ZWITTERIONIC DERIVATIVES OF (PER)FLUOROPOLYETHERS

Abstract

(Per)fluoropolyether polymers comprising a (per)fluoropolyether chain having two ends, wherein one or both ends comprise one or more zwitterionic groups at one or both polymer ends, methods for their manufacture and uses thereof are herein disclosed. The polymers can be used in particular for protecting materials in contact with biological fluids or fluids containing biological material from contamination by organic compounds therein contained.

Claims

1. A polymer comprising a (per)fluoropolyether chain (R.sub.f) having two ends, wherein one or both ends comprise(s) at least one zwitterionic group (Z.sup.w).

2. The polymer according to claim 1 wherein one or both ends comprise one zwitterionic group (Z.sup.w).

3. The polymer according to claim 1 wherein chain (R.sub.f) is a straight or branched fully or partially fluorinated polyoxyalkylene chain that comprises repeating units (R.sup.), said repeating units being independently selected from the group consisting of: (i) CFXO, wherein X is F or CF.sub.3, (ii) CFXCFXO, wherein X, equal or different at each occurrence, is F or CF.sub.3, with the proviso that at least one of X is F, (iii) CF.sub.2CF.sub.2CW.sub.2O, wherein each of W, equal or different from each other, are F, Cl, H, (iv) CF.sub.2CF.sub.2CF.sub.2CF.sub.2O, (v) (CF.sub.2).sub.jCFZO wherein j is an integer from 0 to 3 and Z is a group of general formula OR.sub.fT, wherein R.sub.f is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being selected from: CFXO, CF.sub.2CFXO, CF.sub.2CF.sub.2CF.sub.2O, and CF.sub.2CF.sub.2CF.sub.2CF.sub.2O, with each X being independently F or CF.sub.3 and T being a C.sub.1-C.sub.3 perfluoroalkyl group.

4. The polymer according to claim 1 wherein the zwitterionic group (Z.sup.w) is: a straight or branched alkyl group, optionally partially unsaturated and optionally containing at least one heteroatom and containing a cationic and an anionic group or a 5- to 7-member optionally partially unsaturated cycloaliphatic ring or a 5- to 7-member aromatic ring, optionally containing one or more heteroatoms and optionally substituted with one or more halogens, straight or branched C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy groups containing a cationic and an anionic group.

5. The polymer according to claim 1 wherein the zwitterionic group (Z.sup.w) is linked to chain (R.sub.f) via a spacer group (S.sup.p) that is a straight or branched divalent alkylene chain comprising at least 2 carbon atoms, interrupted by one or more heteroatoms or functional groups independently selected from one or more of S, O, NR.sup.1, C(O)NR.sup.1 wherein R.sup.1 is H or straight or branched C.sub.1-C.sub.4 alkyl, C(O), C(O)O, C(O)S, NH(CO)NH, NH(CS)NH, or OC(O)NH, or by a phenyl ring optionally substituted with one or more halogens, straight or branched C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy groups.

6. The polymer according to claim 5 complying with formula (P-I):
A-OR.sub.fS.sup.pZ.sup.w(P-I) wherein: R.sub.f, S.sup.p, and Z.sup.W are as defined in claim 5 and A is S.sup.pZ.sup.W or is a C.sub.1-C.sub.3 haloalkyl group.

7. The polymer according to claim 1 wherein the zwitterionic group is selected from formulae (Z.sup.w-1) and (Z.sup.w-2):
-Cat.sub.1.sup.+S.sup.1zw-An.sup.(Z.sup.w-1) wherein: Cat.sub.1.sup.+ represents NRR, wherein R and R, equal to or different from one another, represent C.sub.1-C.sub.6 straight or branched alkyl; S.sup.1 is a bond or a straight or branched divalent alkylene chain comprising 1 to 10 carbon atoms, optionally comprising one or more double bonds and/or comprising one or more cycloaliphatic or aromatic rings; An.sup. represents an anionic group selected from SO.sub.3, OP(O)(OH)O.sup., COO and O.sup., with the proviso that, when An.sup. is O.sup., S.sup.1zw is a bond; ##STR00008## wherein: A.sup.zw represents a heterocycloaliphatic or aromatic ring that comprises Cat.sup.+ and from 4 to 6 carbon atoms; Cat.sup.+ represents a quaternary nitrogen; k is 0 or 1, with the proviso that k is 0 when A.sup.zw is an aromatic ring; R.sup.zw represents a C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy group; y is 0 or an integer from 1 to 3 if A.sup.zw comprises 4 carbon atoms or from 1 to 5 if A.sup.zw comprises 6 carbon atoms; S.sup.2zw represents a covalent bond or a C.sub.1-C.sub.4 straight or branched alkyl chain; An.sup. is an anionic group selected from SO.sub.3.sup., OP(O)(OH)O.sup. and COO.sup..

