Source: https://patents.google.com/patent/US9592476B2/en
Timestamp: 2019-05-25 02:28:08
Document Index: 476218862

Matched Legal Cases: ['Application No. 2', 'Application No. 15163452', 'Application No. 2015', 'Application No. 2015', 'Application No. 10', 'Application No. 10201503011']

US9592476B2 - Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb) - Google Patents
Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb) Download PDF
US9592476B2
US9592476B2 US14/292,446 US201414292446A US9592476B2 US 9592476 B2 US9592476 B2 US 9592476B2 US 201414292446 A US201414292446 A US 201414292446A US 9592476 B2 US9592476 B2 US 9592476B2
US14/292,446
US20150343395A1 (en
2014-05-30 Priority to US14/292,446 priority Critical patent/US9592476B2/en
2015-12-03 Publication of US20150343395A1 publication Critical patent/US20150343395A1/en
2016-03-11 Assigned to PALL CORPORATION reassignment PALL CORPORATION CORRECTIVE ASSIGNMENT TO CORRECT THE ADDRESS OF THE ASSIGNEE PREVIOUSLY RECORDED ON REEL 033516 FRAME 0489. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: Grzenia, David Lukas, AAMER, KHALED ABDEL-HAKIM HELMY
2017-03-14 Publication of US9592476B2 publication Critical patent/US9592476B2/en
Disclosed are membranes formed from self-assembling block copolymers, for example, a diblock copolymer of the formula (I):
wherein R1-R4, n, and m are as described herein, which find use in preparing nanoporous membranes. Embodiments of the membranes contain the block copolymer that self-assembles into a cylindrical morphology. Also disclosed is a method of preparing such membrane which involves hybrid casting a polymer solution containing the block copolymer to obtain a thin film, followed by evaporation of some of the solvent from the thin film, and coagulating the resulting this film in a bath containing a nonsolvent or poor solvent for the block copolymer.
The invention provides, in an embodiment, a porous membrane comprising a block copolymer, for example, a diblock copolymer of the formula (I):
The present invention takes advantage of the ability of block copolymers having thermodynamically incompatible blocks to undergo phase separation and self-assemble into nanostructures, thereby creating nanoporous membranes having uniform porosity.
FIG. 2A depicts the AFM image of the topography of the surface of a membrane prepared in accordance with an embodiment of the invention and FIG. 2B depicts the AFM image of the phase of the membrane.
FIG. 3A depicts the AFM image of the topography of the surface of another membrane prepared in accordance with an embodiment of the invention and FIG. 3B depicts the phase of the membrane.
FIG. 4 depicts the AFM phase image of the surface of yet another membrane prepared in accordance with an embodiment of the invention.
FIG. 5 depicts the AFM phase image of the surface of an additional membrane prepared in accordance with an embodiment of the.
FIG. 6 illustrates a nanostructure of an asymmetric membrane in accordance with an embodiment of the invention comprising a first layer and a second layer, the first layer comprising a diblock copolymer and ordered pores in a cylindrical morphology continuously extending to the second layer comprising a diblock copolymer in a network of porous structure in which micro and macro channels are connected so as to provide a tortuous path for fluid flow.
FIG. 7 depicts the line profile of the pore size periodicity extracted from the AFM height image depicted in FIG. 2A.
FIG. 8A depicts the FE-SEM image of the surface of the membrane depicted in FIG. 2A.
FIG. 8B depicts the FE-SEM image of the perspective of the membrane depicted in FIG. 2A.
FIG. 9 depicts the FE-SEM image of the cross-section of the membrane depicted in FIG. 2A.
FIG. 10 depicts the FE-SEM image of the cross-section of the membrane depicted in FIG. 3A.
n and m are independently about 10 to about 2000; 0<x≦n and 0<y≦m; the method comprising:
The “alkyl” group could be linear or branched. In accordance with an embodiment, the alkyl group is preferably a C1-C22 alkyl. Examples of alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, hexadecyl, and the like. This definition also applies wherever “alkyl” occurs such as in hydroxyalkyl, monohalo alkyl, dihalo alkyl, and trihalo alkyl. The C1-C22 alkyl group can also be further substituted with a cycloalkyl group, e.g., a C3-C7 cycloalkyl group.
