Durable asymmetric composite membrane

Abstract

Durable asymmetric composite membranes consisting of a film of cross-linked sulfonated poly(ether ether ketone) adhered to a sheet of sulfonated microporous poly(ethylene) are disclosed. The membranes have application in the recovery of water from feed streams were the ability to clean in situ is desirable, for example in dairy processing. Methods of preparing cross-linked sulfonated poly(ether ether ketone) suitable for use as a rejection layer in such membranes are also disclosed.

Claims

1. A method of removing water from a feed stream that is a dairy product comprising the step of exposing the first layer of an asymmetric composite membrane to the feed stream at a pressure and temperature sufficient to produce a permeate, where the asymmetric composite membrane comprising a first layer of cross-linked sulfonated poly(ether ether ketone) adhered to a second layer of sulfonated microporous poly(ethylene).

2. The method of claim 1 where the feed stream is milk.

3. The method of claim 2 where the pressure is in the range 20 to 40 Bar.

4. The method of claim 3 where the temperature is in the range 4 to 20? C.

5. A method of preparing a cross-linked sulfonated poly(ether ether ketone) comprising the step of incubating in the presence of a Friedel-Crafts type catalyst a mixture of a chlorosulfonated poly(ether ether ketone) and a C.sub.2-9-dioyl halide cross-linking agent solvated in a non-aqueous reactive solvent at a temperature substantially below 180? C. for a period of time sufficient to provide the cross-linked sulfonated poly(ether ether ketone).

6. The method of claim 5 where the Friedel-Crafts type catalyst is ferric chloride (FeCl.sub.3).

7. The method of claim 6 where the C.sub.2-9-dioyl halide is an acyclic, aliphatic C.sub.2-6-dioyl chloride.

8. The method of claim 7 where the C.sub.2-9-dioyl halide is butanedioyl dichloride.

9. The method of claim 8 where the non-aqueous reactive solvent is a cycloalkanone.

10. The method of claim 9 where the non-aqueous reactive solvent is cyclopentanone.

11. The method of claim 5 where the temperature is in the range 120? C. to 170? C.

12. The method of claim 5 where the period of time is 15 to 105 minutes.

13. An asymmetric composite membrane comprising a first layer of cross-linked sulfonated poly(ether ether ketone) adhered to a second layer of sulfonated microporous poly(ethylene).

14. The membrane of claim 13 where the thickness of the first layer is in the range 0.1 to 50 ?M and the thickness of the second layer is in the range 5 to 200 ?M.

15. The membrane of claim 14 where the thickness of the first layer is in the range 1 to 5 ?M and the thickness of the second layer is in the range 5 to 20 ?M.

16. The membrane of claim 13 where the first layer of cross-linked sulfonated poly(ether ether ketone) is prepared according to a method comprising the step of incubating in the presence of a Friedel-Crafts type catalyst a mixture of a chlorosulfonated poly(ether ether ketone) and a C.sub.2-9-dioyl halide cross-linking agent solvated in a non-aqueous reactive solvent at a temperature substantially below 180? C. for a period of time sufficient to provide the cross-linked sulfonated poly(ether ether ketone).

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1. Comparison of FTIR spectra recorded for samples of cross-linked sulfonated PEEK: 150SClPEEK30 (upper trace), 150SClPEEK15 (middle trace) and control sample (lower trace). The scale of the vertical axis (absorbance; not shown) is the same for each trace.

(2) FIG. 2. Comparison of FTIR spectra recorded (2000 to 550 cm.sup.?1) for selected samples of cross-linked sulfonated PEEK: 150SClPEEK302X (upper trace), 150SCl30 (middle trace) and 150SClPEEK30 (lower trace). The scale of the vertical axis (absorbance; not shown) is the same for each trace.

(3) FIG. 3. Comparison of FTIR spectra recorded (4000 to 2000 cm.sup.?1) for selected samples of cross-linked sulfonated PEEK: 150SClPEEK302X (upper trace), 150SCl30 (middle trace) and 150SClPEEK30 (lower trace). The scale of the vertical axis (absorbance; not shown) is the same for each trace.

(4) FIG. 4. Comparison of FTIR spectra recorded (2000 to 550 cm.sup.?1) for samples of cross-linked sulfonated PEEK prepared by casting the same mixture (including the crosslinking agent succinyl chloride) and curing at 150? C. for 30 min or 15 min: 150SCl30 (upper trace) and 150SCl15 (lower trace). The scale of the vertical axis (absorbance; not shown) is the same for each trace.

(5) FIG. 5. Comparison of FTIR spectra recorded (2000 to 550 cm.sup.?1) for samples of cross-linked sulfonated PEEK prepared by casting mixtures with and without the inclusion of the crosslinking agent succinyl chloride and curing at 150? C. for 15 min: 150SCl30 (upper trace) and 50SCl15 (lower trace). The scale of the vertical axis (absorbance; not shown) is the same for each trace.

(6) FIG. 6. Exploded view of the filter assembly (Sterlitech Corp.).

(7) FIG. 7. Graph showing dependency of flux rate (L/m2h) (Y axis) on temperature (degrees C.) of the feed stream where the feed stream was milk (solid circles) or water (solid diamonds).