8. The polymer according to claim 7, wherein the zwitterionic group complies with formula (Z.sup.w-1) wherein R and R are both methyl, S.sup.1zw is a straight alkylene chain comprising 1 to 10 carbon atoms and An.sup. represents a carboxylate anion.

9. The polymer according to claim 7, wherein the zwitterionic group is a group of formula (Z.sup.w-2a) or (Z.sup.w-2b): ##STR00009##

10. The polymer according to claim 1 wherein the spacer group complies with any one of formulae (S.sup.p-I)-(S.sup.p-IX):
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xS.sup.p*;(S.sup.p-I)
CFXC(O)OS.sup.p**;(S.sup.p-II)
CFXC(O)NR.sup.1S.sup.p**;(S.sup.p-III)
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xOCH.sub.2CH(OH)CH.sub.2NR.sup.1S.sup.p**;(S.sup.p-IV)
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xOC(O)NHR.sup.2NHC(O)NR.sup.1S.sup.p**;(S.sup.p-V)
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xOC(O)NHR.sup.2NHC(O)OS.sup.p**;(S.sup.p-VI)
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xOCH.sub.2C(O)NHS.sup.p**;(S.sup.p-VII)
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xCH.sub.2C(O)OS.sup.p**;(S.sup.p-VIII)
CFXCH.sub.2[OCH.sub.2CH(J)].sub.xOAr.sup.halOS.sup.p**(S.sup.p-IX) wherein: J is independently selected from hydrogen, methyl and ethyl; x is 0 or a positive number ranging from 1 to 10; R.sup.1 is H or straight or branched C.sub.1-C.sub.4 alkyl; R.sup.2 is a C.sub.1-C.sub.6 straight or branched divalent alkylene chain or a cycloaliphatic or aromatic ring, optionally substituted with one or more C.sub.1-C.sub.4 straight or branched alkyl groups; S.sup.p* is a bond or a straight or branched divalent alkylene chain comprising from 2 to 20 carbon atoms, optionally comprising one or more double bonds and/or one or more heteroatoms and/or functional groups and/or cycloaliphatic or aromatic rings; S.sup.p** is a straight or branched divalent alkylene chain comprising from 2 to 20 carbon atoms, optionally comprising one or more double bonds and/or one or more heteroatoms and/or functional groups and/or cycloaliphatic or aromatic rings; Ar.sup.hal is an aromatic ring substituted with at least one halogen atom.

11. The polymer according to claim 10 wherein X is F and J is H.

12. The polymer according to claim 10 wherein the spacer is selected from: a spacer of formula (S.sup.p-Ia):
CF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.xS.sup.p*(S.sup.p-Ia) wherein x is 1 or 2 and S.sup.p* is a covalent bond; a spacer of formula (S.sup.p-IIIa):
CF.sub.2C(O)NHS.sup.p**; and(S.sup.p-IIIa) a spacer of formula (S.sup.p-IIIb):
CF.sub.2C(O)NCH.sub.3S.sup.p**(S.sup.p-IIIa) wherein S.sup.p** is a straight alkylene chain of formula (CH.sub.2).sub.3.

13. A composition comprising one or more polymers according to claim 1 in admixture with one or more curable resins.

14. The composition according to claim 13 wherein the one or more curable resin is independently selected from polysiloxane resins acrylic resins, polyurethane resins and epoxyamine resins.

15. The polymer according to claim 6 wherein A 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

EXPERIMENTAL SECTION

Material and Methods

[0139] Starting Material for Example 1:

[0140] PFPE diester of formula:

R.sub.f[CF.sub.2C(O)OCH.sub.2CH.sub.3].sub.2(MW=g/mol 1575; F=1,85)

wherein:
R.sub.f is a perfluoropolyoxyalkylene chain of formula O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2, wherein the a1/a2 ratio is equal to 2.1.