In any of the above embodiments of the block copolymer, for example, diblock copolymer, in is typically about 50 to about 2000, preferably about 675 to about 1525, more preferably about 675 to about 1120, and even more preferably 870.
The block copolymer, for example, diblock copolymer, can have any suitable total molecular weight, for example, a number average molecular weight (Mn) of from about 50 kDa to about 1000 kDa; in certain embodiments, the block copolymer has an Mn of from about 100 kDa to about 600 kDa; in certain other embodiments, the block copolymer has an Mn of from about 180 kDa to about 500 kDa; and in further embodiments, the block copolymer has an Mn of from about 195 kDa to about 441 kDa. In certain embodiments, the block copolymer has an Mn of from about 250 kDa to 500 kDa.
The double bonds in the block copolymer in accordance with embodiments of the invention can have any suitable orientation, cis, trans, and they can be distributed in a random manner.
In an embodiment, the polymerized second monomer (bearing R2) and the polymerized first monomer (bearing R1), after hydrogenation, are present in the diblock copolymer in any suitable volume fraction. For example, the % volume fraction of the first monomer to that of the second monomer can be in the range of about 15:about 85 to about 30:about 70, preferably in the range of about 19:about 81 to about 25:about 75, and more preferably about 20:about 80. In an embodiment, the volume fraction of the second monomer is about 80%, and the mass fraction is about 83%, of the total polymer.
Alternatively, the first monomer can be synthesized by the reaction of exo-7-oxanorbornane-5,6-dicarboxyanhydride with hexadecylamine or N-hexadecyl-maleimide reaction with furan via a Diels-Alder reaction.
The starting homopolymer formed during the preparation of the diblock copolymer precursor, and the diblock or multiblock copolymer of the invention can be characterized for their molecular weights and molecular weight distributions by any known techniques. For example, a MALS-GPC technique can be employed. The technique uses a mobile phase to elute, via a high pressure pump, a polymer solution through a bank of columns packed with a stationary phase. The stationary phase separates the polymer sample according to the chain size followed by detecting the polymer by three different detectors. A series of detectors can be employed, e.g., an Ultraviolet detector (UV-detector), followed by a multi-angle laser light scattering detector (MALS-detector), which in turn, is followed by a refractive index detector (RI-detector) in a row. The UV-detector measures the polymer light absorption at 254 nm wavelength; the MALS-detector measures the scattered light from polymer chains relative to mobile phase.
In an embodiment, the present invention provides a porous membrane comprising a diblock or multiblock copolymer described above. In accordance with an embodiment of the invention, the porous membrane is a nanoporous membrane, for example, a membrane having pores of diameter between 1 nm and 100 nm.
In an embodiment, the porous membrane is prepared by a hybrid casting process, whereby a solution of the block copolymer is cast as a thin film on a support, a part of the solvent or mixture of solvents present in the thin film is evaporated and the thin film coated support is immersed in a bath containing a nonsolvent for the block copolymer. The resulting membrane is composed of a layer of self-assembled nanostructure supported by a porous underlying layer. For example, the membrane is a porous asymmetric membrane comprising a first layer and a second layer, the first layer comprising a diblock copolymer and ordered pores in a cylindrical morphology continuously extending to the second layer comprising the a diblock copolymer in a network of porous structure in which micro and macro channels are connected so as to provide a tortuous path for fluid flow. An embodiment of such membrane is illustrated in FIG. 6.
To prepare the membrane, the block copolymer is first dissolved in a suitable solvent or solvent system to obtain a polymer solution. The polymer solution can be prepared by any suitable method known to those skilled in the art. The block copolymer is added to the solvent system and stirred until a homogeneous solution is obtained. If desired, the solution can be stirred for an extended time to allow for the block copolymer to assume its thermodynamically favorable structure in the solution. The block copolymer is dissolved in good solvent or a mixture containing good solvents.
