WO2013114300A1 - Revêtements acryliques modifiés actifs permettant d'obtenir une résistance améliorée de membranes d'osmose inverse à l'encrassement biologique - Google Patents

Revêtements acryliques modifiés actifs permettant d'obtenir une résistance améliorée de membranes d'osmose inverse à l'encrassement biologique Download PDF

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Publication number
WO2013114300A1
WO2013114300A1 PCT/IB2013/050794 IB2013050794W WO2013114300A1 WO 2013114300 A1 WO2013114300 A1 WO 2013114300A1 IB 2013050794 W IB2013050794 W IB 2013050794W WO 2013114300 A1 WO2013114300 A1 WO 2013114300A1
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Prior art keywords
methacrylate
thin
glycidyl
hydroxyl
film composite
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PCT/IB2013/050794
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English (en)
Inventor
Edoardo Menozzi
Jaleh Mansouri
Matthias Häussler
Jana Habsuda
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Polymers Crc Ltd.
Basf (China) Company Limited
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Publication of WO2013114300A1 publication Critical patent/WO2013114300A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation

Definitions

  • the present invention relates to a method for the preparation of coated thin-film composite (TFC) membranes on a microporous substrate and their functionalization with polymerizable compounds and optionally additional bio active compounds to yield membranes having antifouling and or anti-bacterial properties.
  • Further aspects of the invention are a polymer coating composition on thin-film composite (TFC) membrane, a coated functionalized thin-film composite (TFC) membrane on the microporous substrate itself and the use of such membranes in water purification systems which may be exposed to microbial contamination.
  • RO Reverse Osmosis
  • Interfacial polymerization is copolymerization of two reactive monomers dissolved in two immiscible solutions respectively.
  • the monomers can meet and react only at the interface of the solutions when two solutions are contained in a reaction chamber.
  • polymer film is formed at the interface.
  • the film is usually very thin because the growing interfacial polymer behaves as a barrier to diffusion of the two monomers, and the polymerization levels off at a limiting thickness, typically of the order of a micrometer or less.
  • the interfacial polymerization was frequently carried out at the surface of a microporous substrate, in which case the result is called a thin-film composite membrane. This is for example described by Wamser et al., J. Am. Chem. Soc. 1 1 1 , 1989, 8485-8491 .
  • membranes used for sepa- ration purposes like reverse osmosis and/or ultra and micro filtration.
  • Membranes may be classified according to their pore dimension in most of the application profiles. For example, in water filtration applications ultra filtration membranes (approximate pore diameter: 100 - 1000 nm) are used for wastewater treatment retaining organic and bioorganic material. Much smaller diameters are required in desalination applications (reverse osmosis; approximate pore diameter 1 nm) for retaining ions.
  • the ambient medium is an aqueous phase, where potential blockage may occur by adhesion of microorganisms and bio-film formation.
  • a membrane with anti-adhesion properties is desired, which would reduce bio-film formation and thus require less cleaning cycles.
  • fouling is currently one of the major remaining problems for aromatic polyamide reverse osmosis (RO) membranes. Fouling causes deterioration of the membrane per- formance and shortens membrane lifetime, limiting further application of RO membrane technology. It is thus desirable to improve antifouling and antibacterial properties to RO membranes without impairing their transport characteristics in order to enhance their resistance.
  • RO aromatic polyamide reverse osmosis
  • TFC thin-film-composite
  • UF/NF ultrafiltration/nanofiltration
  • PA polyamide
  • the instant invention relates to a method for the preparation of a hydrophilic anti-fouling coating onto commercial RO membranes by UV-induced photo- polymerization of suitable anti-adhesive polymers and monomers.
  • further antimicrobial agents may be added to the coating.
  • Bacteria contained in the influent water are accumulated by the membranes and consequently accumulate on their surfaces.
  • the rapid growth of bacteria results in fouling of the membrane which reduces the flow of water through the membrane and can ad- versely affect the filtering properties of the membrane.
