P-Xylylenediamide/diimide composite ro membranes

Abstract: Composite RO membranes having good resistance to halogen attack and high fluxes are disclosed, the composite membranes comprising a microporous polymeric support with an inter facially polymerized salt-­ rejecting layer thereon comprising an aromatic aliphatic diamide/diimide.

Description: Background of the Invention Reverse osmosis (RO) membranes are known but there is still a need in the art for RO membranes that are resistant to degradation by halogens such as chlorine, which is often present in the feed waters of an RO process stream. There is also an ongoing need in the art for membranes with high salt rejection and flux rates. One method of making RO membranes is by interfacial polymerization of a salt-rejecting layer on a porous polymeric support so as to form a composite membrane. See, for example, US-A- 4,039,440. Another method is by crosslinking polyamides or polyhydrazides having carbonyl and/or sulfonyl groups and having pendant ionic groups with metal salts. See US-A- 4,086,215. Meta -xylylenediamine has been condensed with trimesoyl chloride in an inter facial polymerization reaction on a polysulfone support so as to form a meta -xylylenediamide composite RO membrane. See NTIS Report No. PB83-243170 entitled "Novel Composite Membranes" by Eric K. L. Lee, et al. dated April 1983. However, the membranes so prepared were not useful for practical desalination applications due to their poor chlorine resistance and low fluxes (on the order of 294 to 489 litres/sq. metre/day; 6 to 10 gfd; for those with salt rejections of 95% or better). Summary of the Invention The novel RO membranes of the present invention are composite membranes comprising a para -aromaticaliphatic diamide or diimide salt-rejecting layer interfacially polymerized on a microporous polymeric support. Detailed Description of the Invention According to the present invention, novel composite RO membranes are provided that possess good chlorine resistance, high salt rejection and extraordinarily high fluxes, the membranes comprising an interfacially-polymerized salt rejection layer on a microporous polymeric support. The salt-rejecting layer is the interfacial polymerization reaction product of a mixture of aromatic polyacylhalides comprising a mixture of trimesoyl chloride (TMC) and isophthaloyl chloride (IPC) containing ≧20 wt% TMC and an aromatic diamine or diimine of the general formula R₂HNR₁-Ph-R₁NHR₂ where Ph is a para -substituted phenylene group, R₁ is an alkylene group containing from 1 to 2 carbon atoms, and R₂ is hydrogen or an alkyl group containing from 1 to 2 carbon atoms. The microporous polymeric support may be in the form of flat sheets or hollow fibers and may be selected from polysulfones, polyethersulfones, polyphenylsulfones, polyvinylidenehalides, including polyvinyl chloride, polyimides and polyetherimides, polyamides, polyesters, and polycarbonates. Such supports are available commercially in flat sheets typically 0.05 to 0.15mm (2 to 6 mils) thick. Preferred hollow fiber supports typically have an internal diameter of 260µm and an external diameter of 620µm. The salt-rejecting layer may be formed on either the inner or lumens side of such hollow fibers or on the outer or external side of the fiber. Flat sheet support membranes may be prepared by machine casting in accordance with known prior art methods. Hollow fiber support membranes may also be prepared according to known methods of hollow fiber spin casting. The composite membrane of the present invention is typically prepared by first immersing the support membrane in an aqueous solution of the diamine or diimine for a short period of time, preferably 1 to 3 minutes, removing it from the aqueous solution and draining it of excess solution, then immersing it in a dilute solution of a cross-linking agent in an organic solvent at ambient temperatures for less than one minute to form the interfacial polymer on the support. The composite membrane so formed is air-dried, then heat-cured at temperatures in the range of 40°C to 120°C for about 10 minutes to complete the reaction. The aqueous solution should contain from about 0.25 wt% to about 5 wt% of the amine or imine, 0.5 wt% to 2 wt% being preferred, together with additives of triethylamine (functioning as an acid scavenger), and a surfactant. The organic phase should contain from about 0.01 wt% to about 1.0 wt% of the cross-linking agent, preferably 0.05 wt% to about 0.5 wt%. The preferred reactants in forming the salt-rejecting layer of the composite membrane of the present invention are para -xylylenediamine (pXDA) and a mixture of TMC and IPC, containing ≧20 wt% TMC. The general class of composite RO membranes prepared according to the present invention exhibit salt rejections in excess of 95%, good chlorine resistance and fluxes of about 735 to 1960 litres/sq. metre/day (15 to 40 gfd), making them especially suitable for desalination of sea water by RO. Examples 1-3 A series of composite membranes of the present invention were prepared from mixtures of TMC and IPC as follows. An asymmetric microporous polysulfone support flat sheet membrane approximately 0.10mm (4 mils) thick and having microporosity on one side was immersed in a 1 wt% aqueous solution of pXDA containing 0.5 wt% triethylamine (as an acid scavenger) and 0.01 wt% of the surfactant Iconol NP-9, drained of excess solution, then immersed in a 0.25 wt% solution of three mixtures of 0.25 wt% TMC and IPC in hexane containing TMC in amounts of 24 wt% (Example 1), 50 wt% (Example 2), and 76 wt% (Example 3), based upon the combined amounts of TMC and IPC. The immersion was for 30 seconds at room temperature, causing formation of a para -xylylenediamide film on the microporous surface of the polysulfone support. The three resulting composite membranes were each air-dried at room temperature overnight, then heat-cured for 10 minutes at 60°C. The so-formed membranes here then RO-tested in the same manner as described in EP-A-0308153. The results, with flux being expressed in litres per square metre of membrane surface area per day and, in parenthesis, gallons per square foot of membrane surface area per day (gfd), are shown in Table I. Example No. Flux (gfd) Rejection (%) 1 684.9 (14) 97.4 2 1028 (21) 98.5 3 1517 (31) 97.5 The so-prepared membranes exhibit excellent resistance to chlorine attack. Example 4 To show the importance of at least 20 wt% TMC in the mixture of TMC and IPC, a composite membrane was prepared in the identical manner as in Examples 1-3 except that, instead of a mixture of TMC and IPC, nothing but 0.25 wt% of pure IPC in hexane was used as the aromatic polyacylhalide. The so-prepared membrane was tested under the same conditions as in Examples 1-3 and, although its flux was 684.9 litres/sq. metre/day (14 gfd), salt rejection dropped to 25.9%.

