Affinity Membranes, Compounds, Compositions and Processes for Their Preparation and Use

Abstract

A porous membrane obtainable by a process comprising curing a composition comprising: (i) cross-linking agent(s) comprising at least one ligand group; (ii) inert solvent(s); (iii) polymerization initiator(s); and (vi) optionally monomer(s) other than component (i) which are reactive with component (i); wherein the composition satisfies the following equation: Z=wt(i)/(wt(i)+wt(iii)+wt(iv)) wherein: Z has a value of at least 0.6; wt(i) is the number of grammes of component (i) present in the composition; wt(iii) is the number of grammes of component (iii) present in the composition; and wt(iv) is the number of grammes of component (iv) present in the composition.

Claims

1-29. (canceled)

30. A porous membrane obtained by a process comprising curing a composition comprising: (i) cross-linking agent(s) comprising at least one ligand group L which comprises a compound of the Formula (1) or Formula (2):
(L)q-(A)m-(R)n   Formula (1)
(R)n-1-(A)m-(L)q-(A)m-(R)n-1   Formula (2) wherein: each L independently is a ligand group capable of binding Cu; each A independently is an organic linking group; each R independently is polymerisable group; q has a value of at least 1; each m independently has a value of 0 or 1; and each n independently has a value of at least 2; (ii) inert solvent(s); (iii) polymerization initiator(s); and (i) optionally monomer(s) other than component (i) which are reactive with component (i); wherein the composition satisfies the following equation:
Z=wt(i)/(wt(i)+wt(iii)+wt(iv)) wherein: Z has a value of at least 0.6; wt(i) is the number of grams of component (i) present in the composition; wt(iii) is the number of grams of component (iii) present in the composition; and wt(iv) is the number of grams of component (iv) present in the composition; and wherein said membrane has a Cu removal capacity between 150 and 1000 μmol/g of the membrane determined by inductively coupled plasma-optical emission spectrometry.

31. The membrane according to claim 30 wherein the composition comprises 1.0 to 80.0 wt % of cross-linking agent(s) (i), 98.9 to 19.9 wt % inert solvent(s) (ii) and 0.1 to 5.0 wt % polymerization initiator(s)(iii).

32. The membrane according to claim 30 having a mean flow pore size of 100 nm to 5,000 nm as determined by a porometer with the membrane under an applied pressure of up to 35 mbar nitrogen gas and/or a porosity of 10% or more as determined by pycnometer measurements of the membrane under helium atmosphere according to formula
Porosity=p.sub.real−p.sub.apparent/p.sub.real×100%.

33. The membrane according to claim 30 wherein the membrane is free from cationic and anionic groups.

34. The membrane according to claim 30 wherein component (i) is completely dissolved in component (ii) and the membrane is insoluble in component (ii).

35. The membrane according to claim 34 having a mean flow pore size of 100 nm to 5,000 nm as determined by a porometer with the membrane under an applied pressure of up to 35 mbar nitrogen gas and/or a porosity of 10% or more as determined by pycnometer measurements of the membrane under helium atmosphere according to formula 1
Porosity=p.sub.real−p.sub.apparent/p.sub.real×100%.

36. The membrane according to claim 34 wherein component (ii) comprises isopropanol and water.

37. The membrane according to claim 30 wherein the curing comprises photocuring.

38. The membrane according to claim 30 wherein the curing comprises polymerisation-induced phase separation of the membrane from the composition.

39. The membrane according to claim 30 which further comprises a porous support.

40. The membrane according to claim 30 which has the following properties (a), (b), optionally (c) and optionally (d): (a) a water flux of at least 1 l/(hr.Math.m.sup.2.Math.bar); (b) a porosity of 10% or more; (c) a binding constant for copper of above 10.sup.4 M.sup.−1; and (d) when left in distilled water for 16 hours increases in volume by less than 3.5%.