  • One aspect of the invention is a method for imparting decreased adhesion of biological material to the surface of a thin-film composite membrane on a microporous substrate by applying a coating comprising the steps
  • anti-fouling is used in the context of the present invention as a synonym for the prevention of adhesion of biological material.
  • Biological material can be proteins, spores, nucleic acids, viruses or biological cells as well as fragments or extracts of biological cells.
  • proteins are fibrous proteins such as actin and tubulin, globular proteins such as albumin, fibrin, thrombin and immunoglobulin, enzymes such as oxidoreduc- tases, transferases and hydrolases, and prions.
  • fibrous proteins such as actin and tubulin
  • globular proteins such as albumin, fibrin, thrombin and immunoglobulin
  • enzymes such as oxidoreduc- tases, transferases and hydrolases, and prions.
  • Examples of spores are spores of fungi, ferns and fern allies.
  • Examples of nucleic acids are deoxyribonucleic acid and ribonucleic acid.
  • viruses are adenovirus, AIDS virus, lambda phage, T4 phage and T7 phage.
  • biological cells are archaea, bacterial cells or eukaryotic cells.
  • Examples of bacterials cells are cells from the phyla Actinobacteria, Chlamydia, Cya- nobacteria, Firmicutes, Proteobacteria and Spirochaetes.
  • Examples of genera of the phylum Actinobacteria are Actinomyces, Arthrobacter, Corynebacterium, Nocardia and Streptomyces.
  • Examples of genera of the phylum Firmicutes are Bacillus, Enterococ- cus, Lactobacillus, Lactococcus, Streptococcus, Acetobacterium, Clostridium, Eubac- trium and Heliobacterium.
  • Examples of genera of the phylum Proteobacteria are Enter- obacter, Escherichia, Klebsiella, Salmonella, Pseudomonas, Vibrio, Burkholdria, Helicobacter and Campylobacter.
  • Cells of the species Escherichia coli are particular pre- ferred bacterial cells.
  • Examples of eukaryotic cells are fungal cells, human cells, animal cells and plant cells.
  • yeast cells are molds, mushrooms and yeast cells.
  • yeast cells are cells of generae Saccharomyces and Candida.
  • Cells of the species Saccha- romyces cerevisae and Candida albicans are particular preferred yeast cells.
  • the degree of adhesion of biological matter to the surface of a substrate can be determined, for example, by comparing the flux and the retention parameters of the membrane after a period of time.
  • the top layer of the thin-film composite membrane is a polyamide layer.
  • Polyamides can be polymers formed from at least one monomer having an amide group or an amino as well as a carboxy group or from at least one monomer having two amino groups and at least one monomer having two carboxy groups.
  • An example of a monomer having an amide group is caprolactam.
  • An example of a diamine is 1 ,6- diaminohexane.
  • dicarboxylic acids are adipic acid, terephthalic acid, isophthalic acid and 1 ,4-naphthalenedicarboxylic acid.
  • polyamides are polyhexamethylene adipamide and polycaprolactam.
  • one or more biocides are additionally added to the coating before exposing it to UV-light.
  • biocides are 5-chloro-2-(2,4-dichlorophenoxy)phenol, which is sold, for example, under the tradename Irgasan® DP300, N'-fert-butyl-N-cyclopropyl-6-(methyl- thio)-1 ,3,5-triazine-2,4-diamine, which is sold under the tradename Irgarol® 1051 , 2- thiazol-4-yl-1 H-benzoimidazole, which is sold under the tradename Irgaguard® F3000, chlorhexidine, gallic acid, mucobromic acid, itaconic acid and 3-iodo-2-propynyl butyl carbamate, which is sold under the tradename MaguardTM 1-100.
  • Irgasan® DP300 N'-fert-butyl-N-cyclopropyl-6-(methyl- thio)-1 ,3,5-triazine-2,4-diamine
  • QA quarternary amines
  • zwitterionic methacrylates such as 3-((2- (methacryloyloxy)ethyl) dimethylammonio) propanesulfonate.
  • quaternary ammonium compounds carrying one or more ethylenically unsaturat- ed groups are given below. Usually these compounds have biocidal activity.
