Selectively-permeable membrane and the use thereof

Claim 3

A method according to claim 1, wherein the synthetic polymer of the selectively-permeable membrane is an olefinic polymer including repeating units each having at least one polar functional group.

Claim 4

A method according to claim 2, wherein the olefinic polymer is selected from the group consisting of polyvinyl alcohol, copolymers of an olefinic monomer selected from ethylene, propylene, isobutene and styrene with a monomer selected from acrylic acid, methacrylic acid and salts thereof, vinyl alcohol and vinyl acetate and mixtures thereof.

Claim 5

A method according to claim 2, wherein the olefinic polymer is selected from the group consisting of polyvinylpyrrolidone/vinyl acetate, polyvinylpyridine and polyhydroxyethyl methacrylate.

Claim 6

A method according to claim 2 wherein the olefinic polymer is a polymer of ethylene-vinyl alcohol produced by the hydrolysis of the corresponding ethylene-vinyl acetate with a degree of hydrolysis of the acetate groups of from 50 to 100% and an ethylene content of less than 40% by weight.

Claim 7

A method according to claim 2, wherein the olefinic polymer is a polymer of ethylene-vinyl alcohol or polyvinyl alcohol having alcoholic functional groups which are at least partially etherified by reaction with a compound selected from the group consisting of ethylene oxide unsubstituted or substituted with C 1 -C 20 alkyl radicals or with aromatic radicals, acrylonitrile, acrylamide, arylalkylhalides, chloroacetic acid, methylchloromethyl ether and silanes.

Claim 8

A method according to claim 2, wherein the olefinic polymer is a polymer of ethylene-vinyl alcohol or polyvinyl alcohol including esterified alcoholic functional groups selected from the group consisting of sulfates, nitrates, phosphates, arsenates, xanthates, borates, titanates, urethanes and carbomates.

Claim 9

A method according to claim 2, wherein the olefinic polymer is a polymer of ethylene-vinyl alcohol or polyvinyl alcohol including alcoholic functional groups which have been esterified by reaction with aliphatic or aromatic acids, chloroacyls or anhydrides.

Claim 10

A method according to claim 2, wherein the olefinic polymer is a polymer of ethylene-vinyl alcohol or polyvinyl alcohol including acetal functional groups produced by reaction with compounds selected from the group consisting of saturated and unsaturated aliphatic aldehydes having up to 22 carbon atoms, aromatic aldehydes, cycloaliphatic aldehydes, chloroacetaldehyde, glyoxal, aliphatic ketones, alkylcycloalkyl ketones and arylalkyl ketones.

Claim 11

A method according to claim 2, wherein the olefinic polymer is a multifunctional ethylene-vinyl alcohol copolymer with an ethylene content of up to 40% by weight and with a degree of hydrolysis of the acetate of between 100 and 50%, in which up to 50% of the ethylene may be substituted by co-monomers selected from the group consisting of: propylene, isobutene, styrene, vinyl chloride, 1,1-dichloroethene, vinyl ethers of the formula CH 2 ═CR--OR' in which R is hydrogen or a methyl group and R' is an alkyl group with from 1 to 18 carbon atoms, a cycloalkyl group or a polyether, acrylonitrile, methacrylonitrile, vinyl ketones of the formula CH 2 ═CR--CO--CH 2 --R' in which R is hydrogen or a methyl group and R' is hydrogen or a C 1 -C 6 alkyl group, acrylic acid, methacrylic acid and their esters of the formula CH 2 ═CR--COOR' in which R is hydrogen or a methyl group and R' is hydrogen or a C 1 -C 6 alkyl group, and the alkali metal or alkaline-earth metal salts of those acids, vinyl derivatives of the formula CH 2 ═CR--OCOR' in which R is hydrogen or a methyl group and R' is hydrogen, a methyl group, a methyl group mono-, bi-, or trisubstituted with chloro- and fluoro- groups, or a C 2 -C 6 alkyl group, vinyl carbamates of the formula CH 2 ═CR--CONR'R" in which R is hydrogen or a methyl group and R' and R" are the same or different and are hydrogen or C 1 -C 3 alkyl groups, maleic anhydride, fumaric anhydride, vinylpyrrolidone, vinylpyridine, or 1-vinylimidazole.