41. Use of a membrane according to claim 34 for detecting, filtering and/or purifying biomolecules.

42. Use of a membrane according to claim 34 for detecting metal ions or for filtering and/or purifying compositions comprising metal-ions.

43. A process for purifying a biomolecule and/or separating a biomolecule from other biomolecules comprising contacting the biomolecules with a membrane according to claim 30.

44. A process for purifying metal-ions and/or separating metal-ions from other particles or ionic species comprising contacting the metal-ions with a membrane according to claim 30.

45. The process according to claim 44 wherein the process comprises membrane size-exclusion chromatography or ion exchange chromatography.

Description

[0160] The invention will now be illustrated by the following, non-limiting examples in which all parts and percentages are by weight unless otherwise specified. The following abbreviations are used in the Examples:

TABLE-US-00001 FO-2223-10 is a non-woven, polypropylene-based, porous cloth of thickness 100 μm obtained from Freudenberg Group. This acts as a porous support. IPA is isopropanol. AMPS-Na is the sodium salt of 2-acrylamido-2-methylpropane sulphonic acid having the structure shown below (from Sigma Aldrich). CN132 is a cross-linking agent having no ligand groups and having the structure shown below (from Sartomer). MBA is a cross-linking agent having no ligand groups and having the structure shown below (from Sigma-Aldrich). (M49) is a cross-linking agent ha ving a ligand group and anionic groups and having the structure shown (from FUJIFILM). (M49) may be prepared by the method described for compound (M-11) in EP2,965,803, paragraph [0211]. BAMPS Is 1,1-bis(acryloylamido)-2-methylpropane-2-sulphonic acid (a cross- M50 linking agent comprising a ligand group). is a monofunctional reactive monomer with di-(2-picoyl)amine ligand functionality. M50 may be prepared by the method described for compound (11) in Sterk, M. and Bannwarth, W. (2015), Modulation of Reactivities of Dienophiles for Diels-Alder Reactions via Complexation of α, β-Unsaturated Chelating Amides. HCA, 98: 287- 307. (M3) may be prepared by the method described below in the Examples. (M7) may be prepared by the method described below in the Examples. (M19) may be prepared by the method described below in the Examples. V-50 is a thermal initiator having the structure as depicted below and can be obtained from FUJIFILM Wako Pure Chemical Corporation. [00013][00014][00015][00016][00017][00018][00019]

[0161] The water flux, metal removal capacity, porosity and thickness of the membranes described in the Examples and Comparative Example were measured as described below:

I) Water Flux (L/(m.SUP.2./Bar/Hr)) of the Membrane

[0162] Water flux of the membranes was measured using a device where the weight of water passing through the membrane was measured over time. A column of feed solution (pure water) was brought into contact with the membrane under evaluation and the feed solution was forced through the membrane by a constant applied air pressure on top of the water column. By achieving a constant flow of water at a constant applied pressure, the water flux could be determined.

[0163] Typically the membrane under evaluation was stored for 12 hours in pure water prior to use. The feed solution (250 ml of pure water) was brought into contact with the membrane (film contact area of 12.19 cm.sup.2). The water column was closed and pressurized with air pressure and the membrane was flushed with one water column (250 ml). The feed solution was refreshed and a constant air pressure of 100 mbar was applied. Finally, the measurements were performed by monitoring the weight by balance at a constant flow.

II) Metal Removal Capacity (μmol/q) of the Membrane

[0164] Prior to measuring a membrane's metal removal capacity, the membrane was weighed in the dry state. The membrane was then flushed 3× with demineralized water and 3× with iso-propanol. Subsequently, the membrane was placed in a filter holder and 50 ml of a 2.0 mM solution of CuSO.sub.4 in MeOH was passed through the membrane. The membrane was digested in acid solution and analysed by ICP-OES to determine the amount of Cu per unit weight of membrane in μmol/g (i.e. micromoles of copper per gram of dry membrane).