(8) FIG. 8. Flux rates (L/m.sup.2h) (Y axis) where the feed stream was milk at a pressure of 20 bar (solid diamonds) or 28 bar (solid squares) with in situ cleaning (vertical lines).

(9) FIG. 9. Graph showing the rejection of fat (solid diamonds), lactose (solid triangles), protein (solid squares) and total solids (crosses) determined for samples of permeate where the feed stream was skim milk at a pressure of 20 bar or 28 bar (third and fourth samples).

(10) FIG. 10. Flux rates (L/m.sup.2h) (Y axis) obtained following disinfection of the asymmetric composite membrane where the feed stream was water at a pressure of 20 bar.

(11) FIG. 11. Flux rates (L/m.sup.2h) (Y axis) obtained following disinfection of the asymmetric composite membrane where the feed stream was skim milk at a pressure of 20 bar.

(12) FIG. 12. Graph showing the rejection of fat (solid circles), lactose (solid inverted triangles), protein (open circles) and total solids (open inverted triangles) determined for samples of permeate where the feed stream was whole milk at a pressure of 20 bar and temperature of 7? C.

DETAILED DESCRIPTION

(13) A chlorosulfonated poly(ether ether ketone) is used as the substrate for cross-linking, specifically csPEEK. It is desirable to retain the degree of hydrophilicity imparted to the PEEK substrate by chlorosulfonation when crosslinking for the purpose of preparing a polymer for use in the fabrication of membranes for use in processes driven by hydrostatic or osmotic pressure. When crosslinking via the introduced chlorosulfonyl groups the degree of hydrophilicity may be reduced. Crosslinking of the csPEEK substrate via a Friedel-Crafts type reaction promotes maintenance of the desired degree of hydrophilicity. Furthermore, curing at temperatures substantially below those known to promote thermally induced crosslinking between chlorosulfony/sulfonyl groups favours the DXL being attributable to participation of the cross-linking agent in the crosslinking reaction. Curing at lower temperatures also reduces the likelihood of thermal degradation of the substrate polymer.

(14) The microstructure of the polymer network formed by cross-linking will also be influenced by the structure of the cross-linking agent selected for use. The combination of a film of cross-linked sulfonated poly(ether ether ketone) rejection layer adhered to a sheet of sulfonated microporous polyethylene backing layer provide an asymmetric composite membrane with the advantage of resistance to chemical decomposition and hence durability in commercial processing operations. In addition, the asymmetric composite membrane is tolerant of desiccation facilitating storage and transport.

EXAMPLE

(15) Preparation of Sulfonated Microporous Poly(Ethylene) (Support Layer)

(16) A sheet of sulfonated microporous poly(ethylene) was prepared substantially as described in the publication of Briggs (2015). An amount of 250 g of phosphorous pentoxide was added to a volume of 469 mL of sulfuric acid to provide a mixture of 1:5 (mol/mol) phosphorous pentoxide-sulfuric acid and heated to 90? C. to dissolve the phosphorous pentoxide (sulfonating agent).

Example 1

(17) Sheets of microporous poly(ethylene) were cut in to 15?20 cm pieces and wetted with a mixture of DMSO-trichloromethane (9:1 (v/v)). Excess of the mixture was removed from the pieces before they were frozen by covering them in liquid nitrogen. Immediately after freezing the pieces were added to the sulfonating agent at room temperature and incubated at 80? C. for 90 minutes. The incubated pieces were removed from the sulfonating agent and allowed to sit for 3 hours in order to dilute the acid before rinsing twice with methanol to remove all residual sulfonating agent.

Example 2

(18) Sheets of microporous poly(ethylene) were cut in to 14?28 cm pieces and whetted with a mixture of 20% chloroform and 8% dimethyl sulfoxide (DMSO) before being placed between glass fibre sheets and keeping on dry ice overnight. The sheets were then immersed in the sulfonating agent before being covered and cured in an oven at 85? C. for 90 minutes. Following curing the glass fibre sheets were removed and the sulfonated microporous poly(ethylene) sheet humidified overnight. The sheet was then rinsed with methanol and stored dry before use as a backing layer.

(19) Preparation of Cross-Linked Sulfonated PEEK (Rejection Layer)

Example 3

(20) Solutions of dry chlorosulfonated poly(ether ether ketone), the cross-linking agent ethanedioic acid (oxalic acid), and the chloride catalyst ferric chloride (FeCl.sub.3), were prepared in the non-aqueous reactive solvent cyclopentanone under ambient conditions (room temperature and pressure): 6.6 g of dry chlorosulfonated poly(ether ether ketone) was dissolved in 50 mL of cyclopentanone (solution 1); 0.769 g of ethanedioic acid (oxalic acid) was dissolved in 25 mL of cyclopentanone (solution 2); and 0.138 g of ferric chloride (FeCl.sub.3) was dissolved in 25 mL of cyclopentanone (solution 3). A 3 mL volume of solution 2 was added to a 6 mL volume of solution 1 and the two solutions mixed thoroughly. A 3 mL volume of solution 3 was then added and the combined solutions mixed to provide a cross-linking solution. The molar ratio of chlorosulfonated poly(ether ether ketone) to ethanedioic acid (oxalic acid) was approximately 1:0.5. The molar ratio of chlorosulfonated poly(ether ether ketone) to ferric chloride (FeCl.sub.3) was approximately 1:0.05. The cross-linking solution was incubated at a temperature of 85? C. for two hours and then allowed to cool for 30 minutes under ambient conditions. The cooled cross-linking solution was then cast onto a glass plate to provide a film with a thickness of approximately 0.2 mm. The film was cast under ambient conditions and left for two to five minutes before being cured at 85? C. for 2.5 hours. During curing the upper surface of the film was protected with a second glass plate located approximately 1 cm above the surface.

