Method Of Producing A Polymeric Membrane

Abstract

The present invention relates to a method of producing a polymeric membrane having a homogeneous porosity throughout the entire polymeric phase. The method comprises the steps of dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, and contacting the extruded solution with non-solvent to induce phase separation and thereby producing an integral asymmetric polymeric membrane, wherein the amphiphillic block copolymer is an amphiphillic diblock copolymer, containing blocks of a polar copolymer and blocks of a benzocyclobutene copolymer, and wherein the integral asymmetric polymeric membrane is crosslinked by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase.

Claims

1. A method for producing a polymeric membrane comprising the steps of: (a) dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, (b) extruding the casting solution onto a carrier substrate to form a film, (c) evaporating a portion of the solvent near the surface during a standing period, (d) contacting the extruded solution with non-solvent to induce phase separation and thereby producing an integral asymmetric polymeric membrane in flat sheet geometry, and (e) crosslinking the integral asymmetric polymeric membrane by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase, wherein the amphiphillic block copolymer is a amphiphillic block copolymer is an amphiphillic diblock copolymer, containing blocks of a polar copolymer and blocks of a benzocyclobutene copolymer.

2. The method of claim 1, wherein the amphiphillic block copolymer is an amphiphillic diblock copolymer containing blocks of a polar copolymer and blocks of a vinylbenzocyclobutene copolymer.

3. The method of claim 2, wherein the vinylbenzocyclobutene copolymer is 4-vinylbenzocyclobutene.

4. The method of claim 1, wherein the polar copolymer is selected from the group consisting of vinylpyridine copolymers, acrylate copolymers, and methacylate copolymers.

5. The method of claim 1, wherein the amphiphillic block copolymer is selected from the group consisting of poly(4-vinylbenzocyclobutene)-block-poly(4-vinylpyridine) diblock copolymer and poly(4-vinylbenzocyclobutene)-block-poly(methylmethacrylate) di-block copolymer.

6. The method of claim 1, wherein the casting solution is extruded through a rectangular die onto a substrate to produce a polymeric membrane in flat sheet geometry.

7. The method of claim 6, wherein the substrate is provided as a first reel of substrate material, which is unwound prior to applying the casting solution onto the carrier.

8. The method of claim 7, wherein the flat sheet polymer membrane is wound to a second reel, optionally together with the substrate material, after the integral asymmetric membrane has formed.

9. The method of claim 1, wherein the casting solution is extruded through an annular die to produce a polymeric membrane in hollow fibre geometry.

10. The method of claim 9 comprising the steps of (a) dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, extruding the casting solution through a first annular die in a spinneret while simultaneously pressing a core gas stream through at least one orifice encircled by the first annular die and extruding a sheath liquid comprising at least one non-solvent through a second annular die encircling the first die into air, and (b) contacting the extruded solution with non-solvent in a coagulation bath to induce phase separation and thereby producing an integral asymmetric polymeric membrane in hollow fibre geometry, and (c) crosslinking the integral asymmetric polymeric membrane by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase.

11. The method of claim 9 comprising the steps of: (a) dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, providing a hollow fibre support membrane having a lumen surrounded by the support membrane, (b) coating and the inner surface thereof by first passing the casting solution through the lumen of the hollow fibre support membrane and along the inner surface thereof, (c) thereafter pressing a core gas stream through the lumen of the coated hollow fibre membrane, (d) thereafter passing a non-solvent (precipitant) through the lumen of the coated hollow fibre membrane thereby producing an integral asymmetric polymeric membrane in hollow fibre geometry, and (e) crosslinking the integral asymmetric polymeric membrane by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase.

12. A method of separating a fluid stream into a permeate stream and a retentate stream using a polymeric membrane manufactured by the method of claim 1.

13. The method of claim 12, wherein the fluid stream is a liquid stream and/or a gaseous stream.

14. A method of separating a fluid stream into a permeate stream and a retentate stream using a polymeric membrane manufactured by the method of claim 10.

15. A method of separating a fluid stream into a permeate stream and a retentate stream using a polymeric membrane manufactured by the method of claim 11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0020] In an embodiment the invention relates to a method of producing a polymeric membrane in flat sheet geometry. The method comprises the steps of steps of [0021] (a) dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, [0022] (b) extruding the casting solution onto a carrier substrate to form a film, [0023] (c) evaporating a portion of the solvent near the surface during a standing period, [0024] (d) contacting the extruded solution with non-solvent to induce phase separation and thereby producing an integral asymmetric polymeric membrane in flat sheet geometry, and [0025] (e) crosslinking the integral asymmetric polymeric membrane by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase,
wherein the amphiphillic block copolymer is a amphiphillic block copolymer is an amphiphillic diblock copolymer, containing blocks of a polar copolymer and blocks of a benzocyclobutene copolymer.