Claim 12

A method according to claim 1, wherein the membrane composition comprises non-ionic starch, at least an olefinic polymer selected from the group consisting of ethylene-vinyl alcohol and polyvinyl alcohol copolymer, and a polymer selected from hydrophobic polymers of polyethylene or of its vinyl copolymers, aliphatic polyesters including polyvinyl acetate, polyepsilon caprolactone, polyhydroxybutyrate, polyhydroxybutyrate valerate, polylactic acid, polyethylene and polybutylene adipates and sebacates, polyethers including polyoxymethylene, polyoxyethylene, polyoxypropylene, and polyphenylene oxide, polyamides, polyacrylonitrile, polyurethanes, polyester/polyurethane copolymers, polyester/polyamide copolymers, polyglycolide, and hydrophilic polymers including polyvinylpyrrolidone, polyoxazoline, cellulose acetates and nitrates, regenerated cellulose, alkyl cellulose, carboxymethyl cellulose, casein-type proteins and salts thereof, natural gums, chitin and chitosan.

Claim 13

A method according to claim 1, wherein the membrane composition includes from 5 to 60% by weight of synthetic polymer with reference to the weight of the anhydrous starch.

Claim 14

A method according to claim 1, wherein the membrane composition further comprises a plasticiser selected from the group consisting of: a) polyols formed by from 1 to 20 repeating hydroxylated units each including 2 to 6 carbon atoms; b) ethers, thioethers, inorganic and organic esters, acetals and amino-derivatives of polyols formed by from 1 to 20 repeating hydroxylated units each including from 2 to 6 carbon atoms; c) reaction products of polyols having from 1 to 20 repeating hydroxylated units each including from 2 to 6 carbon atoms with chain extenders; and d) oxidation products of polyols having from 1 to 20 repeating hydroxylated units each including from 2 to 6 carbon atoms, and including at least one aldehydric or carboxylic functional group or a mixture thereof.

Claim 15

A method according to claim 13, wherein the plasticiser is selected from the group consisting of ethylene glycol, propylene glycol, polyglycols, glycerol, polyglycerols having from 2 to 10 monomeric units, polyvinyl alcohol having from 3 to 20 monomeric units, erthythritol, arabitol, adonitol, xylitol, mannitol, iditol, galactitol, allitol, trimethylolpropane, pentaerythritol, and sorbitol.

Claim 16

A method according to claim 13, wherein the plasticiser is a monoethoxylate, monopropoxylate or monoacetate derivate of a polyol, the polyol being selected from the from the group consisting of ethylene glycol, propylene glycol, polyglycols, glycerol, polyglycerols having from 2 to 10 monomeric units, polyvinyl alcohols having from 3 to 20 monomeric units, erthythritol, arabitol, adonitol, xylitol, mannitol, iditol, galactitol, allitol, trimethylolpropane, pentaerythritol, and sorbitol.

Claim 17

A method according to claim 13, wherein the plasticiser is a derivative of an aliphatic polyol having from 3 to 6 carbon atoms, in which at least one alcoholic functional group is replaced by a functional group R selected from the group consisting of: --O--(CH 2 ) n --H in which n=1-18, --O--CH═CH--R 1 in which R 1 =H or --CH 3 , --O--(CH 2 --CHR 1 --O) n --H in which R 1 =H or CH 3 and n=1-20, --O--(CH 2 ) n --Ar in which Ar is a simple, substituted, or heterocyclic aromatic radical and n=0-4, --OCO--H, --OCO--CR 1 R 2 R 3 in which the R 1 , R 2 , and R 3 groups are the same or different and are selected from H, Cl, and F, --OCO--(CH 2 ) n --H in which n=2-18, --ONO 2 , --OPO 3 M 2 in which M may be H, ammonium, an alkali metal, an alkaline-earth metal, or an organic cation including trimethylammonium, pyridinium or picoline, --SO 3 --Ar in which the Ar is benzene or toluene, --OCO--CH(SO 3 M)--COOM in which the Ms are the same or different and are selected from H, an alkali metal, an alkaline-earth metal, ammonium, and an organic cation including pyridinium, picoline or methylammonium, --OCO--B--COOM in which B is (CH 2 ) n in which n=1-6 or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or--(CH 2 ) n H in which n=1-6, or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or--(CH 2 ) n H in which n=1-6, or an aryl group, --OCONH--R 1 in which R 1 may be --H or an aliphatic or aromatic radical, --O--(CH 2 ) n --COOM in which n=1-6 and M may be H, an alkali metal, an alkaline-earth metal, ammonium, or an organic cation including pyridinium, trimethylammonium, or picoline, --O--(CH 2 ) n --COOR 1 in which n=1-6, R 1 =H(CH 2 ) n -- in which m=1-6, --NR 1 R 2 in which R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, --CH 2 --CH 2 OH or a salified amino group, --O--(CH 2 ) n --NR 1 R 2 in which n=1-4, R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, or CH 2 --CH 2 --OH and in which the amino group may be salified ##STR5## --O--CH 2 --CHOH--CH 2 --NR 1 R 2 in which R 1 and R 2 are the same or different and are selected from H and H(CH 2 ) n in which n=1-6 and in which the amino group may be salified, --O--CH 2 --CHOH--CH 2 R + 1 Cl - in which R + 1 is a trialkylammonium, pyridinium or picoline group, --O--(CH 2 ) n --CN in which n=1-6, --O--(CH 2 ) n --CONH 2 in which n=1-6, --O--(CH 2 ) m --SO 2 --(CH 2 ) n --H in which m and n=1-4, --SCSNH 2 , --O--SiX 3 and --O--SiOX 3 in which X may be an aliphatic or an aromatic radical.