Example 4

(21) Solutions of dry chlorosulfonated poly(ether ether ketone), the cross-linking agent tartaric acid, and the chloride catalyst ferric chloride (FeCl.sub.3), were prepared in the non-aqueous reactive solvent cyclopentanone under ambient conditions (room temperature and pressure): 6.6 g of dry chlorosulfonated poly(ether ether ketone) was dissolved in 50 mL of cyclopentanone (solution 1); and 1.281 g of tartaric acid and 0.138 g of ferric chloride (FeCl.sub.3) were dissolved in 25 mL of cyclopentanone (solution 2). A 3 mL volume of cyclopentanone was added to a 6 mL volume of solution 1 and mixed thoroughly. A 3 mL volume of solution 2 was then added and the combined solutions mixed to provide a cross-linking solution. The molar ratio of chlorosulfonated poly(ether ether ketone) to tartaric acid was approximately 1:0.5. The molar ratio of chlorosulfonated poly(ether ether ketone) to ferric chloride (FeCl.sub.3) was approximately 1:0.05. The cross-linking solution was incubated at a temperature of 85? C. for two hours and then allowed to cool for 30 minutes under ambient conditions. The cooled cross-linking solution was then cast onto a glass plate to provide a film with a thickness of approximately 0.2 mm. The film was cast under ambient conditions and left for two to five minutes before being cured at 85? C. for 2.5 hours. During curing the upper surface of the film was protected with a second glass plate located approximately 1 cm above the surface.

Example 5

(22) Solutions of dry chlorosulfonated poly(ether ether ketone), the cross-linking agent citric acid, and the chloride catalyst ferric chloride (FeCl.sub.3), were prepared in the non-aqueous reactive solvent cyclopentanone under ambient conditions (room temperature and pressure): 6.6 g of dry chlorosulfonated poly(ether ether ketone) was dissolved in 50 mL of cyclopentanone (solution 1); and 1.640 g of citric acid and 0.138 g of ferric chloride (FeCl.sub.3) were dissolved in 25 mL of cyclopentanone (solution 2). A 3 mL volume of cyclopentanone was added to a 6 mL volume of solution 1 and mixed thoroughly. A 3 mL volume of solution 2 was then added and the combined solutions mixed to provide a cross-linking solution. The molar ratio of chlorosulfonated poly(ether ether ketone) to citric acid was approximately 1:0.5. The molar ratio of chlorosulfonated poly(ether ether ketone) to ferric chloride (FeCl.sub.3) was approximately 1:0.05. The cross-linking solution was incubated at a temperature of 85? C. for two hours and then allowed to cool for 30 minutes under ambient conditions. The cooled cross-linking solution was then cast onto a glass plate to provide a film with a thickness of approximately 0.2 mm. The film was cast under ambient conditions and left for two to five minutes before being cured at 85? C. for 2.5 hours. During curing the upper surface of the film was protected with a second glass plate located approximately 1 cm above the surface.

Example 6

(23) Solutions of dried chlorosulfonated poly(ether ether ketone), the cross-linking agents ethanedioic acid (oxalic acid) and tartaric acid, and the chloride catalyst ferric chloride (FeCl.sub.3), were prepared in the non-aqueous reactive solvent cyclopentanone under ambient conditions (room temperature and pressure): 6.6 g of chlorosulfonated poly(ether ether ketone) was dissolved in 50 mL of cyclopentanone (solution 1); 0.769 g of ethanedioic acid (oxalic acid) was dissolved in 25 mL of cyclopentanone (solution 2); 1.281 g of tartaric acid and 0.138 g of ferric chloride (FeCl.sub.3) was dissolved in 25 mL of cyclopentanone (solution 3); and 0.138 g of ferric chloride (FeCl.sub.3) was dissolved in 25 mL of cyclopentanone (solution 4). A 1.5 mL volume of cyclopentanone and a 1.5 mL volume of solution 2 was added to a 6 mL volume of solution 1 and mixed thoroughly. A 1.5 mL volume of solution 3 and a 1.5 mL volume of solution 4 was then added and the combined solutions mixed to provide a cross-linking solution. The molar ratio of chlorosulfonated poly(ether ether ketone) to tartaric acid was approximately 1:0.5. The molar ratio of chlorosulfonated poly(ether ether ketone) to ferric chloride (FeCl.sub.3) was approximately 1:0.05. The cross-linking solution was incubated at a temperature of 85? C. for two hours and then allowed to cool for 30 minutes under ambient conditions. The cooled cross-linking solution was then cast onto a glass plate to provide a film with a thickness of approximately 0.2 mm. The film was cast under ambient conditions and left for two to five minutes before being cured at 85? C. for 2.5 hours. During curing the upper surface of the film was protected with a second glass plate located approximately 1 cm above the surface.