The polymer solution can contain any suitable amount of the block copolymer. In accordance with an embodiment, the polymer solution contains about 10 to about 35% or more, preferably about 12 to about 18%, and more preferably about 12 to about 16% by weight of the block copolymer. In an example, the polymer solution contains about 15% by weight of the block copolymer. The polymer concentration can control the thickness of the film, and hence the thickness of the membrane obtained. The polymer concentration can also control the porosity of the membrane, with high concentrations producing less porous membrane.
In accordance with embodiments, the polymer solution contains a block copolymer, NMP, and THF at a ratio of 15:34:51 mass %, the polymer solution contains a block copolymer, DMF, and THF at a ratio of 15:51:34 mass %, the polymer solution contains a block copolymer, DMF, and THF at a ratio of 15:34:51 mass %, or the polymer solution contains a block copolymer, DMF, and THF at a ratio of 12:35.2:52.8 mass %. In an embodiment, the polymer solution contains a block copolymer, DMF, and THF at a ratio of 12:44:44 mass %.
Without wishing to be bound by any theory or mechanism, the formation of a nanostructure is believed to take place as follows. The block copolymer in solution experiences certain thermodynamic forces. Since the block copolymer comprises at least two chemically different blocks of polymer chains connected by a covalent bond, there exists an incompatibility between the two blocks. In addition, there exists a connectivity constraint imparted by the connecting covalent bond. As a result of these thermodynamic forces, the block copolymer when dissolved in an appropriate solvent system self-assemble into micro-phase separated domains that exhibit ordered morphologies at equilibrium. When a film is cast from a dilute solution, the block copolymer forms micelles composed of a core and a corona, each made of a different block. In dilute solution, the micelles tend to be isolated from each other. However, in concentrated solution, as for example, when the solvent is removed from a thin film of the solution by evaporation, the micelles tend to aggregate with the result that the coronas merge to form a continuous matrix and the cores merge to form porous channels.
After a nanostructure is formed, the thin film is immersed into a coagulation bath. The coagulation bath contains a nonsolvent or poor solvent, or a mixture of a good solvent and a nonsolvent or poor solvent. Any of the solvents listed above for preparing the polymer solution can be used here as a good solvent. The coagulation bath can contain the good solvent and the nonsolvent or poor solvent in any suitable amounts. For example, in a binary mixture, either of the good solvent and the nonsolvent or poor solvent can be present in a volume or mass ratio of 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, or 50/50, or any ratio therebetween. In a ternary solvent system, any of the solvents can be present in any suitable ratio, for example, a volume or mass ratio of 80/10/10, 75/15/10, 70/20/10, 65/25/10, 60/30/10, 55/25/30, 40/40/20, or 30/30/40 or any ratio therebetween.
In accordance with an embodiment, water and lower alcohols such as methanol, ethanol, isopropanol, and butanol are nonsolvents and/or poor solvents for the block copolymer. Aliphatic hydrocarbons such as pentane, hexane, and cyclohexane are additional examples of poor solvents. In an embodiment, the coagulation bath includes or is entirely composed of isopropanol. In another embodiment, the coagulation bath contains a mixture of isopropanol, dimethylsulfoxide, and water. For example, in an embodiment, the coagulation bath is composed of isopropanol and DMSO at a ratio of about 80:20 mass %; in another embodiment, the coagulation bath is composed of a mixture of isopropanol, DMSO, and water at a ratio of about 60:20:20 mass %; in yet another embodiment, the coagulation bath is composed of a mixture of isopropanol, DMSO, and water at a ratio of about 60:20:20 mass %.
The film can reside in the coagulation bath for any suitable length of time, for example, from about 1 min to about 20 min, preferably about 2 min to about 10 min, and more preferably about 3 to about 5 minutes. During this time, the block copolymer that remains in the film as a solution, rather than as a nanostructure, undergoes phase inversion to produce a porous structure.
In accordance with an embodiment, the membrane is an asymmetric membrane comprising a first layer and a second layer, the first layer comprising the block copolymer and ordered pores in a cylindrical morphology continuously extending to the second layer comprising the block copolymer in a network of porous structure in which micro and macro channels are connected so as to provide a tortuous path for fluid flow.
