METHOD FOR THE MANUFACTURE OF FLUORINATED POLYMERS AND POLYMERS OBTAINABLE THEREFROM

Abstract

A method for the manufacture of fluorinated polymers and polymers obtainable therefrom are herein disclosed. The method envisages the reaction of a) first reagent [reagent (R1)] which is an alcohol selected from a (per)fluoropolyether (PFPE) alcohol a fluoroalkylene diol and a mixture thereof; b) a second reagent [reagent (R2)] which is a sulfonic ester of a PFPE, a sulfonic diester of a fluoroalkylene diol or a mixture thereof and, optionally, c) a third reagent which is a mono-functional (per)haloalkyl alcohol or a sulfonic ester thereof in the presence of an organic or inorganic base. At least reagent (R1) is a PFPE alcohol (A) or at least reagent (R2) is a PFPE sulfonic ester (B) and the overall equivalents of alcohols are the same as the overall equivalents of sulfonic esters. The method allows to obtain in a convenient way non-functional polymers comprising at least a PFPE segment and having high molecular weight.

Claims

1. A method for the manufacture of a fluorinated polymer (P), said method comprising the reaction of: a) a first reagent (R1), wherein reagent (R1) is an alcohol selected from: a PFPE alcohol (A) wherein PFPE alcohol (A) is a (per)fluoropolyether alcohol having an average functionality (F.sub.A) ranging from 1.2 to 2, an alcohol (Aa) wherein alcohol (Aa) is a fluoroalkylene diol, and mixtures thereof; b) a second reagent (R2), wherein reagent (R2) is a sulfonic ester selected from: a PFPE sulfonic ester (B), wherein PFPE sulfonic ester (B) is a sulfonic ester of a PFPE alcohol having an average functionality (F.sub.B) ranging from 1.2 to 2, a sulfonic ester (Bb), wherein sulfonic ester (Bb) is a sulfonic diester of a fluoroalkylene diol, and mixtures thereof; and c) a third reagent (R3), wherein reagent (R3) is: an alcohol (C), wherein alcohol (C) is a mono-functional (per)haloalkyl alcohol, or a sulfonic ester (Cc), wherein sulfonic ester (Cc) is a sulfonic ester of alcohol (C), reagent (R3) being optional when (F.sub.A) and/or (F.sub.B) is lower than 1.98, in the presence of an organic or inorganic base, wherein: (i) at least reagent (R1) is a PFPE alcohol (A) or at least reagent (R2) is a PFPE sulfonic ester (B) and in that: (iia) when reagent (R3) is not used, the overall equivalents of alcohols are the same as the overall equivalents of sulfonic esters; and (iib) when reagent (R3) is used, the overall equivalents of alcohols are the same as the overall equivalents of sulfonic esters or reagent (R3) can be used in excess with respect to the amount required to comply with this proviso.

2. The method according to claim 1 wherein reagent (R1) is a PFPE alcohol (A) and reagent (R2) is a PFPE sulfonic ester (B).

3. The method according to claim 1 wherein reagent (R1) is a PFPE alcohol (A) and reagent (R2) is a sulfonic ester (Bb).

4. The method according to claim 1 wherein reagent (R1) is an alcohol (Aa) and reagent (R2) is a PFPE sulfonic ester (B).

5. The method according to claim 1 wherein at least one of (F.sub.A) or (F.sub.B) is higher than 1.80.

6. The method according to claim 1 wherein PFPE alcohol (A) complies with formula (A 1):
ZOR.sub.fZ(A-1) wherein (R.sub.f) is a fluoropolyoxyalkylene chain and Z and Z, equal to or different from one another, represent a hydrocarbon group containing one hydroxy group, said hydrocarbon group being partially fluorinated and optionally containing one or more ethereal oxygen atoms, or a C.sub.1-C.sub.3 haloalkyl group.

7. The method according to claim 6 wherein groups Z and Z comply with formula (Z-1):
CFXCH.sub.2(OCH.sub.2CHY).sub.nOH (Z-1) wherein: X is F or CF.sub.3, Y is hydrogen or methyl and n is 0 or an integer equal to or higher than 1.