Example 7

(24) An amount of 50 g of poly(ether ether ketone) (Victrex) having a density of 1.3 g cm.sup.?3 and a melt viscosity of 400? C. of 90 Pa.Math.s was added to a volume of 250 mL of chloroform (Fisher Chemicals) followed by the addition of a volume of 250 mL of chlorosulfonic acid (Nacalai Tesque Inc.). The mixture was stirred for two hours at 50? C. and then washed twice with two separate volumes of 200 mL of chloroform and thrice with three separate volumes of 400 mL of chloroform. Washing was indicated to be complete when the volume of chloroform used in the washing remained colourless.

(25) The orange coloured, viscous residue remaining following the chloroform washings was washed repeatedly with volumes of deionized water until the pH of the wash water had increased to 5. The resulting whitish coloured product was then broken into small flakes and dried in a vacuum oven at 65? C. for five days.

(26) An amount of 1.9932 g of flakes of the dried, whitish coloured product was added to a volume of 15 mL cyclopentanone (A K Scientific) to provide a 13.2% (w/v) solution of the product. An amount of 0.235 g zinc chloride (Sigma-Aldrich) was added to a volume of 5 mL cyclopentanone (A K Scientific) to provide a 0.55% (w/v) solution of the catalyst.

(27) To a volume of 15 mL of the solution of product in a vial either a volume of 0.3 mL of succinyl chloride (Sigma-Aldrich) or an amount of 0.4 g of 1,3,5-benzenetricarboxylic chloride (Sigma-Aldrich) was added. Following one of these additions a volume of 1.5 mL of the solution of the catalyst was added to provide a mixture of product, cross-linker and catalyst in a molar ratio of 1:0.5:0.1.

(28) Following shaking of the vial the mixture was cast on a glass plate and cured at a predetermined temperature for a predetermined period of time. The temperatures and times used to provide samples of membrane consisting of putatively cross-linked chlorosulfonated poly(ether ether ketone) are presented in Table 1 and Table 2.

(29) For comparative purposes, samples of membrane were also prepared without the addition of cross-linker and catalyst to the cast mixture. The curing conditions used in the preparation of these latter samples are presented in Table 3.

(30) TABLE-US-00001 TABLE 1 Curing temperatures and times used for the preparation of putatively cross-linked chlorosulfonated poly(ether ether ketone) membranes where the crosslinking agent was succinyl chloride. Molar ratio (product to Molar ratio Sample Curing temp Curing time crosslinking (product to designation (?5? C.) (min) agent) catalyst) 120SCl15 120 15 1:0.5 1:0.1 120SCl30 120 30 1:0.5 1:0.1 120SCl45 120 45 1:0.5 1:0.1 120SCl60 120 60 1:0.5 1:0.1 120SCl75 120 75 1:0.5 1:0.1 120SCl90 120 90 1:0.5 1:0.1 150SCl15 150 15 1:0.5 1:0.1 150SCl30 150 30 1:0.5 1:0.1 150SCl45 150 45 1:0.5 1:0.1 150SCl60 150 60 1:0.5 1:0.1 150SCl75 150 75 1:0.5 1:0.1 150SCl90 150 90 1:0.5 1:0.1 150SCl105 150 105 1:0.5 1:0.1 160SCl15 160 15 1:0.5 1:0.1 170SCl15 170 15 1:0.5 1:0.1 150SCl302x 150 30 1:1 1:0.1

(31) TABLE-US-00002 TABLE 2 Curing temperatures and times used for the preparation of putatively cross-linked chlorosulfonated poly(ether ether ketone) membranes where the crosslinking agent was 1,3,5-benzenetricarboxylic chloride. Molar ratio (product to Molar ratio Sample Curing temp Curing time crosslinking (product to designation (?5? C.) (min) agent) catalyst) 120TMC15 120 15 1:0.33 1:0.1 120TMC30 120 30 1:0.33 1:0.1 120TMC45 120 45 1:0.33 1:0.1 120TMC60 120 60 1:0.33 1:0.1 120TMC75 120 75 1:0.33 1:0.1 120TMC90 120 90 1:0.33 1:0.1 150TMC15 150 15 1:0.33 1:0.1 150TMC30 150 30 1:0.33 1:0.1 150TMC45 150 45 1:0.33 1:0.1 150TMC60 150 60 1:0.33 1:0.1 150TMC75 150 75 1:0.33 1:0.1 160TMC15 160 15 1:0.33 1:0.1 170TMC15 170 15 1:0.33 1:0.1