The first layer comprises the block copolymer and the pores are ordered in a cylindrical morphology and perpendicular to the plane of the membrane and the cylindrical pores whose diameters are in the range of about 40 to about 60 nm and the average pore lengths are about 50 nm, and the second layer comprises a microporous layer of the block copolymer. The pore size of the microporous layer can be from about 100 nm to about 10 microns, about 200 nm to about 5 microns, and in embodiments, about 100 nm to about 2 μm. The membrane is an integral skinned porous membrane having cylindrical pores in the skin oriented perpendicular to the plane of the membrane and the skin is supported by a microporous support of the same block copolymer.
Alternatively, the thin film can be coated on a porous support. The porous membrane prepared in this manner will have a first layer comprising the diblock copolymer and ordered pores in a cylindrical morphology continuously extending to a second layer comprising the diblock copolymer in a network of porous structure in which micro and macro channels are connected so as to provide a tortuous path for fluid flow, which in turn in supported by a support of larger pores, thereby constituting a composite membrane.
In a clean 500 mL RBF equipped with magnetic stirring bar, a mixture of exo-7-oxanorbomene-5,6-dicarboxyimide (C1) (10 g, 61 mmol), Ph3P (23.84 g, 91 mmol), and 1-hexadecanol (17.6 g, 72.7 mmol) were dissolved in anhydrous THF (130 mL) under a stream of dry nitrogen gas. The solution was cooled in ice bath. DIAD (22.1 g, 109.3 mmol) was added from a dropping funnel drop-wise to the cooled solution. The reaction mixture was allowed to warm up to room temperature and stirred for 24 h. THF was removed by rotary evaporator till dryness to obtain white solid. The first monomer was obtained from the crude as white solid upon crystallization from methanol (2×) and drying at room temperature under vacuum for 24 h (yield of 18.6 g, 80%). 1H-NMR (300 MHz, CDCl3): δ (ppm) 6.5 (s, 2H), 5.26 (s, 2H), 5.32 (s, 2H), 3.45 (t, 2H), 2.82 (s, 2H), 1.56-1.38 (m, 2H), 1.28-1.1 (m, 26H), 0.88 (t, 3H).
This example illustrates the preparation of a diblock copolymer suitable for preparing a membrane in accordance with an embodiment of the invention.
The diblock copolymer precursor was dissolved in DCM (15 g in 400 mL). The Grubbs' 2nd generation catalyst (480 mg, 565 mmol) with silica gel substrate (10 g, 40-63 microns flash chromatography particle) and the precursor solution were transferred to a Parr high pressure reactor and the reactor was charged with hydrogen gas (1500 psi). The reactor was heated to 50° C. for 24 h. The resulting polymer mixture was filtered and precipitated into methanol (2×) to obtain white precipitate (yield 12 g, 80%). 1H-NMR (300 MHz, CDCl3): δ (ppm) 7.6-7.45 (m, 3H, phenyl), 7.4-6.8 (m, 2H, phenyl), 4.5-3.55 (broad m, 2H), 3.5-2.6 (broad m, 2H), 2.5-1.6 (broad s, 2H), 1.6-1.4 (broad s, 2H), 1.4-1.0 (s, 26H), 0.88 (t s, 3H).
The homopolymer and the diblock copolymer obtained in Example 6 were characterized for their molecular weight and molecular weight distribution properties by the MALS-GPC technique under the following conditions:
Casting solutions containing the diblock copolymer from Example 7 were prepared by mixing the diblock copolymer with DMF and THF until clear solutions were obtained. The solutions contained the diblock copolymer, DMF, and THF at a ratio of either 15:51:34 mass % or 12:44:44 mass %.