Claim 18

A method according to claim 13 wherein the plasticiser is a compound of the formula: R--CH.sub.2 --(CHR).sub.n --CH.sub.2 --O--A--O--CH.sub.2 --(CHR).sub.m --CH.sub.2 --R in which n and m are the same or different and have values of from 1 to 6, the R groups are the same or different and are selected from the group consisting of --OH --O--(CH 2 ) n --H in which n=1-18, --O--CH═CH--R l in which R 1 =H or --CH 3 , --O--(CH 2 --CHR 1 --O) n --H in which R 1 =H or CH 3 and n=1-20, --O--(CH 2 ) n --Ar in which Ar is a simple, substituted, or heterocyclic aromatic radical and n=0-4, --OCO--H, --OCO--CR 1 R 2 R 3 in which the R 1 , and R 2 , and R 3 groups are the same or different and are selected from H, C1, and F, --OCO--(CH 2 ) n --H in which n=2-18, --ONO 2 , --OPO 3 M 2 in which M may be H, ammonium, an alkali metal an alkaline-earth metal, or an organic cation including trimethylammonium, pyridinium or picoline, --SO 3 --Ar in which the Ar is benzene or toluene, --OCO--CH(SO 3 M)--COOM in which the Ms are the same or different and are selected from H, an alkali metal, an alkaline-earth metal, ammonium, and an organic cation including pyridinium, picoline or methylammonium, --OCO--B--COOM in which B is (CH 2 ) n in which n=1-6 or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, or an aryl group, --OCONH--R 1 in which R l may be --H or an aliphatic or aromatic radical, --O--(CH 2 ) n --COOM in which n=1-6 and M may be H, an alkali metal, an alkaline-earth metal, ammonium, or an organic cation including pyridinium, trimethylammonium, or picoline, --O--(CH 2 ) n --COOR 1 in which n=1-6, R 1 =H(CH 2 ) m -- in which m=1-6, --NR 1 R 2 in which R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, --CH 2 --CH 2 OH or a salified amino group, --O--(CH 2 ) n --NR 1 R 2 in which n=1-4, R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, or CH 2 --CH 2 OH and in which the amino group may be salified ##STR6## --O--CH 2 --CHOH--CH 2 --NR 1 R 2 in which R 1 and R 2 are the same or different and are selected from H and H(CH 2 ) n in which n=1-6 and in which the amino group may be salified, --O--CH 2 --CHOH--CH 2 --R + 1 Cl - in which R + 1 is a trialkylammonium, pyridinium or picoline group, --O--(CH 2 ) n --CN in which n=1-6, --O--(CH 2 ) n --CONH 2 in which n=1-6, --O--(CH 2 ) m --SO 2 --(CH 2 ) n --H in which m and n=1-4, --SCSNH 2 , and --O--SiX 3 and --O--SiOX 3 in which X may be an aliphatic or an aromatic radical; and in which A is selected from the group consisting of: --CHR 1 in which R 1 =H or H--(CH 2 ) n -- in which n=1-5 (acetals), --(CH 2 ) n -- in which n=1-6, --(CH 2 --O--CH 2 ) n in which n=1-20, --(CH 2 CH 2 --O) n --CH 2 CH 2 -- in which n=1-20, --OC--(CH 2 ) n --CO-- in which n=0-6, --OC--Ar--CO-- in which Ar is an aromatic radical which is also heterocyclic, --PO 2 --, and --CONH--(CH 2 ) n --NHCO--.