(32) TABLE-US-00003 TABLE 3 Curing temperatures and times used for the preparation of chlorosulfonated poly(ether ether ketone) membranes without the addition of catalyst or crosslinking agent. Molar ratio Curing (product to Molar ratio Sample temp Curing time crosslinking (product to designation (?5? C.) (min) agent) catalyst) 120SClPEEK15 120 15 120SClPEEK30 120 30 120SClPEEK45 120 45 120SClPEEK60 120 60 120SClPEEK75 120 75 120SClPEEK90 120 90 150SClPEEK15 150 15 150SClPEEK30 150 30 150SClPEEK45 150 45 150SClPEEK60 150 60 150SClPEEK75 150 75 150SClPEEK90 150 90 150SClPEEK105 150 105 150SClPEEK120 150 120 160SClPEEK15 160 15 170SClPEEK15 170 15
Characterisation of Membranes

(33) Solubilities of samples of membrane were determined at room temperature by placing a small piece (circa 25 mm.sup.2) of sample in a volume of 3 mL of a solvent. A lack of solubility in various solvents was indicative of the sample of membrane consisting of cross-linked polymer. The appearances and solubilities of the samples in the solvent cyclopentanone are presented in Table 4. The solubility of selected samples of membrane (150SClPEEK30, 150SCl30 and 150SCl302x) in the solvents acetone, dimethylsulfoxide and methanol and acid (nitric acid) and alkali (sodium hydroxide)) are presented in Table 5.

(34) Fourier transform infrared spectra (FTIR) were recorded using a Thermo Electron Nicolet 8700 spectrometer equipped with a single bounce ATR and diamond crystal. An average of 32 scans with a 4 cm.sup.?1 resolution were recorded for each sample. For comparative purposes the FTIR spectrum of a sample of membrane prepared by the casting of a mixture without the addition of crosslinking agent or catalyst (control sample) was also recorded. All samples were washed with deionised water before recording scans. Comparisons

(35) TABLE-US-00004 TABLE 4 Appearance and solubility in cyclopentanone (after 24 hours) of samples of membrane. Sample Appearance Solubility 120SClPEEK15 Brown film Soluble 120SClPEEK30 Dark brown film Soluble 120SClPEEK45 Dark brown film Soluble 120SClPEEK60 Dark brown film Soluble 120SClPEEK75 Dark brown film Soluble 120SClPEEK90 Black film Soluble 150SClPEEK15 Dark brown film Soluble 150SClPEEK30 Black film Soluble 150SClPEEK45 Black film Soluble 150SClPEEK60 Black film, brittle Soluble 150SClPEEK75 Black film, brittle Soluble 150SClPEEK90 Black film brittle Partially soluble 150SClPEEK105 Black film, brittle Partially soluble 150SClPEEK120 Black film brittle Partially soluble 160SClPEEK15 Black film Soluble 170SClPEEK15 Black film Soluble 120SCl15 Brown film Soluble 120SCl30 Dark brown film Soluble 120SCl45 Dark brown film Soluble 120SCl60 Dark brown fim Soluble 120SCl75 Dark brown film Soluble 120SCl90 Dark brown film Soluble 150SCl15 Black film Partially soluble 150SCl30 Black film Insoluble 150SCl45 Black film, brittle Insoluble 150SCl60 Black film, brittle Insoluble 150SCl75 Black film, brittle Insoluble 150SCl90 Black film, brittle Insoluble 150SCl105 Black film, brittle Insoluble 160SCl15 Black film Soluble 170SCl15 Black film Partially soluble 150SCl302x Black film Insoluble 120TMC15 Brown film Soluble 120TMC30 Dark brown film Soluble 120TMC45 Dark brown film Soluble 120TMC60 Dark brown film Soluble 120TMC75 Dark brown film Partially soluble 120TMC90 Dark brown film Partially soluble 150TMC15 Black film Partially soluble 150TMC30 Black film, brittle Partially soluble 150TMC45 Black film, brittle Insoluble 150TMC60 Black film, brittle Insoluble 150TMC75 Black film, brittle Insoluble 160TMC15 Black film Soluble 170TMC15 Black film Partially soluble
of the FTIR spectra recorded for the selected samples of membrane and the control sample are presented in FIGS. 1 to 5.

(36) The observed solubilities and FTIR spectra of the selected samples of membrane are consistent with crosslinking of the csPEEK substrate having occurred.

(37) TABLE-US-00005 TABLE 5 Solubilities of selected samples (shaded, Table 4) in different solvents. Solvent 150SClPEEK30 150SCl30 150SCl302x Dimethylsulfoxide Dissolved Undissolved, swollen Undissolved, swollen Cyclopentanone Dissolved Undissolved, swollen Undissolved, swollen Acetone Undissolved, Undissolved, Undissolved, slightly swollen slightly swollen slightly swollen Methanol Undissolved, swollen Undissolved, Undissolved, slightly swollen slightly swollen Sodium hydroxide Undissolved Undissolved Undissolved solution (pH 13) Nitric acid (pH 2) Undissolved Undissolved Undissolved Cyclonentanone Undissolved, Undissolved Undissolved (after 24 hours in slightly swollen sodium hydroxide solution (pH 13)) Cyclopentanone Dissolved partially, Undissolved, swollen Undissolved, swollen (after 24 hours in swollen nitric acid (pH 2))