8. The method according to claim 1, wherein PFPE sulfonic ester (B) complies with formula (B-1):
E-O-R.sub.f-E(B-1) wherein (R.sub.f) is a fluoropolyoxyalkylene chain and E and E, equal to or different from one another, represent a hydrocarbon group bearing one sulfonic ester group, said hydrocarbon group being partially fluorinated and optionally containing one or more ethereal oxygen atoms, or a C.sub.1-C.sub.3 haloalkyl group.

9. The method according to claim 8, wherein groups E and E comply with formula (E-1):
CFXCH.sub.2(OCH.sub.2CHY).sub.nE* (E-1) wherein: X is F or CF.sub.3, Y is hydrogen or methyl, n is 0 or is an integer equal to or higher than 1, and E.sup.* is selected from a mesylate, nonaflate or tosylate group.

10. The method according to claim 8, wherein chain (R.sub.f) complies with formula (R.sub.f-III) here below:
(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2(R.sub.f-III) wherein: a1, and a2 are integers >0 such that the number average molecular weight is between 400 and 4,000, with the ratio a2/a1 being comprised between 0.2 and 5.

11. The method according to claim 1, wherein alcohol (Aa) complies with formula (Aa-1):
HO(CH.sub.2).sub.n*(R.sub.f1a)(CH.sub.2).sub.n*OH (Aa-1) wherein: (R.sub.f1a) is a straight or branched fully or partially fluorinated alkylene chain and n* is 1 or 2.

12. The method according to claim 1, wherein sulfonic ester (Bb) complies with formula (Bb 1):
RSO.sub.2O(CH.sub.2).sub.n*(R.sub.f1a)(CH.sub.2).sub.n*OSO.sub.2R wherein: (R.sub.f1a) is a straight or branched fully or partially fluorinated alkylene chain; n* is 1 or 2; and R is selected from: (halo)alkyl and aryl, wherein the aryl moiety optionally bears one or more (halo)alkyl substituents and/or one or more nitro groups.

13. The method according to claim 1, wherein reagent (R3) is used and wherein reagent (R3) is an alcohol (C) or a sulfonic ester (Cc) respectively complying with formulae (C-1) or and (Cc-1):
R.sub.f2OH (C-1)
R.sub.f2OSO.sub.2R (Cc-1) wherein: (R.sub.f2) is a straight or branched fully or partially halogenated alkyl chain, said chain optionally comprising one or more ethereal oxygen atoms and R is selected from: (halo)alkyl and aryl, wherein the aryl moiety optionally bears one or more (halo)alkyl substituents and/or one or more nitro groups.

14. The method according to claim 1 wherein reagent (R3) is used and: either all reagents are mixed together and reacted to provide polymer (P) or PFPE alcohol (A) and/or alcohol (Aa) and PFPE ester (Bb) and/or ester (Bb) are first reacted together to provide an intermediate functional polymer (Pi) comprising at least one hydroxy end group or at least one sulfonic end group, which is reacted, without being isolated, with alcohol (C) or sulfonic ester (Cc).

15. A polymer complying with formula (P-a): (P-a)
T.sub.N-(S.sup.F1)(R.sub.h)O(R.sub.h)(S.sup.F2)[(R.sub.h)O(R.sub.h)(S.sup.F1)(R.sub.h)O(R.sub.h)(S.sup.F2)].sub.p[(R.sub.h)O(R.sub.h)(S.sup.F1)].sub.q-T.sub.N in which: one of (S.sup.F1) or (S.sup.F2) is a (per)fluoropolyether segment and the other one is a (per)fluoroalkylene segment; (R.sub.h) and (R.sub.h) equal to or different from one another, are selected from straight or branched divalent alkylene segments, each comprising at least one carbon atom; when (R.sub.h) and (R.sub.h) comprise more than one carbon atom, they can optionally be interrupted by one or more ethereal oxygen atoms each T.sub.N, equal to or different from one another, is selected from: a C.sub.1-C.sub.3 haloalkyl group, typically selected from CF.sub.3, CF.sub.2Cl, CF.sub.2CF.sub.2Cl, C.sub.3F.sub.6Cl, CF.sub.2Br, CF.sub.2CF.sub.3 and CF.sub.2H, CF.sub.2CF.sub.2H; and a non-functional group of formula R.sub.f2OR.sub.h wherein R.sub.f2 is as defined above and R.sub.h is a straight or branched divalent alkylene segment comprising at least one carbon atom; when R.sub.h comprises more than one carbon atom, it can be interrupted by one or more ethereal oxygen atoms; p is 0 or a positive number and q is 0 or 1 with the proviso that p and q are not both 0.