  • the quaternary ammonium compounds carrying one or more ethylenically unsaturated groups can be of formula
  • R 58 , R 59 and R 60 can be the same or different and are hydrogen, halogen or Ci-6-alkyl
  • R 61 , R 62 and R 63 can be the same or different and are Ci-30-alkyl, C2-3o-alkenyl, C3-8- cycloalkyl, aryl, or R 61 and R 62 together with the N of the ammonium group form a 4 to 8 membered cycle, wherein one CH2 group of the cycle may be replaced with NH or O
  • Q and Y can be the same or different and are Ci-15-alkylene
  • M is a bridging group
  • n and m can be the same or different and are 0 or 1 ,
  • J- is an anion, wherein Ci-30-alkyl, C2-3o-alkenyl, C3-8-cycloalkyl or Ci-15-alkylene can be unsubstituted or substituted with one or more aryl, OC2-6-alkenyl, halogen, CN, C(0)OR 64 ,
  • Ci-3o-Alkyl can be branched or unbranched.
  • Examples of Ci-30-alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, fert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, heneico- syl, docosyl, tetracosyl and triacontyl.
  • Ci-15-alkylene examples include methylene, propylene and butylene.
  • bridging groups M are C3-8-cycloalkylene, arylene, polymer, OC(O), C(0)0, NH(CO) and C(0)NH.
  • Arylene can be phenylene.
  • An example of a polymer is polyethyleneimine.
  • J- can be any anion, for example sulfate, sulfite, carbonate, phosphate or halogenide.
  • Halogenide can be fluoride, chloride, bromide or iodide.
  • Examples of quaternary ammonium compounds carrying one or more ethylenically unsaturated group are trimethylaminoethyl acrylate chloride, trimethylaminoethyl meth- acrylate chloride, trimethylaminotetradecyl acrylate chloride, trimethylaminohexadecyl acrylate chloride, tnmethylaminooctadecyl acrylate chloride and diallyldimethylammo- nium chloride and the compounds of formulae
  • More preferred quaternary ammonium compounds carrying one or more ethylenically unsaturated group are of formula
  • R 58 , R 59 and R 60 can be the same or different and are hydrogen or Ci-6-alkyl
  • R 61 , R 62 and R 63 can be the same or different and are Ci-30-alkyl or C2-3o-alkenyl, Q and Y can be the same or different and are Ci-15-alkylene,
  • M is a bridging group selected from the group consisting of arylene, polymer, OC(O) and C(0)0,
  • n and m can be the same or different and are 0 or 1 ,
  • J- is a halogenide, wherein Ci-30-alkyl, C2-3o-alkenyl or Ci-15-alkylene can be unsubstituted or substituted with one or more OC 2 - 6 -alkenyl, C(0)OR 64 , C(0)NR 65 R 66 , OR 67 , NR 68 R 69 ,
  • Most preferred quaternary ammonium compounds carrying one or more ethylenically unsaturated groups are of formula
  • R 58 , R 59 and R 60 can be the same or different and are hydrogen or Ci-6-alkyl
  • R 61 , R 62 and R 63 can be the same or different and are Ci-30-alkyl
  • Q and Y can be the same or different and are Ci-6-alkylene
  • M is a bridging group selected from the group consisting of polymer and OC(O), n and m can be the same or different and are 0 or 1 ,
  • Examples of Ci-6-alkylene are methylene, propylene and butylene.
  • Compounds 3A and 3B are especially preferred quaternary ammonium compounds carrying one or more ethylenically unsaturated groups.
  • Compound 3A can be prepared by reacting polyethyleneimine with A/-3-chloro-2- hydroxypropyl-A/-lauryl-dimethylammonium chloride and allyl bromide.
  • Compound 3B can be prepared by reacting A/,A/-dimethylaminoethyl methacrylate with dodecyl bromide as described in S.M. Hamid and D.C. Sherrington, Polymer 1987, 28, 325 to 331.
  • Inorganic biocides are for example copper, silver and zink, in particular silver in the form of nano-scale silver (as for example described in Water Research, (2008), 42(18), 4591 -4602).