III) Mean Flow Pore Size (MFP) of the Membrane

[0165] The mean flow pore size of the membrane was measured using a porometer, e.g. a Porolux™ porometer. The membrane to be tested was fully wetted with a wetting fluid (e.g. Porefil™ wetting Fluid, an inert, non-toxic, fluorocarbon wetting fluid with zero contact angle). Place the wetted membrane in the sample holder of the porometer and apply a pressure of up to 35 mbar nitrogen gas. The porometer can then measure the flow of gas through the sample, as the liquid is displaced out of the porous membrane. This will provide the bubble point, maximum pore size, mean flow pore size, minimum pore size, average pore size distribution (of uniform materials) and air permeability of the membrane under test. The mean flow pore diameter is the pore size at which 50% of the total gas flow can be accounted. This means that half the flow is through pores larger than this diameter.

IV) Porosity (%) of the Membrane

[0166] The porosity of the membrane under evaluation was determined from the apparent density (ρ.sub.apparent) and the real density of the membrane. The ρ.sub.apparent was measured in air by weighing the membrane and determining its volume from the dimensions of the membrane (length, width and thickness). The real density of the membrane was determined from pycnometer measurements of the membrane with known weight under helium atmosphere. The Helium occupied the pores of the membrane with known weight, and therefore the volume of polymer could be determined. From this the porosity could be determined according to Formula (1):

[00002]$\begin{array}{cc}\mathrm{Porosity}=\frac{{\rho }_{\mathrm{real}}-{\rho }_{\mathrm{apparent}}}{{\rho }_{\mathrm{real}}}\times 100\%& \left(1\right)\end{array}$

[0167] The pycnometer used was the AccuPyc™ II 1340 gas displacement pycnometry system from Micromeritics Instrument Corporation.

V) Thickness (μm) of the Membrane

[0168] The thickness of the membranes was determined by contact mode measurement. The measurements were performed at five different positions of the membrane and the average thickness of these five measurements in μm was calculated.

VI) Swelling (%)

[0169] The swelling (%) of the membranes in water was determined as follows: A circular membrane of 47 mm diameter was dried by open air for 16 hours to give a dry membrane. The volume of the dry membrane was then determined by measuring the width and thickness in 2-3 locations. The average of the dimensions are taken and the volume is calculated according to the following formula:

[00003]$\mathrm{Volume}={\pi \left(\frac{\mathrm{width}}{2}\right)}^2*\mathrm{thickness}$

[0170] The dry membrane was then allowed to stand in distilled water (100 cm.sup.3) for 16 hours to give a wet membrane. The volume of the wet membrane was then determined by measuring the width and the thickness again in 2-3 locations. Also the average of the dimensions are taken and the volume is calculated according to the formula above. The swelling % was then determined by performing the following calculation:

[00004]$\mathrm{Swelling}=\frac{{\mathrm{Volume}}_{\mathrm{wet}}-{\mathrm{Volume}}_{\mathrm{dry}}}{{\mathrm{Volume}}_{\mathrm{dry}}}\times 100\%$

VII) Pore Surface Area, S.sub.BET (M.sup.2/g):

[0171] The method for measuring the pore surface area was in accordance with ISO 9277.

[0172] Samples of each membrane under test were degassed in vacuum at 25° C. for 16 hours. The dry weight of the resultant, degassed membrane was recorded.

[0173] The ability of the degassed samples to absorb nitrogen gas was then recorded at 77 K using a Micromeritics TriStar II 3020 adsorption analyser as follows.

[0174] A cell containing a degassed sample of membrane under test was evacuated and then cooled using liquid nitrogen to a temperature of 77 Kelvin. Portions of nitrogen gas were then dosed into the cell and the nitrogen gas was partly adsorbed onto the surface of the membrane under test until an equilibrium was reached with the gas phase. In this way adsorption and desorption points were recorded at different pressures and an adsorption and desorption isotherm was constructed. Adsorbed nitrogen first formed a quasi-monolayer on the membrane surface whereas further increases in pressure resulted in the formation of multilayers. In the region where monolayer and multilayers were formed, the specific surface area (S.sub.BET) was determined according to the BET (Brunauer, Emmet and Teller) theory. This model is applicable to non-porous and meso- and macroporous materials and adsorption points in the relative pressure range between 0.05 and 0.25 were used.