Example 8

(38) An amount of 13.97 g of poly(ether ether ketone) (Victrex) having a density of 1.3 g cm.sup.?3 and a melt viscosity at 400? C. of 90 Pa.Math.s was added to a volume of 66.5 mL of chloroform (Fisher Chemicals) mixed with 3.5 mL thionyl chloride. An amount of 70 g cholorsulfonic acid (Nacalai Tesque Inc.) was then added and the mixture stirred for two hours at 50? C. The mixture was then washed twice with two separate volumes of 200 mL of chloroform and thrice with three separate volumes of 400 mL of chloroform. Washing was indicated to be complete when the volume of chloroform used in the washing remained colourless. The orange coloured, viscous residue remaining following the chloroform washings was washed repeatedly with volumes of deionized water until the pH of the wash water had increased to 5. The resulting whitish coloured product was then broken into small flakes and dried in a vacuum oven at 65? C. for four days. Following drying the product was added to a volume of 100 mL tetrachloroethylene and a volume of 20 mL thionyl chloride and stirred for five hours. The product was then dried in a vacuum oven at 65? C. overnight.

(39) Preparation of Asymmetric Composite Membrane

Example 9

(40) The cooled crosslinking solution was cast onto a borosilicate glass plate to provide a wet film with a thickness of 50 to 600 ?M prior to curing. A sheet of the sulfonated microporous poly(ethylene) was adhered by applying directly to the wet film ensuring full contact between the abutting surfaces of the film and sheet. The asymmetric composite was then transferred to an oven and cured for a period of ten to ninety minutes at a temperature of greater than 85? C., but not exceeding the melting point of the sheet. Following cooling the asymmetric composite membrane was removed from the glass plate in warm water.

Example 10

(41) The cooled crosslinking solution was cast onto a borosilicate glass plate to provide a wet film with a thickness of 50 to 600 ?M prior to curing. The cast crosslinking solution was allowed to stand under ambient conditions (room temperature and non-condensing humidity) for a period of at least 30 minutes. A sheet of the sulfonated microporous poly(ethylene) was then adhered by applying directly to the film formed by coagulation ensuring full contact between the abutting film and sheet surfaces. The asymmetric composite was then transferred to an oven and cured for a period of ten to ninety minutes at a temperature of greater than 85? C., but not exceeding the melting point of the sheet. Following cooling the asymmetric composite membrane is removed from the glass plate in warm water.

Example 11

(42) A solution of chlorosulfonated poly(ether ether ketone) product obtained according to Example 8 was prepared at a concentration of 0.132 g/mL in cyclopentanone. To a volume of 15 mL of this solution an amount of 0.3 mL succinyl chloride (as cross-linking agent) and 1.5 mL zinc chloride (as catalyst) was added to provide a mixture of product, cross-linking agent and catalyst in a molar ratio of 1:0.5:0.1. The mixture was cast on a glass plate and the solvent evaporated at 85? C. before curing of the film at 120? C. for one hour. The cured film was then whetted with 50% tetrachloroethylene in chloroform before adhering a sheet of dry sulfonated microporous poly(ethylene) as the backing layer. To adhere the sheet of sulfonated microporous poly(ethylene) prepared according to Example 2, the sheet was flattened using 25% tetrachloroethylene in chloroform and 20% tetrachloroethylene in a mixture of 10% cyclopentanone and 90% chloroform followed by cyclopentanone. The asymmetric composite was then dried at 85? C. for 15 minutes and the membrane evaluated.

(43) Performance of Asymmetric Composite Membrane

(44) The performance of the asymmetric composite membranes prepared according to Examples 10 and 11 were evaluated using a reverse osmosis (RO) filter assembly of the type illustrated in FIG. 6.

Example 10

(45) Flux Testing

(46) A section of the asymmetric composite membrane (1) was pre-wetted by dipping in distilled water and then placed on a coarse support mesh (2) located in the lower half (3) of the filter assembly housing, with a shim (4) optionally interposed. The section was placed with the rejection layer of the asymmetric composite membrane facing downwards. A fine mesh (5) located in the upper half of the filter assembly (6) housing was placed over the upper surface of the section of the asymmetric composite membrane (1). The filter assembly was sealed by sealing rings (7,8) and held in a hydraulic press pressurised to 60 Bar. The inlet port (9) of the lower half of the filter assembly housing (3) was in fluid connection with a feed reservoir (not shown) from which a feed stream was pumped at a rate to maintain the feed stream pressure measured on the pressure gauge (10). A pressure of 5 Bar was maintained for feed streams comprising water and salts. A pressure of 10 Bar was maintained for feed streams of milk. Feed streams were pre-chilled to 8? C. to mimic commercial processing conditions. Permeate was collected from the outlet port (11) of the upper half of the filter assembly housing (6) in a graduated cylinder (not shown). Collection was started at least 5 minutes after the commencement of permeate being discharged from the outlet port (11) in order to exclude water from the pre-wetting of the membrane or permeate from previously used feed streams.

(47) In Situ Cleaning of Membrane

(48) To mimic commercial processing operations the asymmetric composite membrane was subjected to repeated in situ washing protocols. The intermediate and subsequent flux rates were determined to assess the likely durability of the membrane in commercial processing operations. The in situ washing protocol was based on that employed in a commercial processing operation, but modified in duration to compensate for the greater exposure of the membrane to the cleaning agents (caustic and acid) in the filter assembly. Prior to the washing steps the membrane was rinsed by circulating water at an initial temperature of 65? C. through the filter assembly for a period of three minutes before draining the system.