  • Silver particles in nano-form have preferably a particle size of 10-100 nm, more preferably 30-80 nm.
  • biocides When additional biocides are added to the coating composition they are added in an amount of from 0.1 % to 10% by weight, based on the weight of the partially methacrylated hydroxyl or amine functional polyacrylate, for example, a partially methacrylated polyhydroxyethyl-methacrylate.
  • the porous substrate is a polymer selected from the group consisting of a polyester, polysulfone, polycarbonate, polypropylene, polyamide and polyether sulfone.
  • Polyolefins such as polypropylene can be polymers formed from at least one olefin monomer or from at least one olefin monomer and maleic monomer.
  • poly- olefines are low-density polyethylene (LDPE), high-density polyethylene (HDPE), poly- propylene (PP), biaxially orientated polypropylene (BOPP), polybutadiene, polytetraflu- oroethylene (Teflon-PTFE), chlorinated polyethylene and isopropylene-maleic anhydride copolymer.
  • Polyamides can be polymers formed from at least one monomer having an amide group or an amino as well as a carboxy group or from at least one monomer having two amino groups and at least one monomer having two carboxy groups.
  • An example of a monomer having an amide group is caprolactam.
  • An example of a diamine is 1 ,6- diaminohexane.
  • dicarboxylic acids are adipic acid, terephthalic acid, isophthalic acid and 1 ,4-naphthalenedicarboxylic acid.
  • polyamides are polyhexamethylene adipamide and polycaprolactam.
  • Polyesters can be polymers formed from at least one monomer having a hydroxy as well as a carboxy group or from at least one monomer having two hydroxy groups and at least one monomer having two carboxy groups or a lactone group.
  • An example of a monomer having a hydroxy as well as a carboxy group is adipic acid.
  • An example of a diol is ethylene glycol.
  • An example of a monomer having a lactone group is carprolac- tone.
  • dicarboxylic acids are terephthalic acid, isophthalic acid and 1 ,4- naphthalenedicarboxylic acid.
  • An example of a polyester is polyethylene terephthalate (PET). So-called alkyd resins are also regarded to belong to polyester polymers.
  • polycarbonates are poly(aromatic carbonates) and poly(aliphatic carbonates).
  • Poly(aliphatic carbonates) can be formed from carbon dioxide and at least one epoxide.
  • sulfone-based polymers are polyarylsulfone, polyethersulfone (PES), poly- phenylsulfone (PPS) and polysulfone (PSF).
  • PES polyethersulfone
  • PPS poly- phenylsulfone
  • PSF polysulfone
  • Polysulfone (PSF) is a polymer formed from 4,4-dichlorodiphenyl sulfone and bisphenol A.
  • the hydroxyl or amine functional polyacrylate is polyhydroxyethyl-acrylate or polyhydroxyethyl-methacrylate.
  • Polyhydroxyethyl-acrylate or polyhydroxyethyl-methacrylate can be obtained according to standard radical polymerization methods using a suitable radical source, such as, for example, azoisobutyronitnle (AI BN) or the like. Both polymers are also commercially available.
  • a suitable radical source such as, for example, azoisobutyronitnle (AI BN) or the like. Both polymers are also commercially available.
  • the average molecular weight Mw of the hydroxyl or amine functional polyacrylate is from 25 000 to 100 000, preferably 40 000 to 60 000.
  • the hydroxyl or amine functional polyacrylate is reacted with methac- ryloylchloride to give a partially methacrylated hydroxyl or amine functional polyacrylate.
  • the reaction is well known in the art and can be carried out according to standard procedures. Typically the polymerization above and the polymer analogous reaction are carried out in solution.
  • organic solvents are Ci-4-alkanols, C2-4-polyols, C3-6-ketones, C 4 -6-ethers, C2-3-nitriles, nitromethane, dimethylsulfoxide, dimethylformamide, dimethylacetamide, A/-methylpyrolidone and sulfolane, whereby Ci -4 -alkanols and C2- 4 -polyols may be sub- stituted with Ci -4 -alkoxy.
  • Ci -4 -alkanols are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and feri-butanol.