16. The method according to claim 6, wherein the C.sub.1-C.sub.3 haloalkyl group is selected from CF.sub.3, CF.sub.2Cl, CF.sub.2CF.sub.2Cl, C.sub.3F.sub.6Cl, CF.sub.2Br, CF.sub.2CF.sub.3, CF.sub.2H, and CF.sub.2CF.sub.2H.

17. The method according to claim 8, wherein the C.sub.1-C.sub.3 haloalkyl group is selected from CF.sub.3, CF.sub.2Cl, CF.sub.2CF.sub.2Cl, C.sub.3F.sub.6Cl, CF.sub.2Br, CF.sub.2CF.sub.3, CF.sub.2H, and CF.sub.2CF.sub.2H.

Description

EXAMPLES

[0237] Examples 1-6 illustrate method (M) comprising the use of an alcol (C) or a sulfonic ester (Cc) and carried out in two steps (referred to as steps 1 and 2 in the examples), while example 7 illustrate method (M) carried out without using an alcohol (C).

Example 1Synthesis of a Polymer (P) of the Invention Starting from Fomblin Z DOL PFPE (2)

[0238] Step 1aSynthesis of Fomblin Z DOL PFPE (2) Nonaflate

[0239] A glass reactor was charged with triethylamine (TEA) (4.95 g, 49 meq) and perfluoro-1-butanesulfonyl fluoride (12.3 g, 40.8 meq) and the resulting mixture was kept under mechanical stirring. The internal temperature of the reaction mass was lowered to 5 /+5 C. using a dry ice bath. Fomblin Z DOL PFPE (2) (76 g, 19 mmoles, 38 meq) was added drop-wise under vigorous stirring. After that, the reaction mixture was warmed up to room temperature, under mechanical stirring. The reaction was monitored by .sup.19F-NMR. After 2 hours at room temperature, a sample was taken for .sup.19F-NMR analysis (conversion 70%). The internal temperature was increased to 70 C. until completion of the reaction. After complete conversion, the reaction mixture was cooled to room temperature and washed twice with ethanol (20 g per washing). An organic bottom phase formed; this phase was separated and the solvent was stripped at 70 C. under vacuum. Fomblin Z DOL PFPE nonaflate (M.sub.n=4,560 E.sub.w=2.280) was isolated with a purity >95% and a yield >90%.

Step 1Reaction of Fomblin Z DOL PFPE (2) with Fomblin Z DOL PFPE nonaflate of

Step 1 (Molar Ratio 1.1:1)

[0240] A glass reactor was charged with Fomblin Z DOL PFPE (2) (80 g, 20 mmoles, 40 meq). The internal temperature of the resulting mixture was lowered to 10 C. using an ice bath. Anhydrous potassium tert-butoxide (2.4 g, 21 meq) was added using a tailed tube, under mechanical stirring. Thereafter, the mixture was warmed up to room temperature, under mechanical stirring, and subsequently heated to 40 C. for 3 hours and then at 80 C. under vacuum for 3 further hours, in order to remove the tert-butanol formed in the course of the reaction.

[0241] Hexafluoroxylene (HFX; 40 ml; 44% w/w vs. the formed Fomblin Z DOL

[0242] PFPE potassium salt) was then added and the Fomblin Z DOL PFPE nonaflate prepared in Step 1a (82 g, 18 mmoles, 36 meq) was added drop-wise under vigorous stirring in 4 hours. The resulting mixture was heated at 120 C. for 20 hrs. The progress of the reaction was followed by .sup.19F-NMR and typically one addition of 10% by moles vs. the original amount of potassium tert-butoxide every 5 hours reaction time was necessary to maintain reasonable reaction kinetics. After complete conversion, the product was diluted with HFX/ethanol and was washed with aqueous HCl 10% w/w. The bottom organic phase was separated and washed again with basic water at 50 C. and separated. Finally, neutral water was used. Complete phase separation was carried out by centrifugation (3500 rpm, 20 min) and any residual solvents were distilled at 70 C. under vacuum.

