POLYMER ADDITIVE COMPRISING ZWITTERIONIC MOIETIES FOR PVDF BASED MEMBRANES
The present invention pertains to composition suitable for manufacturing membranes based on vinylidene fluoride (VDF) polymers, to porous membranes thereof, to methods for their manufacture and to uses thereof, especially for the filtration of water phases. Said composition comprising vinylidene fluoride (VDF) polymers and polymer additives comprising zwitterionic moieties delivers outstanding hydrophilization performances of manufactured membranes.
1 . A composition (composition (C)) comprising:
at least one vinylidene fluoride (VDF) polymer (polymer (VDF)), and
at least one copolymer (copolymer (N-ZW) comprising
(a) recurring units (units (R ZW )) derived from at least one zwitterionic monomer (monomer (A)), and
(b) recurring units (units (R N )) derived from at least one at least one additional monomer (monomer (B)), different from monomer (A),
wherein units (R ZW ) represent 0.1 to 7 mol % based on molar composition of the copolymer (N-ZW), and
wherein molecular weight of the copolymer (N-ZW) measured by gel permeation chromatography ranges from 25,000 g/mol to 350,000 g/mol, and
wherein weight ratio polymer (N-ZW)/polymer (VDF) is at least 0.1/99.9 and/or is less than 25/75.
2 . The composition (C) according to claim 1 , wherein polymer (VDF) is selected among polyaddition polymers comprising units derived from VDF and, optionally, units derived from at least one ethylenically unsaturated monomer comprising fluorine atom(s) different from VDF, which is selected from the group consisting of:
(a) C 2 -C 8 perfluoroolefins;
(b) hydrogen-containing C 2 -C 8 fluoroolefins different from VDF;
(c) C 2 -C 8 chloro- and/or bromo-containing fluoroolefins;
(d) perfluoroalkylvinylethers (PAVE) of formula CF 2 ═CFOR f1 , wherein R f1 is a C 1 -C 6 perfluoroalkyl group;
(e) perfluorooxyalkylvinylethers of formula CF 2 ═CFOX 0 , wherein X 0 is a a C 1 -C 12 perfluorooxyalkyl group comprising one or more than one ethereal oxygen atom, including perfluoromethoxyalkylvinylethers of formula CF 2 ═CFOCF 2 OR f2 , with R f2 being a C 1 -C 3 perfluoro(oxy)alkyl group; and
(f) (per)fluorodioxoles of formula:
wherein each of R f3 , R f4 , R f5 and R f6 , equal to or different from each other, is independently a fluorine atom, a C 1 -C 6 perfluoro(oxy)alkyl group, optionally comprising one or more oxygen atoms.
3 . The composition (C) of claim 2 , wherein polymer (VDF) is a polymer comprising:
(a′) at least 60% by moles of units derived from vinylidene fluoride (VDF);
(b′) optionally from 0.1 to 30% by moles of units derived from a fluorinated monomer different from VDF; and
(c′) optionally from 0.1 to 10%, by moles of units derived from one or more hydrogenated monomer(s),
all aforementioned % by moles being referred to total moles of units of the polymer (VDF).
4 . The composition (C) according to claim 1 , wherein units (R ZW ) are derived from at least one monomer (A) selected from a list consisting of
a) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl acrylates or methacrylates, acrylamido or methacrylamido;
b) heterocyclic betaine monomers;
c) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl allylics;
d) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl styrenes;
e) betaines resulting from ethylenically unsaturated anhydrides and dienes;
f) phosphobetaines of formulae
and
g) betaines resulting from cyclic acetals.
5 . The composition (C) according to claim 1 , wherein units (R N ) are derived from at least one monomer deprived of ionisable groups.
6 . The composition (C) according to claim 5 , wherein units (R N ) are derived
from at least one monomer selected from the list consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, vinyl acetate and N,N-dimethylacrylamide (units (R N-1 ));
from at least one monomer selected from a list consisting of 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate, 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, 4-hydroxybutyl acrylate, poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) methyl ether methacrylate (mPEGMA), poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) methyl ether acrylate and poly(ethylene glycol) ethyl ether acrylate (units (R N-2 ));
from at least one monomer selected from the list consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate and N,N-dimethylacrylamide (units (R N-1 )) and from at least one additional monomer selected from the list consisting of 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate, 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, 4-hydroxybutyl acrylate, poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) methyl ether methacrylate (mPEGMA), poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) methyl ether acrylate and poly(ethylene glycol) ethyl ether acrylate (units (R N-2 )).
7 . The composition (C) according to claim 1 , wherein polymer (N-ZW) comprises 80% or more by moles of units (R N ), with respect to total moles of recurring units of polymer (N-ZW).
8 . The composition (C) according to claim 6 , wherein polymer (N-ZW) comprises recurring units (R N-1 ) and comprises from 0.1 to 50% by moles of recurring units (R ZW ) and (R N-2 ), with respect to total moles of recurring units of polymer (N-ZW).
9 . The composition (C) according to claim 6 , wherein units (R N ) are composed of units (R N-1 ).
10 . The composition (C) according to claim 1 , wherein polymer (N-ZW) is a statistical copolymer.
11 . The composition (C) according to claim 1 , which further comprises at least one liquid medium (medium (L)) comprising at least one organic solvent (composition (C L )).
12 . The composition (C L ) according to claim 11 , which composition comprises an overall amount of polymer (N-ZW) and polymer (VDF) of at least 1 wt. % based on total weight of medium (L), polymer (N-ZW) and polymer (VDF), and/or composition (C L ) comprises an overall amount of polymer (N-ZW) and polymer (VDF) of at most 60 wt. % based on the total weight of medium (L), polymer (N-ZW) and polymer (VDF) and/or composition (C L ).
13 . A method for manufacturing a porous membrane, said method comprising:
step (i): preparing a composition (C L ) according to claim 11 ;
step (ii): processing the composition provided in step (i) thereby providing a film; and,
step (iii): processing the film provided in step (ii), including contacting the film with a non-solvent medium (medium (NS)), thereby providing a porous membrane.
14 . A porous membrane comprising:
at least one vinylidene fluoride polymer (polymer (VDF)), and
at least one copolymer [copolymer (N-ZW)],
(a) comprising recurring units (units (R ZW )) derived from at least one zwitterionic monomer (monomer (A)),
(b) comprising recurring units (units (R N )) derived from at least one at least one additional monomer (monomer (B)), different from monomer (A),
wherein units (R ZW ) represent 0.1 to 7 mol % based on molar composition of the copolymer (N-ZW), and
wherein the molecular weight of the copolymer (N-ZW) measured by gel permeation chromatography ranges from 25000 g/mol to 350000 g/mol, and
wherein weight ratio polymer (N-ZW)/polymer (VDF) is at least 0.1/99.9 and/or is less than 25/75.
15 . A method of separating an aqueous medium, said method comprising contacting said aqueous medium with a porous membrane according to claim 14 .
16 . The composition (C) according to claim 1 , wherein the units (R zw ) represent 0.1 to 5 mol % based on the molar composition of the copolymer (N-ZW).