Claims: A composite reverse osmosis membrane comprising an interfacially polymerized salt-rejecting layer on a microporous polymeric support characterized in that said salt-rejecting layer comprises the interfacial polymerization reaction product of (a) a mixture of trimesoyl chloride and isophthaloyl chloride containing ≧20 wt% trimesoyl chloride, and (b) an aromatic aliphatic amine/imine of the formula R₂HNR₁-Ph-R₁NHR₂ where Ph is a para -substituted phenylene group, R₁ is an alkylene group containing from 1 to 2 carbon atoms, and R₂ is hydrogen or an alkyl group containing from 1 to 2 carbon atoms. The membrane of claim 1 wherein the microporous polymeric support is selected from polysulfones, polyethersulfones, polyphenylsulfones, polyvinylidenehalides, polyimides and polyetherimides, polyamides, polyesters, and polycarbonates. The membrane of claim 1 wherein the aromatic aliphatic amine/imine is para -xylylenediamine. The membrane of claim 1 wherein the support is selected from flat sheets and hollow fibers. The membrane of claim 4 wherein the support is a hollow fiber and the membrane is formed on the inside of said hollow fiber. The membrane of claim 4 wherein the support is a hollow fiber and said membrane is formed on the outer surface of said hollow fiber. In a process for desalination of saline water by reverse osmosis comprising contacting the saline water under pressure with a reverse osmosis membrane, the improvement comprising using as the reverse osmosis membrane the membrane of claim 1, 2, 3 or 4.

Inventors: MCCRAY SCOTT B, MCCRAY, SCOTT B.
Applicants: BEND RES INC, BEND RESEARCH, INC.
Application year: 1990
Main classification: B01D69
IPC codes: B01D71, D06M101, D01F6, C02F1, C08J9, D06M15, B01D69