Claim 19

A method according to claim 13 wherein the plasticiser is a compound of the formula: R--CH.sub.2 --(CHR).sub.n --CH.sub.2 --A--CH.sub.2 --(CHR).sub.m --CH.sub.2 --R in which n and m are the same or different and are whole numbers from 1 to 6, the R groups are the same or different and are selected from the group consisting of --OH --O--(CH 2 ) n --H in which n=1-18, --O--CH═CH--R 1 in which R 1 =H or --CH 3 , --O--(CH 2 CHR 1 --O) n --H in which R 1 =H or CH 3 and n=1-20, --O--(CH 2 ) n --Ar in which Ar is a simple, substituted, or heterocyclic aromatic radical and n=0-4, --OCO--H, --OCO--CR 1 R 2 R 3 in which the R 1 , R 2 , and R 3 groups are the same or different and are selected from H, Cl, and F, --OCO--(CH 2 ) n --H in which n=2-18, --ONO 2 , --OPO 3 M 2 in which M may be H, ammonium, an alkali metal, an alkaline-earth metal, or an organic cation including trimethylammonium, pyridinium or picoline, --SO 3 --Ar in which the Ar is benzene or toluene, --OCO--CH(SO 3 M)--COOM in which the Ms are the same or different and are selected from H, an alkali metal, an alkaline-earth metal, ammonium, and an organic cation including pyridinium, picoline or methylammonium, --OCO--B--COOM in which B is (CH 2 ) n in which n=1-6 or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, or an aryl group, --OCONH--R 1 in which R 1 may be --H or an aliphatic or aromatic radical, --O--(CH 2 ) n --COOM in which n=1-6 and M may be H, an alkali metal, an alkaline-earth metal, ammonium, or an organic cation including pyridinium, trimethylammonium, or picoline, --O--(CH 2 ) n --COOR l in which n=1-6, R 1 =H(CH 2 ) m -- in which m=1-6, --NR 1 R 2 in which R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, --CH 2 --CH 2 OH or a salified amino group, --O--(CH 2 ) n --NR 1 R 2 in which n=1-4, R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, or CH 2 --CH 2 OH and in which the amino group may be satisfied ##STR7## --O--CH 2 --CHOH--CH 2 --NR 1 R 2 in which R 1 and R 2 are the same or different and are selected from H and H(CH 2 ) n in which n=1-6 and in which the amino group may be salified, --O--CH 2 --CHOH--CH 2 --R + 1 Cl - in which R + 1 is a trialkylammonium, pyridinium or picoline group, --O--(CH 2 ) n --CN in which n=1-6, --O--(CH 2 ) n --CONH 2 in which n=1-6, --O--(CH 2 ) m --SO 2 --(CH 2 ) n --H in which m and n=1-4, --SCSNH 2 , and --O--SiX 3 and --O--SiOX 3 in which X may be an aliphatic or an aromatic radical; and in which A is selected from the group consisting of --NH-- and --NH--(CH 2 --CH 2 --NH) n -- in which n is a whole number from 1 to 6.

Claim 20

A method according to claim 13 wherein the plasticiser is a compound of the formula: ##STR8## in which the R groups are the same or different and are selected from the group consisting of --OH --O--(CH 2 ) n --H in which n=1-18, --O--CH═CH--R 1 in which R 1 =H or --CH 3 , --O--(CH 2 --CHR 1 --O) n --H in which R 1 =H or CH 3 and n=1-20, --O--(CH 2 ) n --Ar in which Ar is a simple, substituted, or heterocyclic aromatic radical and n=0-4, --OCO--H, --OCO--CR 1 R 2 R 3 in which the R 1 , R 2 , and R 3 groups are the same or different and are selected from H, Cl and F, --OCO--(CH 2 ) n --H in which n=2-18, --ONO 2 , --OPO 3 M 2 in which M may be H, ammonium, an alkali metal, an alkaline-earth metal, or an organic cation including trimethylammonium, pyridinium or picoline, --SO 3 --Ar in which the Ar is benzene or toluene, --O--OCO--CH(SO 3 M)--COOM in which the Ms are the same or different and are selected from H, an alkali metal, an alkaline-earth metal, ammonium, and an organic cation including pyridinium, picoline or methylammonium, --OCO--B--COOM in which B is (CH 2 ) n in which n=1-6 or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, --or an aryl group, --OCONH--R 1 in which R 1 may be --H or an aliphatic or aromatic radical, --O--(CH 2 ) n --COOM in which n=1-6 and M may be H, an alkali metal, an alkaline-earth metal, ammonium, or an organic cation including pyridinium, trimethylammonium, or picoline, --O--(CH 2 ) n --COOR 1 in which n=1-6, R 1 =H(CH 2 ) m -- in which m=1-6, --NR 1 R 2 in which R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, --CH 2 --CH 2 OH or a salified amino group, --O--(CH 2 ) n --NR 1 R 2 in which n=1-4, R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, or CH 2 --CH 2 OH and in which the amino group may be salified ##STR9## --O--CH 2 --CHOH--CH 2 --NR 1 R 2 in which R 1 and R 2 are the same or different and are selected from H and H(CH 2 ) n in which n=1-6 and in which the amino group may be salified, --O--CH 2 --CHOH--CH 2 --R + 1 Cl - in which R + is a trialkylammonium, pyridinium or picoline group, --O--(CH 2 ) n --CN in which n=1-6, --O--(CH 2 ) n --CONH 2 in which n=1-6, --O--(CH 2 ) m --SO 2 --(CH 2 ) n --H in which m and n=1-4, --SCSNH 2 , and --O--SiX 3 and --O--SiOX 3 in which X may be an aliphatic or an aromatic radical.