[0243] The resulting clear product was filtered on a 0.2 m PTFE+glass prefilter. A sample was taken and submitted to vacuum distillation at 170 C. in order to remove some volatile impurities, then analysed by .sup.1H-NMR, .sup.19F-NMR and GPC. The analyses confirmed the obtainment of the following product:

HOR.sub.hS.sup.F1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hSA.sup.F1R.sub.hOH

[0244] wherein:

[0245] p=2

[0246] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0247] and S.sup.F1 and S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2, with a1/a2=2

[0248] M.sub.n=28,500

[0249] E.sub.w=14,250

[0250] The overall yield with respect to nonaflate was 95%.

Step 2Reaction of the product of Step 1 by reaction with the nonaflate of trifluoroethanol

[0251] 50 g (1.76 mmoles, 3.53 meq) of the product obtained in Example 1, Step 1 was reacted with 1.91 g (5 mmoles) of trifluoroethanol nonaflate in the presence of 0.6 g (5.3 mmoles) of ter-ButOK. The reaction was completed after 5 h at 120 C.

[0252] The final product was isolated and the .sup.19F and .sup.1H-NMR analyses confirmed the following structure:

CF.sub.3CH.sub.2OSF.sub.1(R.sub.hOR.sub.hS.sub.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1

R.sub.hOCH.sub.2CF.sub.3

[0253] wherein:

[0254] p=2

[0255] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0256] and S.sup.F1 and S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2, with a1/a2=2.

[0257] M.sub.n=28,500

[0258] E.sub.w=14,250

[0259] polydispersity=1.9

Example 2Synthesis of a Polymer (P) of the Invention Starting from Fomblin Z DOL PFPE (1)

[0260] Step 1aSynthesis of Fomblin Z DOL PFPE (1) nonaflate

[0261] 90 g Fomblin Z DOL PFPE (1) nonaflate (M.sub.n 2,600, E.sub.w 1,300) were prepared following the procedure illustrated in Example 1, Step 1a. Purity >95%; yield >90%.

Step 1Reaction of Fomblin Z DOL PFPE with Fomblin Z DOL PFPE nonaflate of Step 1a (molar ratio 1.06:1)

[0262] A glass reactor was charged with 70 g (70 meq) of Fomblin Z DOL PFPE (1) and reacted, according to the procedure described in Example 1, Step 1, with 85.8 g (66 meq) Fomblin Z DOL PFPE (1) nonaflate of Step 1a in a molar ratio between Fomblin ZDOL PFPE (1)/Fomblin ZDOL PFPE (1) nonaflate=1.06.

[0263] The analyses confirmed the obtainment of the following product:

HOR.sub.hS.sub.F1(R.sub.hOR.sub.hS.sub.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sub.F2R.sub.hOR.sub.hS.sub.F1R.sub.hOH

[0264] wherein:

[0265] p=3

[0266] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0267] and S.sup.F1 and S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2, with a1/a2=2.

[0268] M.sub.n=18,300

[0269] E.sub.w9,150.

[0270] The overall yield with respect to nonaflate was >95%.

[0271] Step 2Reaction of the product of Step 1 by reaction with trifluoroethanol nonaflate

[0272] The product of Step 1 was reacted with 3.5 g (9 mmoles) of trifluoroethanol nonaflate in the presence of 1.2 g (11 mmoles) of ter-ButOK. The reaction was completed after 5 hr at 120 C.

[0273] The final product was isolated and .sup.19F and .sup.1H-NMR analyses confirmed the following structure:

CF.sub.3CH.sub.2OR.sub.hS.sup.F1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1

R.sub.hOCH.sub.2CF.sub.3

[0274] wherein p3

[0275] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0276] and S.sup.F1 and S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2, with a1/a2=2

[0277] M.sub.w=18,500

[0278] E.sub.w=9,250

[0279] Polydispersity=2.0

[0280] The overall yield with respect to FomblinZDOL PFPE (1) nonaflate was >95%.

