Chemically modified semipermeable polysulfone membranes and their use in reverse osmosis and ultrafiltration
First Claim
1. A semipermeable membrane of a modified polysulfone which comprises repeating units of the formula
wherein M1 and M2 are independently a valence bond, --O-- or --NH--, R1 is a valence bond or a group of the formula ##STR38## with the proviso that if R1 is a valence bond, only one of M1 and M2 can be --O--, R2 and R3 are independently a group of the formula ##STR39## the aryl groups of R1, R2 and R3 are optionally further substituted by alkyl of 1 to 4 carbon atoms, R4 is a valence bond, --O--, alkylene of 1 to 4 carbon atoms optionally substituted or interrupted by cycloalkyl(ene) of aryl(ene) of at most 7 carbon atoms, or alkylidene of 2 to 4 carbon atoms, R5 to R10 are independently hydrogen, or --R11 NH2, ##STR40## or --R13 OH radicals, these radicals being modified through a sequence of chemical reactions consisting essentially of steps (a) to (c), wherein;
step (a) is reacting said radicals with a monomeric compound containing at least two functional groups, to bond the --R11 NH--, ##STR41## or --R13 O-- of said radicals to one of the functional groups of the monomeric compound,step (b) is reacting a product of step (a) with a polyfunctional, linear or branched oligomer or polymer, to bond an available functional group of the monomeric compound to one of the functional groups of the oligomer or polymer andstep (c) is reacting a product of step (b) with a non-ionic or ionic compound containing at least one group capable of reaction with the product of step (b), to bond the non-ionic or ionic compound to the product of step (b), --R12 X or --R13 CHO radicals, modified through a sequence of chemical reactions consisting essentially of steps (b) and (c), or --R13 CN radicals, modified through a sequence of chemical reactions consisting essentially of reacting said --R13 CN radicals with hydroxylamine to form an amidoxime group, followed by steps (a), (b) and (c), R11 is a valence bond, --CH2 --, --(CH2)p NH(CH2)2-6, --(CH2)p --O--(CH2)2-6, ##STR42## R'"'"'11 constitutes atoms necessary to form an imidazolone ring condensed with a polymer backbone consisting of the repeating units of the formula (1), R12 is --Cn H2n, R13 is a valence bond or --Cm H2m, Y is --O--, --SO2 -- or ##STR43## X is halogen, m is an integer of 1 to 5 and n is an integer of 1 to 6, p is zero of 1, wherein said membrane contains at least one radical selected from the group consisting of --R11 NH--, ##STR44## --R12 --, --R13 O--, --R13 CH═ and
##STR45## a degree of substitution of substituents R5 to R10 --different from hydrogen--being between 0.3 and 3.5 milliequivalents/g.
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Abstract
Semipermeable membranes of modified polysulfones are provided which comprises repeating units of the formula
--M.sub.1 --R.sub.1 --M.sub.2 --R.sub.2 --SO.sub.2 --R.sub.3 --(1)
wherein M1 and M2 are independently a valence bond, --O-- or --NH--, R1 is a valence bond or a group of the formula ##STR1## with the proviso that if R1 is a valence bond, only one of M1 and M2 can be --O--, R2 and R3 are independently a group of the formula ##STR2## the aryl radicals R1, R2 and R3 are optionally further substituted, R4 is a valence bond, --O--, alkylene of 1 to 4 carbon atoms optionally substituted or interrupted by cycloalkyl(ene) or aryl(ene) of at most 7 carbon atoms, or alkylidene of 2 to 4 carbon atoms, R5 to R10 are independently hydrogen, or --R11 NH2, ##STR3## or --R13 OH radicals, these radicals being modified through chemical reaction with
(a) a monomeric compound containing at least two functional groups,
(b) a polyfunctional, linear or branched oligomer or polymer, and
(c) a non-ionic or ionic compound containing at least one, preferably two groups capable of reaction with (b),
--R12 X or --R13 CHO radicals, modified through chemical reaction with (b) and (c), or --R13 CN radicals, modified through chemical reaction with hydroxylamine, (a), (b) and (c),
R11 is a valence bond, --CH2 --, alkylene or arylene containing oxygen or nitrogen atoms, R11 '"'"' constitutes the atoms necessary to form a heterocyclic ring condensed with the polymer backbone and X is halogen, the degree of substitution of substituents R5 to R10 --different from hydrogen--being between 0.3 and 3 milliequivalents/g.