  • Ci -4 -alkoxy- derivatives thereof are 2-ethoxyethanol and 1 -methoxy-2-propanol.
  • Examples of C2- 4 -polyols are glycol and glycerol.
  • Examples of C3-6-ketones are acetone and methyl ethyl ketone.
  • Examples of C 4 -6-ethers are dimethoxyethane, diisopropylether and tetra- hydrofurane.
  • An example of a C2-3-nitrile is acetonitrile.
  • the organic solvent is selected from the group consisting of Ci -4 -alkanols, C2- 4 -polyols, C3-6-ketones, dimethylformamide and dimethylacetamide, whereby Ci -4 -alkanols and C2- 4 -polyols may be substituted with Ci -4 -alkoxy. More preferably, the organic solvent is a Ci -4 -alkanol.
  • the degree of methacrylation of the partially methacrylated hydroxyl or amine functional polyacrylate is from 0.1 to 20 mol-%, preferably from 0.5 to 15 mol-% and more preferably from 0.1 to 10 mol-%.
  • the weight ratio between the partially methacrylated hydroxyl or amine functional polyacrylate and glycidyl-methacrylate or glycidyl-acrylate is from 200:1 to 50: 1 , preferably 150:1 to 75:1 and more preferably 100: 1 .
  • the thin-film composite membrane on a microporous substrate is coated with the partially methacrylated hydroxyl or amine functional polyacrylate and glycidyl-methacrylate or glycidyl-acrylate.
  • the coating is applied from a solution of the components to which a photoinitiator is added.
  • the solvent may be an organic solvent or a mixture of water with an organic solvent. Examples for suitable organic solvents are outlined above.
  • the solvent is a mixture of water and an alcohol, such as ethanol or propanol.
  • the ratio between organic solvent and water is from 80:20 to 20:80 by volume, preferably from 80:20 to 40:60.
  • the concentration of the components in the solution may be in the range of 1 % to 50%, preferably from 5% to 20% by weight, based on the weight of the total solution.
  • the coating may be applied by any coating technique, such as in the form of a draw down with a doctor blade or a spiral coater or by spin coating.
  • the wet thick- ness of the coating is in the range of 1 ⁇ to 500 ⁇ , preferably from 10 ⁇ to 100 ⁇ .
  • the cured coating layer has a thickness in the range of from 0.1 to 50 ⁇ , preferably, from 1 to 10 ⁇ .
  • the exposure to UV light is carried out under inert gas atmosphere.
  • inert gases examples include Argon, Xenon, Helium and Nitrogen.
  • composition to be coated comprises one or more radical photoinitiators.
  • the photoinitiator can be of formula
  • L can be hydrogen or
  • Ci-6-alkylene can be unsubstituted or substituted with hydroxyl
  • R 27 , R 28 and R 29 can be the same or different and can be hydrogen, halogen, hydroxyl, Ci-6-alkyl, aryl, 0-Ci -6 -alkyl, O-aryl, S-Ci -6 -alkyl, S-aryl or NR 30 R 31 , wherein R 30 and R 31 can be the same or different and can be hydrogen or Ci-6-alkyl, or together with the nitrogen form a five to seven membered cycle, wherein a Chb group of the cycle can be replaced with -0-, and Ci-6-alkyl, O-Ci-6-alkyl and S-Ci-6-alkyl can be unsubstituted or substituted with one or more hydroxyl, C2-3o-alkenyl, OC(0)C2-3o- alkenyl or aryl, and X can be
  • R 32 , R 35 and R 39 can be the same or different and can be hydrogen, Ci-100-alkyl, C3-8- cycloalkyl, C 2 - 3 o-alkenyl, aryl or C(0)R 44 ,