[0026] The substrate material is preferably a material which does not react with the at least one amphiphilic block copolymer in a solvent. Examples of suitable substrate materials onto which the polymer solution is applied include polymeric nonwoven, metal sheets or glass sheets. Preferably, the polymer solution is applied to a substrate in flat sheet geometry by means of a doctor blade while the substrate is unwound from a first reel. According to a preferred embodiment of the present invention, the casting solution is applied onto the substrate in a thickness ranging from 1 μm to 1000 μm, preferably from 50 μm to 500 μm, such as from 100 μm to 300 μm.

[0027] After the membrane has formed, the flat sheet polymer membrane may be wound to a second reel, optionally together with the substrate material. Prior to crosslinking the membrane may be unwound from the second reel or crosslinking may be performed prior to winding the membrane onto a reel.

[0028] In another embodiment the invention relates to a method of producing a polymeric membrane in hollow fibre geometry. The method comprises the steps of [0029] (a) dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, extruding the casting solution through a first annular die in a spinneret while simultaneously pressing a core gas stream through at least one orifice encircled by the first annular die and extruding a sheath liquid comprising at least one non-solvent through a second annular die encircling the first die into air, and [0030] (b) contacting the extruded solution with non-solvent in a coagulation bath to induce phase separation and thereby producing an integral asymmetric polymeric membrane in hollow fibre geometry, and [0031] (c) crosslinking the integral asymmetric polymeric membrane by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase,
wherein the amphiphillic block copolymer is a amphiphillic block copolymer is an amphiphillic diblock copolymer, containing blocks of a polar copolymer and blocks of a benzocyclobutene copolymer. Exemplary method steps for producing an integral asymmetric polymeric membrane in hollow fibre geometry are disclosed for example in EP 3 147 024 A1, which is fully incorporated herein for reference.

[0032] Preferably, the gap between the spinneret and the coagulation bath, through which the extruded first polymer solution passes, has a length of between 1 cm and 50 cm. Furthermore, it is preferred that the carrier solution extruded through the second die comprises polyether sulfone (PES) in admixture with poly(ethylene glycol) (PEG), a methyl pyrrolidone, such as N-methyl-2-pyrrolidone (NMP) and/or water.

[0033] In still another embodiment the invention relates to an alternative method of forming a polymeric membrane in hollow fibre geometry. The method comprises the steps of [0034] (a) dissolving at least one amphiphillic block copolymer in a solvent to form a casting solution of the block copolymer, providing a hollow fibre support membrane having a lumen surrounded by the support membrane, [0035] (b) coating and the inner surface thereof by first passing the casting solution through the lumen of the hollow fibre support membrane and along the inner surface thereof, [0036] (c) thereafter pressing a core gas stream through the lumen of the coated hollow fibre membrane, [0037] (d) thereafter passing a non-solvent (precipitant) through the lumen of the coated hollow fibre membrane thereby producing an integral asymmetric polymeric membrane in hollow fibre geometry, and [0038] (e) crosslinking the integral asymmetric polymeric membrane by application of heat or radiation thereby producing a membrane having a homogeneous porosity throughout the entire polymeric phase,
wherein the amphiphillic block copolymer is a amphiphillic block copolymer is an amphiphillic diblock copolymer, containing blocks of a polar copolymer and blocks of a benzocyclobutene copolymer. Exemplary method steps for producing an integral asymmetric polymeric membrane in hollow fibre geometry are disclosed in WO 2019/020278 A1, which is fully incorporated herein for reference.

[0039] According to an aspect of the invention the crosslinking step is carried out in the absence of a catalyst. The crosslinking step is advantageous in that it no molecules are released which might have to be washed out to ensure an appropriate membrane activity. The following scheme illustrates the assumed thermal crosslinking step when the amphiphillic block copolymer is a poly(4-vinylbenzocyclobutente)-block-poly(4-vinylpyri-dine) (PVBCB-b-P4VP) diblock copolymer.

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[0040] Preferably, thermal crosslinking (crosslinking by application of heat) of the membranes is carried out at temperatures of at least 150° C., preferably at least 180° C. The crosslinking of the polymeric membrane can be monitored via differential calorimetry. Alternatively, crosslinking of the membranes can be initiated via application of radiation, preferably by application of UV-light radiation.

[0041] According to another aspect the present invention relates to a method of separating a fluid stream into a permeate stream and a retentate stream using a polymeric membrane manufactured by any of the methods described hereinbefore. The fluid stream may be a liquid stream and/or a gaseous stream, the latter in particular after the filling of the pores with an adequate media, e.g. ionic liquids.

[0042] The invention is further described in an exemplary manner by means of the following example which shall not be construed as limiting the invention.