The new membranes are suitable in reverse osmosis and ultrafiltration processes. They show good permeability (flux) and rejection characteristics combined with solvent and compaction resistance.
73 Citations
26 Claims
- 1. A semipermeable membrane of a modified polysulfone which comprises repeating units of the formula
- space="preserve" listing-type="equation">--M.sub.1 --R.sub.1 --M.sub.2 --R.sub.2 --SO.sub.2 --R.sub.3 --(1)
wherein M1 and M2 are independently a valence bond, --O-- or --NH--, R1 is a valence bond or a group of the formula ##STR38## with the proviso that if R1 is a valence bond, only one of M1 and M2 can be --O--, R2 and R3 are independently a group of the formula ##STR39## the aryl groups of R1, R2 and R3 are optionally further substituted by alkyl of 1 to 4 carbon atoms, R4 is a valence bond, --O--, alkylene of 1 to 4 carbon atoms optionally substituted or interrupted by cycloalkyl(ene) of aryl(ene) of at most 7 carbon atoms, or alkylidene of 2 to 4 carbon atoms, R5 to R10 are independently hydrogen, or --R11 NH2, ##STR40## or --R13 OH radicals, these radicals being modified through a sequence of chemical reactions consisting essentially of steps (a) to (c), wherein; step (a) is reacting said radicals with a monomeric compound containing at least two functional groups, to bond the --R11 NH--, ##STR41## or --R13 O-- of said radicals to one of the functional groups of the monomeric compound, step (b) is reacting a product of step (a) with a polyfunctional, linear or branched oligomer or polymer, to bond an available functional group of the monomeric compound to one of the functional groups of the oligomer or polymer and step (c) is reacting a product of step (b) with a non-ionic or ionic compound containing at least one group capable of reaction with the product of step (b), to bond the non-ionic or ionic compound to the product of step (b), --R12 X or --R13 CHO radicals, modified through a sequence of chemical reactions consisting essentially of steps (b) and (c), or --R13 CN radicals, modified through a sequence of chemical reactions consisting essentially of reacting said --R13 CN radicals with hydroxylamine to form an amidoxime group, followed by steps (a), (b) and (c), R11 is a valence bond, --CH2 --, --(CH2)p NH(CH2)2-6, --(CH2)p --O--(CH2)2-6, ##STR42## R'"'"'11 constitutes atoms necessary to form an imidazolone ring condensed with a polymer backbone consisting of the repeating units of the formula (1), R12 is --Cn H2n, R13 is a valence bond or --Cm H2m, Y is --O--, --SO2 -- or ##STR43## X is halogen, m is an integer of 1 to 5 and n is an integer of 1 to 6, p is zero of 1, wherein said membrane contains at least one radical selected from the group consisting of --R11 NH--, ##STR44## --R12 --, --R13 O--, --R13 CH═ and
##STR45## a degree of substitution of substituents R5 to R10 --different from hydrogen--being between 0.3 and 3.5 milliequivalents/g.- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26)
- 3. A membrane according to claim 2, wherein the modified polysulfone comprises repeating units of the formula
- space="preserve" listing-type="equation">--O--R.sub.1 --O--R.sub.2 --SO.sub.2 --R.sub.3 -- (5)
wherein ##STR46## R2 and R3 are independently ##STR47## R4 '"'"' is a valence bond or alkylene of 1 to 4 carbon atoms, R51 to R101 are independently hydrogen or --CH2 NH2, --CH2 OH or --NH2 radicals, modified through chemical reaction by steps (a), (b), and (c), --CH2 X radicals, wherein X is halogen, modified through chemical reaction by steps (b) and (c), or --CH2 CN radicals, modified through chemical reaction with hydroxylamine, and by steps (a), (b) and (c), the degree of substitution of substituents R51 to R101 --different from hydrogen--being between 0.3 and 3.5 milliequivalents/g.
- -sulfatoethylsulfonyl, β
-chloroethylsulfonyl or β
-sulfatoethylaminosulfonyl radicals.
- space="preserve" listing-type="equation">--O--R.sub.2 --SO.sub.2 --R.sub.3 -- (3)
- space="preserve" listing-type="equation">--R.sub.1 --O--R.sub.2 --SO.sub.2 --R.sub.3 -- (4)
Specification