Claim 21

A method according to claim 13, wherein the plasticiser is an aldohexoses or a derivative thereof having the formula: ##STR10## or a ketohexose or a derivative thereof having the formula: ##STR11## in which the R groups are the same or different and are selected from the group consisting of --OH --O--(CH 2 ) n --H in which n=1-18, --O--CH═CH--R 1 =in which R 1 =H or --CH 3 , --O--(CH 2 --CHR 1 --O) n --H in which R 1 =H or CH 3 and n=1-20, --O--(CH 2 ) n --Ar in which Ar is a simple, substituted, or heterocyclic aromatic radical and n=0-4, --O--OCO--H, --OCO--CR 1 R 2 R 3 in which the R 1 , R 2 , and R 3 groups are the same or different and are selected from H, Cl, and F, --OCO--(CH 2 ) n --H in which n=2-18, --ONO 2 , --OPO 3 M 2 in which M may be H, ammonium, an alkali metal, an alkaline-earth metal, or an organic cation including trimethylammonium, pyridinium or picoline, --SO 3 --Ar in which the Ar is benzene or toluene, --OCO--CH(SO 3 M)--COOM in which the Ms are the same or different and are selected from H, an alkali metal, an alkaline-earth metal, ammonium, and an organic cation including pyridinium, picoline or methylammonium, --OCO--B--COOM in which B is (CH 2 ) n in which n=1-6 or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, or --CH═CH--, M may be H, an alkali metal, an alkaline-earth metal, or --(CH 2 ) n H in which n=1-6, 3or an aryl group, --OCONH--R 1 in which R 1 may be --H or an aliphatic or aromatic radical, --O--(CH 2 ) n --COOM in which n=1-6 and M may be H, an alkali metal, an alkaline-earth metal, ammonium, or an organic cation including pavridinium, trimethylammonium, or picoline, --O--(CH 2 ) n --COOR 1 in which n=1-6, R 1 =H(CH 2 ) m --in which m=1-6, --NR 1 R 2 in which R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, --CH 2 --CH 2 OH or a salified amino group, --O--(CH 2 ) n --NR 1 R 2 in which n=1-4, R 1 and R 2 =H, CH 3 --, CH 3 CH 2 --, or CH 2 --CH 2 OH and in which the amino group may be salified ##STR12## --O--CH 2 --CHOH--CH 2 --NR 1 R 2 in which R l and R 2 are the same or different and are selected from H and H(CH 2 ) n in which n=1-6 and in which the amino group may be salified, --O--CH 2 --CHOH--CH 2 --R + 1 Cl - in which R + 1 is a trialkylammonium, pyridinium or picoline group, --O--(CH 2 ) n --CN in which n=1-6, --O--(CH 2 ) n --CONH 2 in which n=1-6, --O--(CH 2 ) m --SO 2 --(CH 2 ) n --H in which m and n=1-4, --SCSNH 2 , and --O--SiX 3 and --O--SioX 3 in which X may be an aliphatic or an aromatic radical.

Claim 22

A method according to claim 13, wherein the plasticiser is selected from the group consisting of arabinose, lyxose, ribose, xylose, glucose, fructose, mannose, allose, altrose, galactose, gulose, idose, inositol, sorbose, talitol and their monoethyloxylate, monopropoxylate and monoacetate derivatives.

Claim 23

A method according to claim 13, wherein the plasticiser d) is the product of oxidation with an oxidizing reagent selected from periodic acid, hypochlorite and lead tetracetare.

Claim 24

A method according to claim 13, wherein the membrane composition contains from 1 to 50% by weight of the plasticiser, with reference to the weight of the composition.

Claim 25

A method according to claim 19, wherein all but one of the R groups is an --OH group.

Claim 26

A method according to claim 20, wherein all but one of the R groups is an --OH group.