  • R 36 , R 37 and R 38 can be the same or different and can be hydrogen, Ci-100-alkyl, O-C1- 100-alkyl, S-Ci-100-alkyl, NR 45 Ci-ioo-alkyl, Cs-s-cycloalkyl, C 2 - 3 o-alkenyl, aryl or C(0)R 44 , wherein R 45 can have the same meaning as R 32 and R 44 can have the same meaning as R 36 ,
  • photoinitiators of formula 2 are benzoin ethers such as benzoin ethyl ether, benzyl monoketals such as 2,2-diethoxy-1 -phenylethanon and 2,2-diethoxy-1 ,2- diphenylethanon, alpha-substituted acetophenone derivatives such as 2-hydroxy-2- methylpropiophenone, 1 -hydroxycyclohexyl phenyl ketone, 2-methyl-4'-(methylthio)-2- morpholino-propiophenone and 2-benzyl-2-(dimethylamino)-4'- morpholinobutyrophenone, acylphosphine oxides such as diphenyl(2,4,6- trimethylbenzoyl)-phosphine oxide or phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, alpha-acyloximester such as 1-[4-(phenylthio)phenyl]-2-(0-benzoyl
  • R 27 , R 28 and R 29 can be the same or different and are hydrogen, hydroxyl, Ci-6-alkyl, O-Ci-6-alkyl, S-Ci-6-alkyl, S-aryl or NR 30 R 31 , wherein R 30 and R 31 can be the same or different and can be hydrogen or Ci-6-alkyl, or together with the nitrogen form a five to seven membered cycle, wherein a Chb group of the cycle can be replaced with -0-, and Ci-6-alkyl and O-Ci-6-alkyl can be unsubstituted or substituted with one or more hydroxyl, C2-3o-alkenyl or aryl, and
  • E and G are -O- or NR 40 , wherein R 40 can be hydrogen or Ci-6-alkyl, or R 40 and R 32 , respectively, R 35 can, together with the nitrogen, form a five to seven membered cycle, wherein a Chb group of the cycle can be replaced with -0-, NH,
  • NC(0)C(R 41 )C C(R 42 )R 43 and/or
  • R 32 , R 35 and R 39 can be the same or different and are hydrogen, Ci-100-alkyl, C2-30- alkenyl, aryl or C(0)R 44 ;
  • R 36 , R 37 and R 38 can be the same or different and are hydrogen, Ci-100-alkyl, O-Ci-100-alkyl or C(0)R 44 ;
  • R 33 and R 34 can have the same meaning as R 36 and in addition can, together with the linking carbon atom, form a five to seven membered cycle, R 44 has the same meaning as R 36 ,
  • R 41 , R 42 , R 43 , R 52 , R 53 , R 54 , R 55 and R 56 and R 57 can be the same or different and are hydrogen or Ci-6-alkyl, aryl can be unsubstituted or substituted with one or more Ci-4-alkyl, and one or more Chb-groups of Ci-100-alkyl or C2-3o-alkenyl can be replaced with -O- and/or -NR 40 -.
  • R 27 , R 28 and R 29 can be the same or different and are hydrogen, hydroxyl, Ci-e-alkyl, O-Ci-6-alkyl, S-Ci-6-alkyl or NR 30 R 31 , wherein R 30 and R 31 can be the same or different and are hydrogen or Ci-6-alkyl; wherein Ci-6- alkyl and O-Ci-6-alkyl can be unsubstituted or substituted with one or more hydroxyl, C2-3o-alkenyl or aryl, and
  • R 35 is hydrogen, Ci-100-alkyl or C2-3o-alkenyl, wherein Ci-100-alkyl and C2-3o-alkenyl can be unsubstituted or substituted with one or more amino, hydroxyl,
  • R 41 , R 42 , R 43 , R 52 , R 53 and R 54 can be the same or different and are hydrogen or Ci-6-alkyl, and one or more Chb-groups of Ci-100-alkyl or C2-3o-alkenyl can be replaced with -O- and/or -NR 40 -.
  • R 27 , R 28 and R 29 are hydrogen or Ci-6- alkyl
  • G is -0-;
  • R 35 is Ci-100-alkyl, wherein Ci-100-alkyl can be unsubstituted or substi tuted with one or more
  • Chb-groups of Ci-100-alkyl can be replaced with -O-
  • Especially preferred photoinitiators of formula 2 are diethyleneglycol
  • polyethylene glycol (600) di(phenylglyoxylate) is especially preferred.
