anhydrous CH.sub.3CN, and the homogeneous solution was stirred at 900 rpm at 20° C. Next, 2.14 g tetramethyl guanidine (18.63 mmol) was slowly added in the reactor and 11° C. exothermicity was recorded. Tetramethyl guanidinium fluoride salt was observed to precipitate out of solution. The thus obtained crude mixture was measured to have a pH value of 11.9 and it was titrated to pH ˜1 with 1 ml of 37% HCl (w/w). The titrated, acidic crude mixture was then washed with 150 ml H.sub.2O. An orange-colour solid precipitated out of solution, which was diluted in 50 ml CH.sub.2Cl.sub.2. The homogeneous organic mixture was then dried over MgSO4, filtered, and the solvent was evaporated under a reduced pressure. A dark-yellow coloured oil was obtained.

[0154] (BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2).sub.2NH was obtained in 99% Yield, with a selectivity of 99%.

[0155] .sup.19F-NMR(ppm): (Br.sup.aCF.sub.2.sup.bCFBr.sup.cCF.sub.2O.sup.dCF.sub.2.sup.eCF.sub.2SO.sub.2).sub.2NH a: -58 (AB); (4F); b: −133.6 (2F); s; c: −81.3 (AB); (4F); d: −75.6 (AB); (4F); e: −116.5 (s), (4F). FT-IR (cm.sup.−1; KBr): 1526; 1573, 1475 (—SO2—NH2 st); 3353 (—NH st); 1993 (CF st).

(d) Preparation of (CF.SUB.2.═CFCF.SUB.2.OCF.SUB.2.CF.SUB.2.SO.SUB.2.).SUB.2.NH

[0156] 1.796 g of powdery Zn (28.35 mmol) was suspended in 50 ml anhydrous DMF in a 100 ml glass reactor equipped with a dropping funnel, an internal thermometer and a magnetic stirring bar, the reactor being connected with a reflux condenser having a latex balloon connected to its top off-gas exit port. Air in the reactor was removed by nitrogen flux in order to create an inert atmosphere. The heterogeneous mixture was heated to 80° C. and was stirred at a speed of 1000 rpm. 9.08 g (BrCF.sub.2CFBrCF.sub.2OCF.sub.2CF.sub.2SO.sub.2).sub.2NH (9.5 mmol; 19 meq) was diluted in 10 ml of anhydrous DMF, placed in the dropping funnel and slowly added to the Zn suspension. During the addition an exothermicity of 7° C. was observed, which lasted for about 40 minutes as the duration of the debromination reaction. The mixture was stirred at 80° C. for another 2 hours after the exothermicity dropped. At the end of the reaction, the crude organics were placed in a separatory funnel containing 350 ml H.sub.2O acidified with 10 ml 37% HCl (w/w). A yellow-coloured oil very slowly separated to the bottom layer. The oil was first diluted in 50 ml CH.sub.2Cl.sub.2, and then retro-extracted with 100 ml H.sub.2O to remove residual tetraguanidinium salts from the previous reaction. The homogeneous organic mixture was dried over MgSO.sub.4, filtered, and the solvent was evaporated under a reduced pressure.

[0157] (CF.sub.2═CFCF.sub.2OCF.sub.2CF.sub.2SO.sub.2).sub.2NH was obtained in 74 mol % Yield, with a density measured to be 1.633 g/ml.

[0158] .sup.19F-NMR (ppm; DMSO d6): (.sup.a,bCF.sub.2═.sup.cCF.sup.dCF.sub.2O.sup.eCF.sub.2.sup.fCF.sub.2SO.sub.2).sub.2N.sup.gH a: −92 dd (2F); b: −104, dd (2F); c: −190, ddt (2F); d: −72 s (4F); e: −81, m (4F); f: −117 s, (4F). 1H-NMR (ppm; DMSO d6) g: 3.3 (broad).

[0159] FT-IR (cm.sup.−1; KBr): 1793 (CF2═CFCF2O— st.); 1328 (—SO2-NH st); 3482 (NH st).