(49) The membrane was subjected to a first wash by circulating a circa 2% (w/v) sodium hydroxide solution (caustic wash) through the filter assembly for a period of five minutes before draining and flushing the system by circulating water at an initial temperature of 65? C. through the filter assembly system for a period of five minutes. The membrane was subjected to a second wash by circulating a circa 2% (w/w) nitric acid solution (acid wash) through the filter assembly system for a period of ten minutes before draining and flushing the system of circulating water at an initial temperature of 65? C. for a period of ten minutes. The membrane was subjected to a third wash (a caustic wash) before flushing the system by circulating water at an initial temperature of 65? C. for a period of five minutes before circulating chilled water for a period of five minutes to cool the system. All rinsing and washing steps were performed with no pressure recorded on the pressure gauge (8).

(50) Samples of the asymmetric composite membrane were tested for tensile strength and burst strength following flux testing and in situ washing to assess the likely durability of the membrane in commercial processing operations. All testing methods were performed in accordance with ASTM standards (Anon (2009), Anon (2010) and Anon (2012)).

(51) Tensile Strength Testing

(52) Samples for testing were excised from a sheet of the asymmetric composite membrane used in flux testing using a die and hydraulic press. The die was positioned on the upper surface of the sheet of the asymmetric composite membrane supported on a wooden board. Sufficient pressure was applied to the die using the hydraulic press to cut through the sheet. The sample was carefully removed from the die and subjected to testing according to the following protocol.

(53) Samples were preconditioned at 23? C. plus or minus 2? C. and 50% plus or minus 10% relative humidity prior to testing. The thicknesses and widths of samples were measured at three points along the gage length of each sample. The calibrated load weighting system was zeroed and the machine crosshead adjusted to provide the required grip separation. Samples were placed in alignment in the grips of the universal testing machine ensuring sufficient tension on both edges of the sample. Where necessary, blotting or filter paper was used on the surface of the grips to prevent slippage. The extension indicator and recording system of the universal testing machine were reset before starting the machine and testing the samples to failure. Parts of samples tested to failure were removed from the universal testing machine and labelled. Data from testing of samples that failed outside the gage length, i.e. where contacting the grips of the universal testing machine or by tearing with an angle of separation greater than 30 degrees from the perpendicular, were excluded from analyses.

(54) Bursting Strength Testing

(55) The bursting strength of a sheet of the asymmetric composite membrane used in flux testing was measured (according to Mullen) using a tester (Burst-o-Matic?, Lorentzen and Wittre). Measurements were taken at multiple locations on the sheet. Data are presented in Table 6.

(56) TABLE-US-00006 TABLE 6 Comparison of burst pressures for the used asymmetric composite membrane and an unused commercially available porous poly(ethylene) (K2045, 20 ?m thick, porosity 45%, CELGARD?). Tensile strength (MPa) Sample Mean Standard deviation CELGARD? K2045 98.3 10 composite membrane 84.9 2.6
Rejection Assessment

(57) Samples of permeate collected from a milk feed stream with periodic in situ cleaning of the membrane were analysed for fat, lactose, protein and total solids content. The results of these analyses are presented in FIG. 9.

(58) In Situ Disinfection of Membrane

(59) Prior to the washing steps the membrane was rinsed by circulating water at an initial temperature of 65? C. through the filter assembly for a period of three minutes before draining the system. The membrane was subjected to a first wash by circulating a circa 2% (w/v) sodium hydroxide solution (caustic wash) through the filter assembly for a period of five minutes before draining and flushing the system by circulating water at an initial temperature of 65? C. through the filter assembly system for a period of five minutes. The membrane was subjected to a second wash by circulating a circa 2% (w/w) nitric acid solution (acid wash) through the filter assembly system for a period of ten minutes before draining and flushing the system by circulating water at an initial temperature of 65? C. for a period of ten minutes. The membrane was subjected to a third wash by circulating a 2% (w/w) sodium hypochlorite solution (disinfection wash) through the filter assembly system for a period of five minutes before draining and flushing the system with circulating water at an initial temperature of 65? C. for a period of ten minutes. The membrane was subjected to a final wash (a caustic wash) before flushing the system by circulating water at an initial temperature of 65? C. for a period of five minutes before circulating chilled water for a period of five minutes to cool the system. As before all rinsing and washing steps were performed with no pressure recorded on the pressure gauge (8).

(60) Post Disinfection Flux Testing

(61) The performance of the asymmetric composite membrane was evaluated following exposure to 2% (w/w) sodium hypochlorite. Flux rates obtained for water as the feed solution at a pressure of 23 bar are provided in FIG. 10. Permeate flux rates obtained when the feed stream was homogenised milk (blue top) are provided in FIG. 11. Stable flux rates of ca. 15 liters per m.sup.2 per hour were obtainable. An operating pressure of 20 bar for a flux rate of 13 liters per m.sup.2 per hour was considered optimal for long-term use of the membrane.