Example 3Synthesis of a polymer (P) of the Invention Comprising C6 Dodecafluoroalkylene Sequences

[0281] Step 1aSynthesis of Fomblin Z DOL PFPE (2) nonaflate

[0282] 500 g Fomblin Z DOL PFPE (2) nonaflate was prepared following the procedure of Example 1, Step 1a above.

Step 1Reaction of 1H, 1H, 8H, 8H-dodecafluoro-1,8-octanediol with Fomblin Z DOL PFPE (2) nonaflate of Step 1 a (molar ratio 1.10:1)

[0283] A glass reactor was charged with 1H, 1h, 8H, 8H-dodecafluoro-1,8-octanediol (36.2 g, 100 mmoles, 200 meq) and 80 ml hexafluoroxylene. The internal temperature of the resulting mixture was lowered to 10 C. using an ice bath. Anhydrous potassium tert-butoxide (24.1 g, 210 meq) dissolved in 300 ml of tert-butanol was added via a tailed tube, under mechanical stirring. Thereafter, the mixture was warmed up to room temperature, under mechanical stirring, and subsequently heated at 40 C. for 3 hours and then at 80 C. under vacuum for 3 further hours, in order to remove 80% of the tert-butanol present in the reaction mixture.

[0284] Fomblin Z DOL PFPE (2) nonaflate prepared in Step la (416 g, 91 mmoles, 182 meq) was added drop-wise under vigorous stirring during 4 hours. The resulting mixture was heated at 120 C. for 20 hrs. The progress of the reaction was followed by .sup.19F-NMR and typically one addition of 10% by moles vs. the original amount of potassium tert-butoxide every 5 hours reaction time was necessary to maintain adequate reaction kinetics.

Step 2Reaction with Trifluoroethanol Nonaflate

[0285] After complete conversion of the Fomblin Z DOL PFPE (2) nonaflate, the reaction mixture was added with trifluoroethanol nonaflate (11.6 g, 30 meq). After complete conversion of the residual OH groups, the a polymer (P) was isolated.

[0286] The .sup.19F and .sup.1H-NMR analyses confirmed the following structure:

CF.sub.3CH.sub.2OR.sub.hS.sup.F1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1

R.sub.hOCH.sub.2CF.sup.3

[0287] wherein p=2.6

[0288] S.sup.F1(CF.sub.2).sub.6

[0289] S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2 with a1/a2=2 and

[0290] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0291] M.sub.n=9,200

[0292] E.sub.w=4,600

[0293] Polydispersity=2.05

[0294] The overall yield with respect to Fomblin Z DOL PFPE (2) nonaflate was >95%.

Example 4Synthesis of a Polymer (P) According to the Invention Comprising C8 Hexadecafluoroalkylene Sequences

[0295] Step 1aSynthesis of Fomblin Z DOL PFPE (2) Nonaflate

[0296] This step was carried out as described in Example 1 above.

Step 1Reaction of 1H, 1H, 10H, 10H-hexadecafluoro-1,10-decanediol with Fomblin Z DOL PFPE(2) Nonaflate of Step 1 a (molar ratio 1.10:1)

[0297] A glass reactor was charged 1H, 1H, 10H, 10H-hexadecafluoro-1,10-decanediol (30 g, 65 mmoles, 130 meq) and 80 ml hexafluoroxylene. The internal temperature of the resulting mixture was lowered to 10 C. using an ice bath. Anhydrous potassium tert-butoxide (15.5 g, 135 meq) dissolved in 200 ml of tert-butanol was added via a tailed tube, under mechanical stirring. Thereafter, the mixture was warmed up to room temperature, under mechanical stirring, and subsequently heated to 40 C. for 3 hours and then at 80 C. under vacuum for 3 further hours, in order to remove 80% of the tert-butanol present in the reaction mixture.