Preparative Example 4 (Comparative): Synthesis of a Vinyl-Bearing Fluorinated Compound of Formula CF.SUB.2.═CF—O—(CF.SUB.2.CF.SUB.2.).SUB.2.—O—CF═CF.SUB.2

(a) Synthesis of ClCF.SUB.2.CFClOCF.SUB.2.CF.SUB.21 .(“Compound A”)

[0160] 800 ml H.sub.2O and 250 ml dioxane were placed in a round-bottomed flask glass reactor and were stirred at 750 rpm, at 20° C. for 20 minutes, whilst using nitrogen to inert the atmosphere. Next, 754 g Na.sub.2SO.sub.3 (5.98 mol) was added in the reactor and dissolved in the aqueous layer. The reducing mixture was then heated to 60° C. by means of an oil bath and 700 g of ClCF.sub.2CFClO—CF.sub.2CF.sub.2SO.sub.2F (2 mol; “1”) was slowly added (using 30 min) from a dripping funnel. Exothermicity was observed to have a maximum of 20° C. increase. Following the addition of 1, the reaction temperature was maintained at 80° C. for 5 hours. Afterwards, the crude mixture was cooled, the precipitate was removed by filtration and both dioxane and H.sub.2O were evaporated at 50° C. and a reduced pressure. The resulting solid was washed with 800 ml isopropanol, in order to remove residual inorganic salts. The mixture was filtered and the solid was dried in an oven at 40° C. at a reduced pressure.

[0161] 560 g of sulfinate (ClCF.sub.2CFClOCF.sub.2CF.sub.2SO.sub.2Na; 1.57 mol; “2”) was placed in a round bottomed flask glass reactor equipped with a gas bubble counter, together with 399 g of I.sub.2 (1.57 mol) and 800 ml of CH.sub.3CN used as solvent. The mixture was then heated to 55° C. with stirring at 800 rpm. After 5 hours no more gas bubbles (SO.sub.2) were observed at the exit port of the bubble counter, an indicator that the reaction was complete. The crude mixture was first stripped with a Claisen condenser and the crude distillate was firstly washed twice with a 10% Na.sub.2SO.sub.3 aqueous solution and the organic layer was further washed with a 10% NaCl aqueous solution, to remove the residual CH.sub.3CN. The organic layer was dissolved in CH.sub.2Cl.sub.2, dried over MgSO.sub.4, filtered, and the solvent was removed under reduced pressure.

[0162] ClCF.sub.2CFClOCF.sub.2CF.sub.2I was obtained in 62 mol % Yield, with a 100% conversion vs. 1 and a 81% conversion vs. 2.

[0163] .sup.19F NMR (ppm): Cl.sup.aCF.sub.2.sup.bCFClO.sup.cCF.sub.2.sup.dCF.sub.2I a: −64.5 (AB, 2F); b: −71 (s; 1 F); c: −81 (AB; 2F); d: −62 (s; 2F).

(b) Synthesis of [ClCF.SUB.2.CFClOCF.SUB.2.CF.SUB.2.].SUB.2 .(“Compound B”)

[0164] 60 g of Zinc (920 mmol), 500 ml CH.sub.2Cl.sub.2, and 156 g acetic anhydride (1.52 mol) were placed in a round-bottomed flask glass reactor and were stirred at 750 rpm, at 20° C. for 20 minutes, whilst using nitrogen to inert the atmosphere. Next, 300 g of Compound A (759 mmol) were dripped at 20° C., during which an exothermicity of 10° C. was observed. Once the addition of Compound A was finished, the internal reaction temperature was raised to 40°-45° C. (CH.sub.2Cl.sub.2 reflux) by an oil bath. A white precipitate of ZnI.sub.2 formed after 6 hours. The crude mixture was first cooled, filtered to remove ZnI.sub.2, and washed with 10% NaOH aqueous solution to remove acetic acid, and then the organic layer was stripped under a reduced pressure at 20° C. to remove most of residual CH.sub.2Cl.sub.2. Spalt-Rohr Fischer (60 theoretical plates) distillation of the stripped organic layer gave the desired product “Compound B”.

[0165] Compound B (b.p.: 60° C./10 mm Hg=180° C./760 Torr.) was obtained in 70 mol % Yield, with a 100% conversion vs. Compound A.

[0166] .sup.19F NMR (ppm): [Cl.sup.aCF.sub.2.sup.bCFClO.sup.cCF.sub.2.sup.dCF.sub.2].sub.2 a: −69.5 (AB, 4F); b: −76 (s; 2 F); c: −83 (AB; 4F); d: −124.5 (s; 4F).

(c) Synthesis of [CF.SUB.2.═CFOCF.SUB.2.CF.SUB.2.].SUB.2 .(“Compound C”)

[0167] 35.8 g Zinc (550 mmol), 250 ml DMF and 4 g of ZnCl.sub.2 were placed in a round-bottomed flask glass reactor and were stirred at 900 rpm, at 20° C. for 20 minutes, whilst using nitrogen to inert the atmosphere. The heterogeneous mixture was heated to 80° C. in an oil bath for 30 min. Then, 106 g of compound B was slowly added from a dripping funnel, during which a peak exothermicity of 15° C. was observed. The mixture was continuously stirred at 85° C.-90° C. for 2 hours, after which the conversion is complete with concomitant generation of a white precipitate of ZnCl.sub.2. Claisen distillation at 50° C. and a 60 mm Hg residual pressure gave crude Compound C, which was then distilled at the Spalt-Rohr Fischer (60 theoretical plates) to obtain pure Compound C.

