Non-dewetting porous membranes
Microporous membrane composites that are non-dewetting are disclosed. These microporous membrane composites are wet with solutions of methanol and water and are non-dewetting following autoclave treatment in water. The microporous membrane composites comprise a microporous membrane support that is coated with a crosslinked ionomer comprising hydrophilic groups. Compared to the microporous membrane support, the microporous membrane composite has a flow loss on average in isopropyl alcohol of less than 82%.
1. A fluorocarbon liquid composition comprising a fluorocarbon liquid medium containing a fluorinated ionomer dissolved or dispersed therein, the fluorinated ionomer having iodine and/or bromine atoms at a terminal position, at least 90% by weight of the fluorinated ionomer consisting in particles of size lower than 200 nm, wherein the fluorinated ionomer comprises units from copolymerization of:
i) tetrafluoroethylene;
ii) fluorinated monomer units containing ethylenic groups and functional groups chosen from —SO 2 F, —COOR, —COF or combinations of these, wherein R is a C 1 to C 20 alkyl radical or a C 6 to C 20 aryl radical;
iii) monomeric units deriving from a bis-olefin, chosen from formulae (OF-1), (OF-2), or (OF-3) where:
wherein j is an integer between 2 and 10, and R1, R2, R3, R4, individually equal or different from each other, are H, F or C 1 to C 5 alkyl or (per)fluoroalkyl group;
wherein each of A, equal or different from each other and at each occurrence, is independently F, Cl, or H; each of B, equal or different from each other and at each occurrence, is independently F, Cl, H or ORB, wherein RB is a branched or straight chain alkyl radical which can be partially, substantially or completely fluorinated or chlorinated; E is a divalent group having 2 to 10 carbon atom, optionally fluorinated, which may be inserted with ether linkages;
wherein E, A and B have the same meaning as above defined; R5, R6, R7, independently equal or different from each other, are H, F or C1-5 alkyl or (per)fluoroalkyl group; and
iv) a compound having the formula R f (I) x (Br) y , wherein where R f is a fluoroalkyl or (per)fluoroalkyl or a (per)fluorochloroalkyl group having from 1 to 8 carbon atoms, and wherein x and y are integers from 0 to 2, with 1≦x+y≦2;
wherein the fluorocarbon liquid medium comprises a mixture of perfluoropolyethers, said perfluoropolyethers having the general formula F 3 C—O—[CF 2 —CF(CF 3 )—O] n —[CF 2 —O] m —CF 3 wherein m and n are integers, being n>0 and m≧0, said perfluoropolyethers having molecular weight between 300 atomic mass units (amu) and 600 amu, said mixtures having prevailing average boiling points between 55° C. and 135° C. and an average ratio between the indexes m and n (m/n) below 0.05;
wherein the fluorinated ionomer has an equivalent weight of between 380 g/eq and 620 g/eq; and
wherein the concentration of fluorinated ionomer in the fluorocarbon liquid composition range from 0.1 weight percent to 4 weight percent.
2. The liquid composition of claim 1 , wherein the content of the iodine and/or bromine atoms is between 0.1% and 5% by weight based on the ionomer.
3. The liquid composition of claim 1 wherein the liquid composition contains mixtures of perfluoropolyethers having the general formula F 3 C—O—[CF 2 —CF(CF 3 )—O] n —[CF 2 —O] m —CF 3 , each perfluoropolyether having molecular weight between 400 and 600 amu, said mixture having a prevailing (“average”) boiling point comprised between 80° C. and 100° C. and an average ratio between the indexes m and n (m/n) below 0.05.
4. The liquid composition according to claim 1 wherein the fluorocarbon liquid medium further comprises a hydrogenated fluoropolyether or a mixture of hydrogenated fluoropolyethers (HFPE) having the general formula R*—O—R f ′—R*′ wherein:
—R* and R*′, equal or different from each other, are independently chosen between —C m F 2m+1 and —C n —F 2n+1−h H h groups, with m, n being integers from 1 to 3, h being integer ≧1, chosen so that h≦2n+1, with the proviso that at least one of R* and R*′ is a —C n —F 2n+1−h H h group, as defined above;
R f ′ is chosen from structures (1), (2), or (3) where:
structure (1) is —(CF 2 O) a —(CF 2 CF 2 O) b —(CF 2 —(CF 2 ) z′ —CF 2 O) c , with a, b and c being integers up to 50, and z′ being an integer equal to 1 or 2, a≧0, b≧0, c≧0 and a+b>0;
structure (2) is —(C 3 F 6 O) c′ —(C 2 F 4 O) b —(CFXO) t —, with X being, at each occurrence, independently —F or —CF 3 ; b, c′ and t being integers up to 10, c′>0, b≧0, t≧0; and
structure (3) is —(C 3 F 6 O) c′ —(CFXO) t —, with X being, at each occurrence, independently —F or —CF 3 ; c′ and t being integers up to 10, c′>0, t≧0.
5. The liquid composition of claim 4 where R f ′ is selected from structures (1) or (2).
6. The liquid composition of claim 1 , wherein the fluorocarbon liquid medium comprises the methoxy nonafluorobutane isomers (CF 3 ) 2 CFCF 2 —O—CH 3 and/or CF 3 CF 2 CF 2 CF 2 —O—CH 3 .
7. The liquid composition of claim 1 , wherein the monomeric units deriving from a bis-olefin have the formula:
R 1 R 2 C═CH—(CF 2 ) m —CH═CR 5 R 6
wherein: m=2-10, R 1 , R 2 , R 5 , R 6 , are equal to or different from each other and are H or C 1 -C 5 alkyl groups.
8. The liquid composition of claim 7 , wherein the fluorinated monomeric units containing ethylenic groups and functional groups have the formula:
CF 2 ═CF—O—CF 2 CF 2 SO 2 F.
9. The liquid composition of claim 1 , wherein the liquid composition additionally comprises a crosslinking agent and a radical initiator.
10. The liquid composition of claim 9 , wherein the bis-olefin has the formula:
R 1 R 2 C═CH—(CF 2 ) m —CH═CR 5 R 6
wherein: m=2-10, R 1 , R 2 , R 5 , R 6 , are equal to or different from each other and are H or C 1 -C 5 alkyl groups.
11. The liquid composition of claim 9 , wherein the radical initiator is an organic dialkyl peroxide.
12. The liquid composition of claim 9 wherein the radical initiator is 2,5-di(t-butylperoxy)-2,5-dimethylhexane.
13. The liquid composition of claim 1 , wherein at least 95% by weight of the fluorinated ionomer consists in particles of size lower than 200 nm.
14. The liquid composition of claim 1 , wherein at least 99% by weight of the fluorinated ionomer consists in particles of size lower than 200 nm.
15. The liquid composition of claim 14 , wherein at least 99% by weight of the fluorinated ionomer consists in particles of size lower than 125 nm.
16. The liquid composition of claim 14 , wherein at least 99% by weight of the fluorinated ionomer consists in particles of size lower than 40 nm.
17. The liquid composition of claim 14 , wherein at least 99% by weight of the fluorinated ionomer consists in particles of size lower than 15 nm.