[0141] Starting Material for Example 2:

[0142] PFPE diester of formula:

R.sub.f[CF.sub.2C(O)OCH.sub.2CH.sub.3].sub.2(MW=g/mol 3994; F=1.95; a1/a2=1,1)

wherein:
R.sub.f is a perfluoropolyoxyalkylene chain of formula O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2, wherein the a1/a2 ratio is equal to 1.1.

[0143] Starting Material for Example 3:

[0144] PFPE diol of formula:

R.sub.f[CF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH].sub.2 (MW=g/mol 1725; F=1.85)

wherein R.sub.f is a perfluoropolyoxyalkylene chain O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2, wherein the a1/a2 ratio is equal to 2.1 and p=1.8.

[0145] Starting Material for Example 4:

[0146] PFPE di-isocyanate of formula

##STR00005##

wherein R.sub.f is a perfluoropolyoxyalkylene chain O(CF.sub.2CF.sub.2O).sub.a1(CF.sub.2O).sub.a2, wherein the a1/a2 ratio is equal to 1.1

(MW=g/mol 2363; F=1.95).

[0147] In the above compounds, chain R.sub.f contains also small amounts of CF.sub.2CF.sub.2CF.sub.2O and CF.sub.2CF.sub.2CF.sub.2CF.sub.2O units.

[0148] The diesters were manufactured according to the method disclosed in the aforementioned EP 1980583, followed by esterification of the resulting acyl fluoride with ethanol.

[0149] The PFPE diol was manufactured according to the method disclosed in U.S. Pat. No. 6,509,509 (AUSIMONT SPA) 5 Jul. 2001.

[0150] The PFPE-diisocyanate was manufactured by reacting the PFPE diol of formula:

R.sub.f[CF.sub.2CH.sub.2OH].sub.2

with an excess of TDI (Toluen diisocyanate) in the presence of DBTDL (dibutyltin dilaurate) and further washing with a proper solvent to eliminate the excess of TDI.

[0151] .sup.1H-NMR and .sup.19F-NMR were recorded on a Agilent System 500 operating at 499.86 MHz for .sup.1H and 470.30 MHz for .sup.19F.

[0152] FT-IR spectra were measured with a ThermoScientific FTIR spectrophotometer on liquid samples as thin films on KBr. Spectra were acquired by co-adding 256 scans with a resolution of 2 cm.sup.1.

Example 1 Synthesis of a Polymer of Formula: R.SUB.f.[CF.SUB.2.C(O)NHCH.SUB.2.CH.SUB.2.CH.SUB.2.N+(CH.SUB.3.).SUB.2.CH.SUB.2.COO].SUB.2 .(Wherein R.SUB.f .is as Defined Above for the Starting PFPE Diester; MW=1785 g/Mol; F=1.85)

[0153] A 3-necked round bottom flask with 1 L capacity, equipped with a condenser and a mechanical stirrer, was charged with 200 g (127 mmoles) of the PFPE diester R.sub.f[CF.sub.2C(O)OCH.sub.2CH.sub.3].sub.2 (127 mmoles) and 24 g of dimethylaminopropylamine (MW=102 g/mol; 235 mmoles). The obtained mixture was heated up to 60 C. and let under stirring until complete conversion of the ester functionalities into amido functionalities. The reaction was monitored by means of FT-IR analysis following the disappearance of the COOEt band at 1790 cm.sup.1.

[0154] 200 g ethanol, 10 g deionized water and 27.3 g sodium chloroacetate (MW=116 g/mol; 235 mmoles) were charged into the flask containing the above prepared amido derivative, the temperature was raised up to 80 C. and the reaction was let under stirring for 8 hrs. Thereafter, 300 g 1,3-bis(trifluoromethyl)benzene, 200 g of water and 100 g isobutyl alcohol were added into the reaction mixture to obtain the separation of two phases. The bottom one (fluorinated phase) was evaporated under vacuum, to provide 223 g of title compound. The structure of the product was confirmed by .sup.1H-NMR and .sup.19F-NMR analyses.