[0168] Compound C (b.p.=116° C.-117° C./760 Torr.) was obtained in 90 mol % Yield with a 100% conversion vs. Compound B, giving an overall Yield of 40 mol %.

[0169] .sup.19F NMR (ppm): [.sup.a,bCF.sub.2═.sup.cCFO.sup.dCF.sub.2.sup.eCF.sub.2].sub.2 a: −111.5; dd; .sup.2J.sub.FF=80 Hz; .sup.3J.sub.FF=65 Hz (2F, cis); b: −118.5 (2F); ddt; .sup.2J.sub.FF=84 Hz; .sup.3J.sub.FF=110 Hz (1F, trans); c: −133.5 (2 F); ddt; .sup.3J.sub.FF=65 Hz; 111 Hz; .sup.4J.sub.FF=6 Hz; d: −81; s; 4F; e: −121; s; 4F.

Example 1: Fluorinated Polymer (“P1”) Prepared from the Allyl-Bearing Fluorinated Polyfunctional Compound of Preparative Example 1 (“Crosslinker 1”)

[0170] In a 5 L autoclave the following reagents were charged: [0171] 2.6 L of demineralised water; [0172] 145 g of the monomer with formula: CF.sub.2═CF—O—CF.sub.2CF.sub.2—SO.sub.2F [0173] 720 g of a 5 wt % aqueous solution of CF.sub.2ClO(CF.sub.2CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.m CF.sub.2COOK (avg. MW=521, ratio n/m=10); [0174] 1 ml of a solution containing the crosslinker 1 CF.sub.2═CFCF.sub.2OCF.sub.2CF.sub.2O-PFPE-OCF.sub.2CF.sub.2OCF.sub.2CF═CF.sub.2 (5% by volume) dissolved in Galden® PFPE D02

[0175] The autoclave, stirred at 650 rpm, was heated at 50° C. A water based solution with 27 g/L of potassium persulfate was added in a quantity of 66 mL. The pressure was maintained at a value of 8 bar (abs.) by feeding tetrafluoroethylene.

[0176] After adding 40 g of tetrafluoroethylene in the reactor, 40 g of the monomer CF.sub.2═CF—O—CF.sub.2CF.sub.2—SO.sub.2F and 1 ml of the crosslinker 1 dissolved in Galden® PFPE D02 (5% by volume) were added every 40 g of tetrafluoroethylene fed to the autoclave.

[0177] The reaction was stopped after 300 min by stopping the stirring, cooling the autoclave and reducing the internal pressure by venting the tetrafluoroethylene; a total of 800 g of tetrafluoroethylene was fed into the autoclave.

[0178] The latex was then coagulated by freezing and thawing and the recovered polymer was washed with water and dried at 150° C. for 24 hours.

[0179] Equivalent weight (EW) of the polymer was determined by titration to be 741 g/eq.

[0180] Heat of fusion of the polymer was determined to be 4.04 J/g.

Example 2: Fluorinated Polymer (“P2”) Prepared from the Allyl-Bearing Fluorinated Polyfunctional Compound of Preparative Example 2 (“Crosslinker 2”)

[0181] Example 1 was repeated except that the 1 ml solution containing the crosslinker 1 (5% by volume) dissolved in Galden® PFPE D02 was replaced by 1 ml solution containing a crosslinker 2 (11% by volume) in Galden® PFPE D02.

[0182] Equivalent weight of the polymer was determined to be 693 g/eq.

[0183] Heat of fusion of the polymer was determined to be 2.05 J/g.

Example 3: Fluorinated Polymer (“P3”) Prepared from the Allyl-Bearing Fluorinated Polyfunctional Compound of Preparative Example 3 (“Crosslinker 3”)

[0184] Example 1 was repeated except that the 1 ml solution containing the crosslinker 1 (5% by volume) dissolved in Galden® PFPE D02 was replaced by 1 ml solution containing a crosslinker 3 (8.5% by volume) in Galden® PFPE D02.

[0185] Equivalent weight of the polymer was determined to be 747 g/eq.

[0186] Heat of fusion of the polymer was determined to be 2.96 J/g.

[0187] Noticeably, polymers P1-P3 of the present invention each has a relative low range of EW (i.e. from 650 to 750) compared to many commercially existing ionomers, such as the aforementioned NAFION® from Dupont (whose EW is typically in the range of 1000 to 1200), and therefore provides a desirably high ion exchange capability in electrochemical applications. Moreover, polymers P1-P3 are each characterized by a heat of fusion from 2 to 8 J/g, indicative of their semi-crystalline structure and showing that the polymers are advantageously melt processable.

