Fabrication and modification of polymer membranes using ink-jet printing

Patent metadata

Field	Value
Publication number	US-2016263530-A1
Application number	US-201615162795-A
Country	US
Kind code	A1
Filing date	May 24, 2016
Priority date	Nov 28, 2013
Publication date	Sep 15, 2016
Grant date	—

Abstract

The present invention relates to methods for fabrication or modification of polymer membranes for water treatment utilizing ink-jet printing. The methods of the invention provide substantial advantages over the current state of the art including, inter alia, accurately delivering precise amounts of liquids to surfaces; quickly changing coating parameters; quickly controlling and changing coating compositions; and tailor-making membranes according to customer needs. The membranes fabricated or modified according to these methods have improved antifouling properties.

First claim

1 . A method for fabrication of a membrane for reverse osmosis, nanofiltration or ultrafiltration by forming either a polyamide layer or a nanoparticle layer on a surface of a support membrane, said method comprising a step selected from:
(i) ink-jet printing on said surface of said support membrane a polyfunctional amine or polyamine functionalized nanoparticles which, upon reacting on said surface with a polyfunctional acyl halide or anhydride functional group, forms said polyamide layer; or (ii) ink-jet printing on said surface of said support membrane nanoparticles which, upon reacting on said surface with a matrix and a crosslinker, forms said nanoparticle layer.

2 . The method of claim 1 , wherein said support membrane is a polymer membrane.

3 . The method of claim 1 , wherein the membrane fabricated has salt rejection of 40-99.5%, and flux of 0.3-40 L/h m 2 bar.

4 . The method of claim 1 , for fabrication of a thin film composite (TFC) polyamide membrane, said method comprising:
(i) ink-jet printing of an aqueous solution of a polyfunctional amine or polyamine functionalized nanoparticles on a surface of a support membrane; and (ii) treating the printed surface of said support membrane with a water-immiscible organic solution of a polyfunctional acyl halide or anhydride functional group thereby interfacially polymerizing said polyfunctional amine or polyamine functionalized nanoparticles with said polyfunctional acyl halide or anhydride functional group on said surface of said support membrane, thus forming a polyamide layer on said surface of said support membrane.

5 . The method of claim 4 , wherein step (i) is repeated n times prior to step (ii), and wherein n is an integer of 1 to 5.

6 . The method of claim 4 , wherein:
a) said ink-jet printing is carried out from (i) one reservoir; or (ii) more than one reservoir, wherein each one of said reservoirs contains an aqueous solution of identical or different polyfunctional amine or polyamine functionalized nanoparticles; or b) said ink-jet printing is carried out according to a predetermined pattern.

7 . The method of claim 4 , wherein said treating in step (ii) is conducted by immersing the printed surface of said support membrane in said organic solution; or by ink-jet printing of said organic solution on the printed surface of said support membrane.

8 . The method of claim 7 , wherein:
a) said ink-jet printing is carried out from (i) one reservoir; or (ii) more than one reservoirs, wherein each one of said reservoirs contains an organic solution of identical or different polyfunctional acyl halide or anhydride functional group; or b) said ink-jet printing is carried out according to a predetermined pattern.

9 . The method of claim 7 , wherein said treating in step (ii) is conducted by ink-jet printing of said organic solution on the printed surface of said support membrane, and simultaneously with said ink-jet printing of step (i).

10 . The method of claim 4 , wherein heat treatment is applied in step (ii) to complete the interfacial polymerization.