Example 2Synthesis of a Polymer of Formula: R.SUB.f.[CF.SUB.2.C(O)NHCH.SUB.2.CH.SUB.2.CH.SUB.2.N+(CH.SUB.3.).SUB.2.CH.SUB.2.COO].SUB.2 .(Wherein R.SUB.f .is as Defined Above for the Starting PFPE Diester; MW=4216 g/Mol and F=1.95)

[0155] The procedure described in Example 1 was followed by reacting first 200 g (50 mmoles) of starting PFPE diester R.sub.f[CF.sub.2C(O)OCH.sub.2CH.sub.3].sub.2 as defined above with 10 g of dimethylaminopropylamine (MW=102; 98 mmoles) to provide the corresponding amide. The amide was then reacted with 11.3 g of sodium chloroacetate (MW=116; 98 mmoles).

[0156] The structure of the title compound was confirmed by .sup.1H-NMR and 19 F-NMR analyses.

Example 3Synthesis of a Polymer of Formula

[0157] ##STR00006##

(wherein R.sub.f and p are as defined above for the starting PFPE diol; MW=1950 g/mol and F=1.85)

[0158] A 3-necked round bottom flask with 0.5 L capacity, kept under nitrogen atmosphere and equipped with a condenser, a mechanical stirrer and a dropping funnel, was charged with 150 g (87 mmoles) of starting PFPE ethoxylated alcohol of formula R.sub.f[CF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH].sub.2 as defined above, 70 g CH.sub.2Cl.sub.2 and 23 g trietylamine (MW=g/mol 101; 225 mmoles). Thereafter, the flask was refrigerated and 73 g of a 30% w/w solution in CH.sub.2Cl.sub.2 of methanesulfonyl chloride (MW=114.5 g/mol; 193 mmoles) were added at such a rate as to keep the temperature in the range of 15-30 C. When the methanesulfonyl chloride addition was complete, the reaction mixture was let under stirring for further 4 hrs.

[0159] The reaction mixture was then brought to neutrality by adding a 4M aqueous solution of HCl and the thereby formed organic phase was separated. After distillation of the solvent, 160 g of mesyl derivative of formula: R.sub.f[CF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOSO.sub.2CH.sub.3].sub.2 (MW=1870 g/mol; F=1.85; a1/a2=2.1; p=1.8 and R.sub.f as defined above) were obtained as a limpid liquid characterized by .sup.1H-NMR and .sup.19F-NMR analyses.

[0160] 100 g (54 mmoles) of the mesyl derivative were dropped into a 3-necked round bottom flask of 0.25 L capacity, equipped with a condenser, a mechanical stirrer and containing 60 g 1,3-bis(trifluoromethyl)benzene and 13.7 g methyl nicotinate (MW=137; 100 mmoles). The resulting mixture was heated up to 90 C. for 8 hrs, dried under vacuum and the obtained residue was treated with 200 g of a 0.5M NaOH aqueous solution at room temperature for 2 hours. Thereafter, 150 g 1,3-bis(trifluoromethyl)benzene, and 50 g of isobutyl alcohol were added into the reaction mixture to obtain the separation of the phases. The bottom one was evaporated under vacuum, to provide 103 g of the title compound. The product structure was confirmed by .sup.1H-NMR and .sup.19F-NMR analyses.

Example 4Synthesis of a Polymer of Formula

[0161] ##STR00007##

(wherein R.sub.f is as defined above for the starting PFPE di-isocyanate; MW=2650 g/mol: F=1.95)

[0162] A 3-necked round bottom flask with 1 L capacity, equipped with a condenser and a mechanical stirrer, was charged with 200 g (85 mmoles) of the starting PFPE diisocyanate having the formula defined above, 100 g of MEK (Methyl Ethyl Ketone) and 15 g (166 mmoles) of NN-dimethyl-ethanol amina. The obtained mixture was heated up to 60 C., added with 0.5 ml of 20% solution of DBTDL in MEK and let under stirring until complete conversion of the isocyanate functionalities into urethane functionalities (the reaction was monitored by means of FT-IR analysis following the disappearance of the NCO band at 2264 cm.sup.1). After complete elimination of the MEK by distillation, 150 g of ethanol, 10 g deionized water and 27 g sodium chloroacetate (MW=116 g/mol; 233 mmoles) were charged into the flask containing the above prepared urethane derivative. The temperature was raised up to 80 C. and the reaction was let under stirring for 8 hrs. Thereafter, 270 g 1,3-bis(trifluoromethyl)benzene, 180 g of water and 90 g isobutyl alcohol were added into the reaction mixture to obtain the separation of two phases. The bottom one was evaporated under vacuum, to provide 213 g of title compound. The structure of the product was confirmed by .sup.1H-NMR and .sup.19F-NMR analyses.