Example

[0043] The block copolymers used in the present examples is a poly-(4-vinylbenzocyclobutene)-b-poly(4-vinylpyridine) (PVBCB-bP4VP). In particular the sample nomenclature PVBCB.sub.79P4VP.sub.21.sup.108k attributes PVBCB to poly(4-vinylbenzocyclobutene), P4VP abbreviation for poly(4-vinylpyridine), subscripts the weight percentage of each block in the polymer and the number following is attributed to the total molecular weight in kg/mol.

[0044] The block copolymers were synthesized via anionic polymerization. All monomers and solvents were purified prior to reach the standards required for anionic polymerization. The polymerization procedure was conducted as follows: A 250 mL glass reactor was connected to a vacuum line and evacuated to attain high vacuum. Subsequently purified THF was distilled into the reactor and titrated under argon at −80° C., by a small amount of sec-butyl-lithium (sec-BuLi), until a vivid yellow colour was observed. Upon the disappearance of the colour the reactor was cooled again to a temperature of −80° C. and the first purified monomer 4-vinylbenzocyclobutene (4-VBCB 2.213 g, 0.023 mol) was inserted via a syringe into the reactor, followed by the initiator sec-BuLi (0.28 M in cyclohexane, 0.08 mL, 0.000 022 mol).

[0045] The polymerization solution immediately developed a bright orange colour indicating the formation of a propagating anion of 4-VBCB and the reaction was left to complete for 1 h at −80° C. After the reaction was completed an aliquot was withdrawn and the second purified monomer 4-vinylpyridine (4-VP, 0.5399 0.0056 mol) was inserted into the polymerization reactor. At this point, the solution colour changed rapidly to light yellow-green indicating the propagation of the 4VP block. The polymerization was left to complete overnight, and on the following day it was terminated with vacuum degassed methanol (0.5 mL).

[0046] The diblock copolymer was recovered by precipitation in hexane and dried under vacuum at 50° C. for 48 h. The yield was 96% (2.75 g). The molecular characteristics of the diblock copolymer were determined by the GPC measurements using chloroform as solvent and applying PS standards, as well as by .sup.1H-NMR in CDCl.sub.3. The total molecular weight of the polymer was calculated as 108 kg/mol and the amount of PVBCB blocks was determined to be 79 wt. % and of the P4VP blocks 21 wt. %.

[0047] For the preparation of the membrane casting solution and subsequent membrane casting, the block copolymer PVBCB.sub.79P4VP.sub.21.sup.108k was dissolved in a mixture of dimethylformamide, dioxane and tetrahydrofurane, providing a viscous, but clear solution. The composition of the casting solution was 20 wt. % PVBCB-b-P4VP, wt. % tetrahydrofurane (THF), 36 wt % dioxane (DIOX) and 8 wt. % dimethylformamide (DMF). The casting solution was extruded onto a polyester nonwoven support using a doctor blade with a gap height adjusted to 200 μm. After 10 seconds, the film was immersed in a water bath (non-solvent). Drying of the membrane followed at 60° C. under vacuum. FIGS. 1A to 1D present the images obtained via scanning transmission electron microscopy (SEM). FIG. 1A shows that hexagonal pores, approximately 25 nm (±3 nm) in size have formed on the membrane surface. FIGS. 1B and 1D show that within the membrane body cavities have formed, having the same porosity as the membrane surface. Pure water flux experiments revealed a relative low but constant flux from these membranes. The pure water, although it is forced to pass through the porous walls of the cavities, finds a higher resistance, which leads to lower flux values. Accordingly, the membrane performance was depended from the porosity of the membrane body as well. FIG. 1C shows that the pores of the selective layer are cylindrical and have a length of approximately 150-200 nm. The pores of the cavities appear to be 20 nm in length.

[0048] Further images—not shown here—demonstrate a structural gradient of the comonomers, like in all typical integrally-skinned asymmetric membranes, which structural gradient results from a very high polymer concentration membrane at the onset of phase separation.

[0049] The polymers were then subjected to crosslinking. Differential calorimetry measurements suggest that crosslinking starts at a temperature of about 180° C. and higher. An alternative source for successful crosslinking is UV-irradiation. FIG. 2 shows images of from the cross sections of another PVBCB.sub.79P4VP.sub.21.sup.108K membrane before and after crosslinking. The membrane was cast from a 19 wt % solution with a solvent weight composition DMF/THF/DIOX—10/45/45 wt %. Image A depicts cross section of the integral asymmetric membrane. Image B depicts the cross section of the membrane after crosslinking with UV irradiation for 30 minutes. Image C depicts the cross section of the UV irradiated membrane after subsequent heating at 180° C. for 15 minutes.

[0050] The figures show that upon crosslinking the cavities are closed leading to a membrane structure having a homogeneous porosity throughout the entire polymeric phase.