  • the photoinitiator can also be a titanocene or combinations of a benzophenone as well as thioxanthon-derivative with a coinitiator, for example a tertiary amine. But preferably, the photoinitiator is a compound of formula 2.
  • the photoinitiators are mostly items of commerce and supplied, for example, by BASF SE.
  • the photoinitiators are added in an amount of from 0.1 % to 10% by weight, preferably 0.5% to 5% by weight based on the weight of the partially methacrylated hydroxyl or amine functional polyacrylate, for example, a partially methacrylated polyhydroxyethyl- methacrylate.
  • UV lamps suitable for this process are known in the art and commercially availa- ble. Typically medium or high pressure mercury lamps are used. However, it is also possible to use laser light in the UV region.
  • a further aspect of the invention is a composition comprising
  • composition contains one or more biocides.
  • component b) of the above composition is as a cured film on the thin-film composite membrane on a microporous substrate.
  • compositions as described above as separating membrane which has antifouling properties in a reverse osmosis process.
  • an aspect of the invention is a coated thin-film composite membrane on a mi- croporous substrate obtainable as described above.
  • HEMA Hydroxyethyl-methacrylate
  • GMA glycidyl-methacrylate
  • Methacryloylchloride and silver lactate were purchased from Merck and Fluka, respectively, and used as received. All solvents used were obtained from Merck and were of ACS reagent or HPLC grade.
  • Darocur 1 173 photoinitiator was purchased from CIBA (now BASF) and used as received.
  • the UV coating experiments were carried out inside a UV cabinet with a power output of the lamp of 10 mW/cm 2 .
  • HEMA hydroxyethyl-methacrylate
  • AIBN azoisobutyronitrile
  • LE membranes (DOW-Filmtec) are washed with water/iso-propanol (70:30 v/v) solvent mixture to remove stabilizers and other impurities from the surface.
  • the UV crosslinking is performed in the presence of 1 % GMA (glycidyl-methacrylate), which acts as a surface binder for the polymer coating with or without additional incorporation of antimicrobial silver lactate.
  • GMA glycol-methacrylate
  • CA Contact Angle
  • the contact angle (CA) of dried surfaces is determined by measuring CA of three spots as an average of 6 values after removing first two values when equilibration between a water droplet and the membrane surface is reached. Confidence interval is given for 99% certainty.
  • PolyHEMA-MA-1 shows a reduction in flux from initially 160 LMH (for uncoated DOW- LE) to 126 LMH which is still twice the flux of BW-30FR, the commercially available RO membrane with antifouling coating.
  • the incorporation of silver has a mixed effect on the flux.
  • the flux of PolyHEMA-MA-1 - Ag with 1 % crosslinker concentration it slightly reduced to 98 LMH the flux compared to the silver-free coating (126 LMH).
  • the PolyHEMA-MA-10-Ag with 10% crosslinker concentration has the opposite trend with a higher flux compared to the silver-free film (51 vs. 35 LMH). This might suggest that higher cross-linking improve the dispersion of the silver over the coating layer.
  • DOW-LE membranes coated with PolyHEMA-MA containing 1 mol% methacrylate units as crosslink- ers are prepared with and without silver lactate.
  • the coating thickness is varied by using 24 and 50 ⁇ draw down coater bar.
  • the solution concentration of the polymer is 3 wt% in water/i-propanol (70:30 v/v).
  • Table 4 shows the results. All the PolyHEMA-MA coated membranes with and without Ag show very similar performance with a reduced initial water flux of around 60 LMH compared to uncoated DOW-LE membranes (87 LMH). This however is higher than BW30 (44 LMH).
  • the flux of the fouling solution is very similar between uncoated and coated membranes (-40 LMH) but still higher than BW-30FR. After a gentle rinsing with 30 mL MilliQ water, the recovery of the coated membranes is in the range of 90-100% with PolyHEMA-MA (50 ⁇ ) and PolyHEMA- MA-Ag (24 ⁇ ) showing the best results. This is much higher compared to uncoated DOW-LE, which exhibits only a recovery of -74% supporting the fact that functionaliz- ing RO membrane with these types of coating layer improves membrane anti-fouling properties.