Preparation of Cross-Linking Agents Comprising at Least One Ligand Group

Preparation of (M3)

[0175] The di(2-picolyl)amine (50 mg, 0.25 mmol) was dissolved in water (0.85 ml) and cooled to 0° C. Subsequently, N, N′-{[(2-acrylamido-2-[(3-acrylamidopropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide (531 mg, 0.75 mmol) in a mixture of iso-propanol (0.25 ml) and water (0.8 ml) was added at 0° C. and slowly warmed to 80° C. while stirring. The reaction was monitored by TLC and completed after 75 hours. The solvent was removed and the crude material was purified by silica gel column chromatography (Ethyl acetate 4:1 Methanol) to give M3 as a colourless oil (177 mg) in quantitative yield.

[0176] The compound M3 was characterised by .sup.1H NMR (62 MHz, CDCl.sub.3, δ): 8.56 (m, 2H), 7.78-6.91 (m, 6H), 6.36-6.16 (m, 6H), 5.66-5.46 (m, 3H), 4.69 (s, 1H), 3.84-3.10 (m, 22H), 2.88 (m, 2H), 2.50 (m, 5H) and 1.86-1.66 (m, 6H).

Preparation of (M7)

[0177] N,N′,N″,N′″-tetraacryloyltriethylenetetramine (91 mg, 0.25 mmol) was dissolved in water (1 ml) and di(2-picolyl)amine (100 mg, 0.50 mmol) was added. Subsequently, 4-methoxyphenol (1.24 mg, 0.01 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (19 mg, 0.125 mmol) were also added and stirred at room temperature. The reaction was monitored by reversed phase TLC and complete after 5 days. The solvent was removed and the crude compound consisted of a statistical distribution of products with M7 as the main component according to LC-MS analysis. M7 was directly used without further purification.

[0178] The compound M7 was characterised by .sup.1H NMR (62 MHz, CDCl.sub.3, δ): 8.60-8.52 (m, 4H), 7.97-7.38 (m, 12H), 6.07-5.63 (m, 6H), 5.66-5.46 (m, 3H), 4.69 (br. s, 2H), 3.84 (s, 8H), 3.53-3.01 (m, 16H), and 2.50-2.30 (m, 4H).

Preparation of (M19)

[0179] N-Boc-1,2-ethylenediamine (9.61 g, 60 mmol) was dissolved in EtOAc (200 mL), and a solution of anhydrous potassium carbonate (124.4 g, 900 mmol) in water (200 mL) was added. The resulting mixture was vigorously stirred at 0° C. and acryloyl chloride (18.2 mL, 223.7 mmol) was added dropwise. Next, the resulting solution was allowed to reach room temperature and stirred overnight. The organic layer was separated from the aqueous layer, after which the aqueous layer was extracted three times with EtOAc (3×200 ml). The organic layers were combined and dried with Na.sub.2SO.sub.4, filtered, and evaporated to give N-Boc-1,2-ethylenediamine acrylamide as a white solid (12.6 g, 98%). The N-Boc-1,2-ethylenediamine acrylamide (12.6 g, 58.9 mmol) was dissolved in DCM (50 mL), and trifluoroacetic acid (50 mL) was slowly added. The resulting mixture was stirred at room temperature. After 30 minutes, deprotection was complete (as confirmed by TLC). Afterwards, DCM and TFA were evaporated to give N-(2-aminoethyl)acrylamide as a TFA salt (13.4 g) in quantitative yield. This was directly used by redissolving in anhydrous DMF (45 ml) and addition of the diethylenetriaminepentaacetic dianhydride (2.5 g, 7.0 mmol). Next, triethylamine was added dropwise until the pH of the solution remained stable at pH 8-9 and the resulting mixture was stirred overnight at room temperature. The reaction was monitored by TLC and afterwards the solvents were concentrated and the crude material was purified by reverse phase C18 silica gel column chromatography with water as eluent to give M19 as a colourless oil (1.97 g, 48%).