Example 11

(62) A section of the asymmetric composite membrane was cut to size and mounted in the assembly illustrated in FIG. 6 as described above. A feed stream of homogenised whole milk (blue top) at a temperature of 7? C. was pumped at a rate (600 rpm) to maintain a feed stream pressure of 20 bar. Collection of permeate was alternated with the following clean-in-place (CIP) protocol: Two volumes of two liters tap water at a temperature of 35? C. (flushed for 5 minutes each); Circulating sodium hydroxide (pH 12) at a temperature of 35? C. for a period of 10 minutes; One volume of one liter of tap water at a temperature of 35? C. (flushed for 5 minutes); Circulating hydrochloric acid (pH 1.522) at a temperature of 35? C. for a period of 10 minutes; One volume of one liter of tap water at a temperature of 35? C. (flushed for 5 minutes each); Circulating sodium hydroxide (pH 12) at a temperature of 35? C. for a period of 10 minutes; Two volumes of two liters tap water at a temperature of 35? C. (flushed for 5 minutes each); Rinsing with cold tap water for a period of 5 minutes.

(63) Ten samples of permeate from the milk feed stream were collected and independently analysed (Livestock Improvements Corporation, Hamilton) for fat, lactose, protein and total solids content. The results of these analyses are presented in FIG. 12. The asymmetric composite membrane provided consistently high rejection of fat, lactose, protein and total solids despite the repeated application of the CIP protocol. The performance of the membrane is consistent with its proposed use in food processing applications.

(64) Although the invention has been described with reference to embodiments or examples it should be appreciated that variations and modifications may be made to these embodiments or examples without departing from the scope of the invention. Where known equivalents exist to specific elements, features or integers, such equivalents are incorporated as if specifically referred to in this specification. In particular, variations and modifications to the embodiments or examples that include elements, features or integers disclosed in and selected from the referenced publications are within the scope of the invention unless specifically disclaimed. The advantages provided by the invention and discussed in the description may be provided in the alternative or in combination in these different embodiments of the invention.

REFERENCED PUBLICATIONS

(65) Anon (2009) Standard Practice for Cutting Film and Sheeting Test Specimens (D6287) ASTM International, 100 Barr Harbour Drive, PO Box C700, West Conshohocken, Pa. 19428-2959, United States. Anon (2010) Standard Test Method for Tensile Properties of Plastics (D638) ASTM International, 100 Barr Harbour Drive, PO Box C700, West Conshohocken, Pa. 19428-2959, United States. Anon (2012) Standard Test Method for Tensile Properties of Thin Plastic Sheeting (D882) ASTM International, 100 Barr Harbour Drive, PO Box C700, West Conshohocken, Pa. 19428-2959, United States. Briggs (2015) Microporous polyolefin sulfonic acids and methods for their preparation International application no. PCT/EP2014/066668 [Publ. no. WO 2015/015009 A1]. Deb et al (2007) Modification of sulfonated poly(ether ether ketone) with phenolic resin Polym. Adv. Technol. 18, 419-426. Di Vona et al (2008) Synthetic strategies for the preparation of proton-conducting hybrid polymers based on PEEK and PPSU for PEM fuel cells C. R. Chimie, 11, 1074-1081. Di Vona et al (2009) Analysis of Temperature-Promoted and Solvent-Assisted Cross-Linking in Sulfonated Poly(ether ether ketone) (SPEEK) Proton-Conducting Membranes J. Phys. Chem. B 2009, 113, 7505-7512. Hande et al (2008) Crosslinking of sulfonated poly (ether ether ketone) using aromatic bis (hydroxyethyl) compound, J. Membr. Sci., 322, 67-73. Hirota et al (2010) Hydrolysis of acetic anhydride: non-adiabatic calorimetric determination of kinetics and heat exchange Chem. Eng. Sci., 65, 3849-3858. Hou et al (2012) Building bridges: Crosslinking of sulfonated aromatic polymersa review J. Membr. Sci., 423-424, 113-127. Loeb (1981) The Loeb-Sourirajan Membrane: How It Came About In Synthetic Membranes, ACS Symposium Series, American Chemical Society, Washington, D.C. McCutcheon and Wang (2013) Osmotic Processes for a Sustainable 21st CenturyGuest Editorial Desalination, 312, 1. Merle et al (2014) Friedel Crafts crosslinked highly sulfonated polyether ether ketone (SPEEK) membranes for a vanadium/air redox flow battery, Membranes 4, 1-19. Mikhailenko et al (2004) Proton conducting membrane based on cross-linked sulfonated poly(ether ether ketone) (SPEEK) J. Membr. Sci. 233, 93-99. Mikhailenko et al (2006) Properties of PEMs based on crosslinked sulfonated poly(ether ether ketone) J. Membr. Sci. 285, 306-316. Rhoden et al (2011) Low equivalent weight Friedel-Crafts cross-linked sulfonated poly(ether ether ketone) J. Membr. Sci., 376, 290-301. Ye et al (2009) Sulfonated poly (ether ether ketone) membranes crosslinked with sulfonic acid containing benzoxazine monomer as proton exchange membranes Polymer, 50, 3196-3203.