11 . The method of claim 4 , wherein:
(i) said support membrane is composed of polysulfone (PSf), polyethersulfone (PES), polyacrylonitrile (PAN), polyester, polyphenyleneoxide, polyphenylenesulfide, polyvinyl chloride, polyvinylidine fluoride, polytetrafluoroethylene, polycarbonate, polyetherketone, or polyetheretherketone; or (ii) said polyfunctional amine is m-phenylenediamine (MPD), p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, N,N′-diphenylethylene diamine, 4-methoxy-m-phenylenediamine, 1,3,4-triaminobenzene, 1,3,5-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminoanisole, xylylenediamine, ethylenediamine, propylenediamine, tris(2-diaminoethyl)amine, piperazine, a fluorinated aromatic polyamine, a fluorinated non-aromatic polyamine, a fluorinated alkane substituted with one or more aromatic groups each containing at least one amino group, a fluorinated alkane diol interrupted by one or more aromatic groups each containing at least one amino group, a chiral polyamine, or a mixture thereof; or (iii) said nanoparticles are carbon nanotubes (CNTs), metallic nanoparticles, nanodiamonds, or graphene quantum dots; or (iv) said polyfunctional acyl halide is trimesoyl chloride (TMC), trimellitic acid chloride, terephthaloyl chloride, isophthalolyl chloride, cyclohexane-1,3,5-tricarbonyl chloride, 1,3,5,7-tetracarbonyl chloride, adamantane-2,6-dione, 1-i socyanato-3,5-benzenedicarbonyl chloride (5-i socyanato-isophthaloyl chloride), an aromatic polyfunctional acyl halide, an alicyclic polyfunctional acyl halide, or a mixture thereof; or (v) said anhydride functional group is a polyfunctional acid anhydride, or a polyfunctional acid anhydride halide; or (vi) the organic solvent in said organic solution comprises a straight or iso-(C 5 -C 12 )alkane, a (C 5 -C 12 )cycloalkane, or a mixture thereof such as Isopar™ G Fluid, wherein said (C 5 -C 12 )alkane and (C 5 -C 12 )cycloalkane is optionally halogenated.

12 . The method of claim 11 , wherein:
(i) said fluorinated aromatic polyamine is 5-fluoro-m-phenylenediamine or 2,5-difluoro-m-phenylenediamine; (ii) said fluorinated alkane substituted with one or more aromatic groups each containing at least one amino group is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; (iii) said fluorinated alkane diol interrupted by one or more aromatic groups each containing at least one amino group is 2,2′-(methylenebis(3-amino-6,1-phenylene))bis(1,1,1,3,3,3-hexafluoropropan-2-ol); (iv) said metallic nanoparticles are silver, copper or titanium containing (titanium dioxide) nanoparticles; (v) said aromatic polyfunctional acyl halide is trimesic acid chloride, terephthalic acid chloride, isophthalic acid chloride, biphenyl dicarboxylic acid chloride or naphthalene dicarboxylic acid dichloride; (vi) said alicyclic polyfunctional acyl halide is cyclopropane tricarboxylic acid chloride, cyclobutane tetracarboxylic acid chloride, cyclopentane tricarboxylic acid chloride, cyclopentane tetracarboxylic acid chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentane dicarboxylic acid chloride, cyclobutane dicarboxylic acid chloride, cyclohexane dicarboxylic acid chloride or tetrahydrofuran dicarboxylic acid chloride; (vii) said polyfunctional acid anhydride is mellitic anhydride; (viii) said polyfunctional acid anhydride halide is 4-chloroformyl phthalic anhydride; (ix) said (C 5 -C 12 )alkane is pentane, isopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, nonane, isononane, decane, isodecane, undecane isoundecane, dodecane, or isododecane; or (x) said (C 5 -C 12 )cycloalkane is cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane or cyclododecane.

13 . The method of claim 4 , wherein the polyamide layer formed on said surface of said support membrane has a thickness in the range of 0.01-1 μm.

14 . The method of claim 4 , wherein said support membrane is soaked in an aqueous solution of a polyfunctional amine or polyamine functionalized nanoparticles prior to step (i).

15 . The method of claim 14 , wherein:
a) the concentration of said aqueous solution is in a range of 0.5-10% (w/v %); or b) the polyfunctional amine or polyamine functionalized nanoparticles in the aqueous solution ink-jet printed in step (i) and the polyfunctional amine or polyamine functionalized nanoparticles in the aqueous solution in which the surface of said support membrane is soaked prior to step (i) are identical or different.

16 . The method of claim 4 , comprising

Assignees

• B G Negev Tech And Applications Ltd

Inventors

• Arnusch Christopher J
• Badalov Shai
• Matzkin Ekaterina
• Wardrip Nathaniel Charles

Classifications

• B01D69/105

  Support pretreatment · CPC title

• B01D2323/30

  Cross-linking · CPC title

• B01D2323/345

  UV-treatment · CPC title

• B01D61/145

  Ultrafiltration · CPC title

• B41J2/01

  Ink jet · CPC title