[0180] The compound M19 was characterised by .sup.1H NMR (62 MHz, DMSO-d6, δ): 8.58 (s, 2H), 8.16 (s, 2H), 6.32 (m, 2H), 6.08 (d, 2H, J=32 Hz), 5.56 (d, 2H, J=32 Hz), 3.28 (m, 26H).

EXAMPLES 1 TO 39

(ai) Preparation of Compositions

[0181] Compositions 1 to 39 were prepared by mixing the ingredients indicated in Table 1 below in the specified amounts. In Table 1, component (i) had the structure identified above in the description, component (ii) was as described in Table 1, component (iii) was Irgacure™ 1173 (a photoinitiator), and component (iv) when present was M50 as described above. The compositions were each applied to a porous support (FO-2223-10) by the process described in more detail further in this specification.

TABLE-US-00002 TABLE 1 Compositions Component Composition Amount of (ii) and Component Component water IPA Component Component Value of Example (i) (i) (wt %) (wt %) (wt %) (iii) (wt %) (iv) (wt %) Z 1 (M3) 28.97 27.03 43.81 0.19 0.00 0.993 2 (M3) 26.89 32.27 40.66 0.18 0.00 0.993 3 (M3) 25.09 36.80 37.94 0.17 0.00 0.993 4 (M3) 23.52 40.76 35.56 0.16 0.00 0.993 5 (M3) 22.13 44.26 33.46 0.15 0.00 0.993 6 (M3) 27.31 25.49 47.02 0.18 0.00 0.993 7 (M3) 25.83 24.11 49.89 0.17 0.00 0.993 8 (M3) 24.51 22.87 52.46 0.16 0.00 0.994 9 (M3) 23.31 21.76 54.77 0.16 0.00 0.993 10 (M3) 30.31 26.52 42.98 0.19 0.00 0.994 11 (M3) 33.00 23.00 43.81 0.19 0.00 0.994 12 (M3) 40.00 26.81 33.00 0.19 0.00 0.995 13 (M7) 28.97 27.03 43.81 0.19 0.00 0.993 14 (M7) 26.89 32.27 40.66 0.18 0.00 0.993 15 (M7) 25.09 36.80 37.94 0.17 0.00 0.993 16 (M7) 23.52 40.76 35.56 0.16 0.00 0.993 17 (M7) 22.13 44.26 33.46 0.15 0.00 0.993 18 (M7) 27.31 25.49 47.02 0.18 0.00 0.993 19 (M7) 25.83 24.11 49.89 0.17 0.00 0.993 20 (M7) 24.51 22.87 52.46 0.16 0.00 0.994 21 (M7) 23.31 21.76 54.77 0.16 0.00 0.993 22 (M7) 30.31 26.52 42.98 0.19 0.00 0.994 23 (M7) 33.00 23.00 43.81 0.19 0.00 0.994 24 (M7) 40.00 26.81 33.00 0.19 0.00 0.995 25 (M19) 28.97 27.03 43.81 0.19 0.00 0.993 26 (M19) 26.89 32.27 40.66 0.18 0.00 0.993 27 (M19) 25.09 36.80 37.94 0.17 0.00 0.993 28 (M19) 23.52 40.76 35.56 0.16 0.00 0.993 29 (M19) 22.13 44.26 33.46 0.15 0.00 0.993 30 (M19) 27.31 25.49 47.02 0.18 0.00 0.993 31 (M19) 25.83 24.11 49.89 0.17 0.00 0.993 32 (M19) 24.51 22.87 52.46 0.16 0.00 0.994 33 (M19) 23.31 21.76 54.77 0.16 0.00 0.993 34 (M19) 30.31 26.52 42.98 0.19 0.00 0.994 35 (M19) 33.00 23.00 43.81 0.19 0.00 0.994 36 (M19) 40.00 26.81 33.00 0.19 0.00 0.995 37 (M3) 40.00 15.81 24.00 0.19 20.00 0.665 38 (M3) 40.00 17.81 27.00 0.19 15.00 0.725 39 (M3) 40.00 20.31 31.00 0.19 8.50 0.822
(aii) Application of the Compositions to a Support