[0298] Hexafluoroxylene (HFX; 40 ml; 44% w/w vs. the formed 1H, 1H, 10H, 10H-hexadecafluoro-1,10-decanediol potassium salt) was then added and the Fomblin Z DOL PFPE (2) nonaflate prepared in Step la (269 g, 59 mmoles, 118 meq) was added drop-wise under vigorous stirring in 4 hours. The resulting mixture was heated at 120 C. for 20 hrs. The progress of the reaction was followed by .sup.19F-NMR and typically one addition of 10% by moles vs. the original amount of potassium tert-butoxide every 5 hours reaction time was necessary to maintain adequate reaction kinetics.

Step 2Reaction with Trifluoroethanol Nonaflate

[0299] After complete conversion of the Fomblin Z DOL PFPE (2) nonaflate, the reaction mixture was added with trifluoroethanol nonaflate (11.6 g, 30 meq). After complete conversion of the residual OH groups, a polymer (P) was isolated, according to known methods. The .sup.19F and .sup.1H-NMR analyses confirmed the following structure:

CF.sub.3CH.sub.2OR.sub.hSF.sup.1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1

R.sub.hOCH.sub.2CF.sup.3

[0300] wherein p=2.6

[0301] S.sup.F1=(CF.sub.2).sub.8

[0302] S.sup.F2=CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2 with a1/a2=2 and

[0303] R.sub.hOR.sub.h=CH.sub.2OCH.sub.2

[0304] M.sub.n=9,700

[0305] E.sub.w=4,350

[0306] Polydispersity=2.05

[0307] The overall yield with respect to Fomblin Z DOL PFPE was higher than 95%.

Example 5Synthesis of a Polymer (P) According to the Invention Starting from Fomblin Z DOL PFPE (2) and Fomblin Z DOL TX PFPE (3)

Step 1a Synthesis of Fomblin Z DOL PFPE (2) Nonaflate

[0308] 100 g (44 meq) of Fomblin Z DOL PFPE (2) nonaflate were prepared according to the procedure described in Example 1, Step 1a, with a purity >95% and a yield >90%.

Step 1Reaction of Fomblin Z DOL TX PFPE (3) with Fomblin Z DOL PFPE (2) Nonaflate of Step 1 a (Molar Ratio 1.1:1)

[0309] The same reaction as described in Step 1 of Example 1 was carried out with the sole difference that Fomblin ZDOLTX PFPE (3) 80 g (38 meq) was used and the molar ratio between Fomblin ZDOLTX PFPE (3) and Fomblin ZDOL PFPE nonaflate was 1.1.

Step 2Reaction with Trifluoroethanol Nonaflate

[0310] After complete conversion, the reaction mixture from Step 1 was reacted with 3.9 g (10 mmoles) trifluoroethanol nonaflate in the presence of 0.9 g (8 mmoles) ter-ButOK. The reaction was completed after 5 h at 120 C.

[0311] The final product was isolated and the .sup.19F and .sup.1H-NMR analyses confirmed the following structure:

CF.sub.3CH.sub.2OR.sub.hS.sup.F1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1

R.sub.hOCH.sub.2CF.sup.3

[0312] wherein:

[0313] p=2.2

[0314] R.sub.hOR.sub.hCH.sub.2OCH.sub.2CH.sub.2OCH.sub.2

[0315] S.sup.F1CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2with a1/a2=2 from Fomblin Z DOL TX PFPE (3)

[0316] S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2with a1/a2=2 Fomblin Z DOL PFPE (2) nonaflate

[0317] M.sub.n=30,100

[0318] E.sub.w15,050

[0319] Polydispersity=1.9

Example 6Synthesis of a Polymer (P) According to the Invention from Fomblin Z DOL PFPE (1)

[0320] Step 1aSynthesis of Fomblin Z DOL PFPE (1) Nonaflate

[0321] 100 g Fomblin Z DOL PFPE (1) nonaflate (M.sub.n 2,600, E.sub.w 1,300, meq 77) were prepared following the same procedure as disclosed in Example 1, Step 1a.

[0322] Purity >95%; yield >90%.