  • PolyHEMA samples are stirred in either 0.5wt% HCI or 0.1wt% NaOH aqueous solu- tions for 1 h at 40°C.
  • the polymers are afterwards analysed by gel permeation chromatography (GPC) and compared against non-treated PolyHEMA.
  • the results show an overall good stability to test this material as anti-adhesive model coating (Table 5).
  • Table 5 MWs of PolyHEMA before and after being exposed to cleaning conditions 3

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention porte sur un procédé pour la préparation de membranes composites à couche mince (TFC) revêtues disposées sur un substrat microporeux et leur fonctionnalisation avec des composés polymérisables et éventuellement des composés bioactifs supplémentaires pour produire des membranes ayant des propriétés antisalissure ou antibactériennes. D'autres aspects de l'invention portent sur une composition de revêtement polymère sur une membrane composite à couche mince (TFC), sur une membrane composite à couche mince (TFC) fonctionnalisée revêtue disposée sur le substrat microporeux elle-même et sur l'utilisation de telles membranes dans des systèmes de purification d'eau qui peuvent être exposés à une contamination microbienne.
PCT/IB2013/050794 2012-01-31 2013-01-30 Revêtements acryliques modifiés actifs permettant d'obtenir une résistance améliorée de membranes d'osmose inverse à l'encrassement biologique WO2013114300A1 (fr)

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CN106861468A (zh) * 2017-04-19 2017-06-20 贵州省材料产业技术研究院 复合抗污染聚合物分离膜及其制备方法
US10569227B2 (en) 2013-10-15 2020-02-25 Basf Se Improving the chemical stability of filtration membranes
CN112870990A (zh) * 2021-01-11 2021-06-01 中化(宁波)润沃膜科技有限公司 一种抗菌耐污染反渗透复合膜及其制备方法
US20220193620A1 (en) * 2014-12-24 2022-06-23 Hydroxsys Holdings Limited Asymmetric composite membranes and modified substrates used in their preparation

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CN112044280B (zh) * 2019-06-05 2022-08-16 广州中国科学院先进技术研究所 一种抗膜生物污染涂层及其制备方法

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CN1468649A (zh) * 2002-07-16 2004-01-21 世韩工业株式会社 耐污染性优良的选择性分离膜的制造方法
WO2007127605A2 (fr) * 2006-04-28 2007-11-08 Dow Global Technologies Inc. Membrane d'osmose inverse à surface anti-contaminante modifiée par polyoxyde d'alkylène ramifié
CN101530751A (zh) * 2009-03-13 2009-09-16 浙江理工大学 一种自清洁型反渗透膜
WO2010015599A1 (fr) * 2008-08-05 2010-02-11 Polymers Crc Limited Membranes de polyamide à film mince fonctionnalisées

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CN1468649A (zh) * 2002-07-16 2004-01-21 世韩工业株式会社 耐污染性优良的选择性分离膜的制造方法
WO2007127605A2 (fr) * 2006-04-28 2007-11-08 Dow Global Technologies Inc. Membrane d'osmose inverse à surface anti-contaminante modifiée par polyoxyde d'alkylène ramifié
WO2010015599A1 (fr) * 2008-08-05 2010-02-11 Polymers Crc Limited Membranes de polyamide à film mince fonctionnalisées
CN101530751A (zh) * 2009-03-13 2009-09-16 浙江理工大学 一种自清洁型反渗透膜

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10569227B2 (en) 2013-10-15 2020-02-25 Basf Se Improving the chemical stability of filtration membranes
US20220193620A1 (en) * 2014-12-24 2022-06-23 Hydroxsys Holdings Limited Asymmetric composite membranes and modified substrates used in their preparation
CN106861468A (zh) * 2017-04-19 2017-06-20 贵州省材料产业技术研究院 复合抗污染聚合物分离膜及其制备方法
CN112870990A (zh) * 2021-01-11 2021-06-01 中化(宁波)润沃膜科技有限公司 一种抗菌耐污染反渗透复合膜及其制备方法

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