[0182] The compositions described in Table 1 above were each independently applied to a porous support (FO-2223-10) at 20° C. using a tabletop coating machine (manufactured by TQC, Model AB3000 Automatic film applicator). The supports were attached to a glass plate and the compositions were applied to the supports at a speed of about 1 cm/sec using a wire bar (a stainless steel bar on which a wire of 150 μm had been wound at 1 lap/3 cm (length direction). Any excess composition and air bubbles were removed from the coated supports using a 12 μm wire bar.

(b) Curing the Compositions to Form the Membrane

[0183] The compositions present on the supports were cured by irradiation with UV using a Light Hammer LH6 UV exposure machine (manufactured by Fusion UV Systems, Inc.). The Light Hammer machine was fitted with a Model H-bulb (100% strength). The coated supports were passed through the Light Hammer machine at a speed of 10m/min to expose the composition to the UV light from the H-bulb. The curing time was 0.8 seconds. The exposure time was 0.71 seconds. The resultant membranes were removed from the glass plate and was stored in a polyolefin bag.

EXAMPLE 40

[0184] In this Example a membrane was prepared which did not comprise a support and the curing was thermal curing. A composition was prepared exactly as described for Example 1 except that in place of Irgacure™ 1173 there was used was V-50 (a thermal initiator, 2 wt %) having the structure shown above. Z had a value of 0.935. The composition (5.0 cm.sup.3) was placed in a glass vial having a capacity of 25 cm.sup.3. The vial was sealed and placed in a vacuum oven at 50° C. for 60 minutes. The oven was cooled down to room temperature and the vial was removed from the oven. The resultant membrane was then removed from the vial.

EXAMPLE 41

[0185] Example 1 was repeated except that the membrane did not comprise a porous support.

[0186] The composition described in Example 1 was applied to the glass plate at 20° C. using a tabletop coating machine (manufactured by TQC, Model AB3000 Automatic film applicator) at a speed of about 1 cm/sec using a wire bar (a stainless steel bar on which a wire of 150 μm had been wound at 1 lap/3 cm (length direction).

[0187] The composition present on the glass plate was cured by irradiation with UV using a Light Hammer LH6 UV exposure machine (manufactured by Fusion UV Systems, Inc.). The Light Hammer machine was fitted with a Model H-bulb (100% strength). The coated sample was passed through the Light Hammer machine at a speed of 10m/min to expose the composition to the UV light from the H-bulb. The curing time was 0.8 seconds. The exposure time was 0.71 seconds. The resultant membrane was removed from the glass plate and was stored in a polyolefin bag.

EXAMPLE 42C

(a) Preparation and Application of a Composition

[0188] A composition was prepared by mixing the following components in the specified amounts: (M49) (31.68 wt %); AMPS-Na (6.49 wt %); ethanolamine (0.38 wt %); iso-propanol (30.19 wt %); water (30.49 wt %); and Irgacure™ 1173 (0.77 wt %). Z had a value of 0.814. The composition was applied to a non-woven support (FO-2223-10) at 20° C. using a tabletop coating machine (manufactured by TQC, Model AB3000 Automatic film applicator). The support was attached to a glass plate and the composition was applied to the support at a speed of about 1 cm/sec using a wire bar (a stainless steel bar on which a wire of 150 μm had been wound at 1 lap/3 cm (length direction). Any excess composition and air bubbles were removed from the coated support using a 12 μm wire bar.