Step 1Reaction of Fomblin Z DOL PFPE with Fomblin Z DOL PFPE Nonaflate of Step 1 a (Fomblin ZDOL PFPE (1)/Fomblin ZDOL PFPE (1) Nonaflate=0.9)

[0323] A glass reactor was charged with 62 g (62 meq) Fomblin Z DOL PFPE (1) and reacted, according to the procedure described in Example 1, Step 1, with 90g (69 meq) Fomblin Z DOL PFPE (1) nonaflate of Step 1a in a molar ratio between Fomblin ZDOL PFPE (1)/ Fomblin ZDOL PFPE (1) nonaflate=0.9.

Step 2Reaction with Trifluoroethanol

[0324] After complete conversion, the reaction mixture was added with 1.5 g (15 mmoles) of trifluoroethanol in the presence of 1.2 g (11 mmoles) of ter-ButOK. The reaction was completed after 5 h at 120 C.

[0325] The final product was isolated and the .sup.19F and .sup.1H-NMR analyses confirmed the obtainment of the following product:

[0326] The analyses confirmed the obtainment of the following product:

CF.sub.3CH.sub.2OR.sub.hS.sup.F1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1

R.sub.hOCH.sub.2CF.sub.3

[0327] wherein:

[0328] p=3

[0329] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0330] and S.sub.F1 and S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2, with a1/a2=2

[0331] M.sub.n=18,100

[0332] E.sub.w=9,200

[0333] Polydispersity=1.8

[0334] The overall yield with respect to FomblinZDOL PFPE (1) nonaflate was >95%.

Example 7Synthesis of a Polymer (P) from Fomblin Z DOL PFPE (4) Nonaflate and Fomblin Z DOL PFPE (1)

[0335] Step 1aSynthesis of Fomblin Z DOL PFPE (4) Nonaflate

[0336] 100 g Fomblin Z DOL PFPE (4) nonaflate (M.sub.n2,500, E.sub.w 1,390, meq 72) were prepared following the same procedure as disclosed in Example 1, Step 1a.

[0337] Purity >95%; yield >90%.

Step 1Reaction of Fomblin Z DOL PFPE (1) with Fomblin Z DOL PFPE (4) Nonaflate of Step 1a (Molar Ratio 1:1)

[0338] A glass reactor was charged with 62 g (62meq) of Fomblin Z DOL PFPE (1) and reacted, according to the procedure described in Example 1, Step 1, with 86.2g (62 meq) Fomblin Z DOL PFPE (4) nonaflate of Step 1a in a molar ratio between Fomblin ZDOL PFPE (1)/ FomblinZDOL PFPE nonaflate=1.

[0339] The final product was isolated and the .sup.19F and .sup.1H-NMR analyses confirmed the obtainment of the following product:

T.sub.N-S.sup.F1(R.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1).sub.pR.sub.hOR.sub.hS.sup.F2R.sub.hOR.sub.hS.sup.F1-T.sub.N

[0340] wherein: p=2

[0341] R.sub.hOR.sub.hCH.sub.2OCH.sub.2

[0342] and S.sup.F1 and S.sup.F2CF.sub.2O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2CF.sub.2, with a1/a2=2

[0343] T.sub.N are neutral terminal groups of formula CF.sub.3, CF.sub.2Cl and CF.sub.2H

[0344] M.sub.n=14,000

[0345] E.sub.w=7,000

[0346] Polydispersity=1.85

[0347] The overall yield with respect to)/FomblinZDOL PFPE nonaflate was >95%.

Evaluation of the Thermal-Oxidative Stability

[0348] The stability of the polymer obtained in Example 1 to temperature and oxidation was evaluated and a kinetic equation for the decomposition was obtained. The half-time as a function of temperature is reported in the table below:

TABLE-US-00002 TABLE 2 Temperature ( C.) t (h) 250 870 270 350 290 150

Thermo-Chemical Stability Test

[0349] The product polymer obtained in Example 1 was evaluated under thermo-chemical conditions and a kinetic equation for the decomposition was obtained. The half-time as a function of temperature is reported in the table below:

TABLE-US-00003 TABLE 3 Base vs. mole Temperature ( C.) Base of product (%) solvent t (h) 180 t-BuOK 5 neat 37000 180 K.sub.2CO.sub.3 500 neat 37000 180 t-BuOK 5 DMSO 36000 180 t-BuOK 100 DMSO 30000