Comparative Example 4: Fluorinated Polymer (“P4”) Prepared from the Vinyl-Bearing Fluorinated Compound of Preparative Example 4 (“Crosslinker 4”)

[0188] Example 1 was repeated except that: [0189] the 1 ml solution containing the crosslinker 1 (5% by volume) dissolved in Galden® PFPE D02 was replaced by 1 ml solution containing a vinyl-bearing crosslinker 4 (5% by volume) in Galden® PFPE D02; and [0190] the reaction was stopped after 350 minutes by stopping the stirring.

[0191] Equivalent weight of the polymer was determined to be 740 g/eq.

Comparative Example 5: Fluorinated Polymer (“P5”) Prepared from a Bis-Olefin Crosslinking Agent of CH.SUB.2.═CH—(CF.SUB.2.).SUB.6.—CH═CH.SUB.2

[0192] Example 1 was repeated except that the 1 ml solution containing the crosslinker 1 (5% by volume) dissolved in Galden® PFPE D02 was replaced by 1 ml solution containing a bis-olefin crosslinker (5% by volume) of CH.sub.2═CH—(CF.sub.2).sub.6—CH═CH.sub.2 in Galden® PFPE D02.

[0193] Equivalent weight of the polymer was determined to be 751 g/eq.

Example 6: Manufacture of a Membrane Specimen from P1

[0194] 9g of polymer powder of P1 was molten between two PTFE sheets in a preheated press following the steps described below:

[0195] (1) 5 minutes of heating at 280° C. with no pressure applied;

[0196] (2) 1 minute of degassing at 280° C., with a pressure of 0.11 kN/cm.sup.2 applied;

[0197] (3) 3 minutes of heating at 280° C., with a pressure of 0.15 kN/cm.sup.2 applied; and;

[0198] (4) Cooling down at room temperature for 20 minutes,

[0199] The membrane specimens thus obtained has a thickness of 200 micron, with no presence of bubbles detected.

[0200] 0.4 g of the specimen sample thus obtained was then subjected to fluoride emission determination as described above, and was determined have a Fluoride Emission Rate (FER) of 0.115 mg.sub.F/g.sub.sample.

Examples 7-10: Manufacture of Membrane Specimens from P2-P5

[0201] Membranes prepared from P2-P5 were obtained using the same procedure described in Example 6, and each with the Fluoride Emission

[0202] Rate (FER) determined, as listed in the table below.

TABLE-US-00001 TABLE 1 Fluoride Emission Rate of crosslinked fluorinated ionomers Polymer Sample EW FER* Polymer [g/mol] [mg.sub.F/g.sub.sample] Crosslinker Structure P1 741 0.115 (0.021) (CF.sub.2═CFCF.sub.2O).sub.2—PFPE P2 693 0.175 (0.007) CF.sub.2═CFCF.sub.2O—PFPE—OCF═CF.sub.2 P3 747 0.147 (0.016) (CF.sub.2═CFCF.sub.2OCF.sub.2CF.sub.2SO.sub.2).sub.2NH P4 740 0.162 (0.011) CF.sub.2═CFO(CF.sub.2).sub.4OCF═CF.sub.2 (comp.) P5 751 0.245 (0.049) CH.sub.2═CH—(CF.sub.2).sub.6—CH═CH.sub.2 (comp.) *The FER value was expressed in the form of AVG. (SD)

[0203] Noticeably, as shown in Table 1, all three membranes prepared from the ionomers of the present invention (P1-P3) showed superior resistance to chemical degradation in oxidative environment, especially compared to the specimen prepared from the bis-olefin crosslinker (P5). In this aspect, even comparing to the specimen prepared from the vinyl-bearing crosslinking agent (P4), the polymers of the prevent invention showed better results (P1 and P3), or at least statistically indistinguishable (P2).

[0204] This high chemical stability of the polymer of the present invention, added to its intrinsic mechanical stability induced by the crosslinking, advantageously allows one to make polymer membranes of longer lifetime and consequently broaden its application in many industrial fields.

[0205] Without wishing to be bound by theory, the Applicant believes that he introduction as comonomer of the allyl-bearing fluorinated polyfunctional compounds of formula (II) is advantageous since the particular structure of said comonomer promote pre-crosslinking of the ionomer during the polymerization, and also advantageously increases the length of the primary chains forming the final polymer without introducing in the molecular structure any weak point when subjected to chemical degradation in fuel cell environment.