(b) Curing the Compositions to Form the Membrane

[0189] The composition present on the support was cured by irradiation with UV using a Light Hammer LH6 UV exposure machine (manufactured by Fusion UV Systems, Inc.). The Light Hammer machine was fitted with a Model H-bulb (100% strength). The coated support was passed through the Light Hammer machine at a speed of 10m/min to expose the composition to the UV light from the H-bulb and subsequently the D-bulb. The curing time was 0.8 seconds. The exposure time was 1.42 seconds. The resultant membrane was removed from the glass plate and was stored in a polyolefin bag.

(c) Acid Treatment of the Membrane

[0190] The membrane arising from Step (b) was washed three times with 0.2 M H.sub.2SO.sub.4 (aq.), which resulted in a membrane akin to polymerised monomer (M37)(i.e. non-ionic and in free acid instead of salt form). The resultant membrane had a higher binding affinity for metal ions than when in the salt form. The resultant membrane had a dry thickness of 110 μm, an metal removal capacity of 353 μmol/g, a water flux of 305 l/m.sup.2/bar/hr, an average pore size of 250 nm and a swelling in water of 2.3%.

Properties of the Resultant Membranes

[0191] The membranes obtained in Examples 1 to 41 and 42c had the properties described in Table 2 below:

TABLE-US-00003 TABLE 2 Membrane Properties Metal Pore removal surface Waterflux capacity Porosity Swelling MFP area S.sub.BET Example (l/(m.sup.2/bar/hr)) (μmol/g) (%) (%) (nm) (m.sup.2/g)  1 222 257 41.0 1.0 245 912  2 233 239 43.1 0.8 251 958  3 243 223 44.9 0.8 253 998  4 251 209 46.5 0.9 248 1033  5 259 197 47.9 0.6 246 1064  6 231 243 42.7 0.8 250 949  7 239 230 44.2 0.5 252 982  8 246 218 45.5 0.7 253 1011  9 252 207 46.7 0.8 248 1038 10 215 269 39.7 0.9 248 882 11 210 293 37.0 0.7 253 822 12 202 355 30.0 0.9 251 667 13 222 479 41.0 1.0 200 910 14 233 445 43.1 0.7 198 960 15 243 415 44.9 0.9 195 1000 16 251 389 46.5 1.0 196 1031 17 259 366 47.9 0.6 202 1062 18 231 451 42.7 1.0 202 947 19 239 427 44.2 0.8 199 980 20 246 405 45.5 0.9 198 1009 21 252 385 46.7 0.8 199 1036 22 215 501 39.7 0.7 195 880 23 210 546 37.0 0.7 201 821 24 202 661 30.0 0.5 200 665 25 222 402 41.0 0.6 150 921 26 233 373 43.1 0.8 146 968 27 243 348 44.9 0.8 146 1008 28 251 326 46.5 0.8 151 1043 29 259 307 47.9 0.6 154 1075 30 231 379 42.7 0.7 147 958 31 239 358 44.2 0.6 149 991 32 246 340 45.5 0.5 150 1021 33 252 323 46.7 0.6 150 1048 34 215 420 39.7 0.9 145 891 35 210 458 37.0 0.7 146 831 36 202 555 30.0 0.7 153 673 37 407 325 25.5 1.3 220 753 38 450 380 27.8 1.2 217 788 39 443 376 24.9 1.1 244 726 40 308 375 35.9 3.5 155 805 41 410 312 38.6 1.8 502 867  42c 305 353 41.0 2.3 244 920

COMPARATIVE EXAMPLES 1 TO 8

Preparation of Compositions

[0192] Comparative composition CEx1 to CEx7 were prepared by mixing the ingredients indicated in Table 4 below in the specified amounts. In Table 4, component (i) had the structure identified above in the description, component (ii) consisted of the components specified in Table 4, component (iii) was Irgacure™ 1173 in the amounts indicated.

[0193] The membranes obtained in Comparative Examples CEx1 to CEx7 were prepared using the method described for Example 1 above, except that the compositions indicated in Table 4 below were used. The support used in all cases was FO-2223-10.

[0194] CEx8 was prepared according to the following procedure:

(a) Preparation and Application of a Composition

[0195] A composition was prepared by mixing the following components in the specified amounts: (M49) (31.68 wt %); AMPS-Na (6.49 wt %); ethanolamine (0.38 wt %); iso-propanol (30.19 wt %); water (30.49 wt %); and Irgacure™ 1173 (0.77 wt %). Z had a value of 0.814. The composition was applied to a non-woven support (FO-2223-10) at 20° C. using a tabletop coating machine (manufactured by TQC, Model AB3000 Automatic film applicator). The support was attached to a glass plate and the composition was applied to the support at a speed of about 1 cm/sec using a wire bar (a stainless steel bar on which a wire of 150 μm had been wound at 1 lap/3 cm (length direction). Any excess composition and air bubbles were removed from the coated support using a 12 μm wire bar.

(b) Curing the Compositions to Form the Membrane

[0196] The composition present on the support was cured by irradiation with UV using a Light Hammer LH6 UV exposure machine (manufactured by Fusion UV Systems, Inc.). The Light Hammer machine was fitted with a Model H-bulb (100% strength). The coated support was passed through the Light Hammer machine at a speed of 10m/min to expose the composition to the UV light from the H-bulb and subsequently the D-bulb. The curing time was 0.8 seconds. The exposure time was 1.42 seconds. The resultant membrane was removed from the glass plate and was stored in a polyolefin bag.

[0197] The resultant membrane had a low affinity for metals (lower than the membrane from Example 42-c).

TABLE-US-00004 TABLE 4 Compositions Used in Comparative Examples CEx1 to CEx7 Cross-linking Comparative agent Component (ii) Component (iv) Example Amount Water IPA Other Component Amount Value # Name (wt %) (wt %) (wt %) solvents (iii) (wt %) Name (wt %) of Z CEx1 CN132 37.50 49.00 12.50 0.00 1.00 None 0.00 0.000 CEx2 MBA 1.30 14.36 0.00 9.57% 0.11 None 0.00 0.000 DMF, 61.77% Dioxane, 1.69% Glycerol CEx3 None 0.00 27.03 43.81 0.00 0.19 M50 28.97 0.000 CEx4 BAMPS 37.49 37.29 0.00 0.00 0.50 AMPS- 24.72 0.598 (Component Na (i)) CEx5 M3 5.90 23.38 20.53 0.00 0.19 M50 50.00 0.105 CEx6 M3 5.00 35.81 44.00 0.00 0.19 M50 15.00 0.247 CEx7 M3 5.90 49.00 38.91 0.00 0.19 M50 6.00 0.488

Properties of the Resultant Comparative Membranes

[0198] The membranes obtained in Comparative Examples CEx1 to CEx8 had the properties described in Table 5 below:

TABLE-US-00005 TABLE 5 Properties of the Comparative Membranes Metal Pore removal surface Waterflux capacity Porosity Swelling MFP area S.sub.BET Example (l/(m.sup.2/bar/hr)) (μmol/g) (%) (%) (nm) (m.sup.2/g) CEx1 4228 0 33.3 3.3 448 734 CEx2 10147 0 57.1 80.1 1012 110 CEx3 1125 52 41.2 80.0 0 185 CEx4 0 0 5.0 11.2 0 0 CEx5 120422 56 62.2 33.8 0 0 CEx6 122008 45 60.0 45.8 0 0 CEx7 122407 32 58.9 27.4 0 0 CEx8 310 101 32.0 2.4 249 711