Thin films were cast on a glass plate or a nonwoven polyester fabric (HIROSE 05TH) was used as the substrate, to provide 7-8 mil (or about 177-200 microns) thick wet membrane films. The wet films were allowed to stand for a period of 60 sec or 30 sec to allow them to develop self-assembled nanostructures, subsequent to which, they were immersed in a coagulation bath containing isopropanol at 20° C. for a period of 5 min. The films were washed and dried, and the resulting membranes were imaged with an atomic force microscope (AFM) to reveal their nanostructures.
FIG. 2A depicts the AFM image of the topography (height) of the surface of a membrane prepared from the solution containing the diblock copolymer, DMF, and THF at a ratio of 15:51:34 mass % with a 60 sec standing time before coagulation and FIG. 2B depicts the AFM image of the phase of the membrane. Glass was used as the substrate to cast the film.
FIG. 3A depicts the AFM image of the topography (height) of the surface of a membrane prepared from the solution containing the diblock copolymer, DMF, and THF at a ratio of 12:44:44 mass % with a 60 sec standing time before coagulation and FIG. 3B depicts the phase of the membrane. Glass was used as the substrate to cast the film.
FIG. 4 depicts the AFM phase image of the surface of a membrane prepared from the solution containing the diblock copolymer, DMF, and THF at a ratio of 12:44:44 mass % with a 30 sec standing time before coagulation. Glass was used as the substrate to cast the film.
FIG. 5 depicts the AFM phase image of the surface of a membrane prepared from the solution containing the diblock copolymer, DMF, and THF at a ratio of 15:51:34 mass % with a 60 sec standing time before. Nonwoven polyester fabric was used as the substrate to cast the film.
FIG. 10 depicts the FE-SEM of the cross-section of the membrane depicted in FIG. 3A.
From the AFM images, it can be seen that the diblock copolymer self-assembled into an ordered structure comprising a cylindrical morphology of pores at the air interface and the ordered structure is supported by an underlying porous support structure.
The surface pores have a narrow pore size in the range of about 40 nm to about 70 nm and the cylindrical pores reach to a depth of about 150 mm to about 200 mm in the thickness direction.
wherein the volume fraction of the monomeric unit bearing R2 to that of the monomeric unit bearing R1 in the block copolymer is about 2.3 to about 5.6:1;
12. The method of claim 1, wherein the polymer solution contains about 10 to about 35% by weight of the block copolymer.
15. The method of claim 1, wherein the coagulation bath comprises a nonsolvent or poor solvent for the block copolymer.
18. The porous membrane of claim 17, which is an asymmetric membrane comprising a first layer and a second layer, the first layer comprising the block copolymer and ordered pores in a cylindrical morphology continuously extending to the second layer comprising the block copolymer in a network of porous structure in which micro and macro channels are connected so as to provide a tortuous path for fluid flow.
US14/292,446 2014-05-30 2014-05-30 Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb) Active US9592476B2 (en)
US14/292,446 US9592476B2 (en) 2014-05-30 2014-05-30 Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb)
EP15163452.4A EP2949382A1 (en) 2014-05-30 2015-04-14 Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting
SG10201503011PA SG10201503011PA (en) 2014-05-30 2015-04-16 MEMBRANE COMPRISING SELF-ASSEMBLED BLOCK COPOLYMER AND PROCESS FOR PRODUCING THE SAME BY HYBRID CASTING (IIb)
JP2015084284A JP5967503B2 (en) 2014-05-30 2015-04-16 Method for producing the same film, and a hybrid casting comprising a self-assembled block copolymer (IIb)
KR1020150057196A KR101697562B1 (en) 2014-05-30 2015-04-23 MEMBRANE COMPRISING SELF-ASSEMBLED BLOCK COPOLYMER AND PROCESS FOR PRODUCING THE SAME BY HYBRID CASTING (IIb)
CA2889445A CA2889445C (en) 2014-05-30 2015-04-24 Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (iib)
CN201510423982.XA CN105175660B (en) 2014-05-30 2015-04-30 Comprising a self-assembled block copolymer film and the film produced by the method for mixing casting (lib)
US20150343395A1 US20150343395A1 (en) 2015-12-03
US9592476B2 true US9592476B2 (en) 2017-03-14
ID=53365706
US14/292,446 Active US9592476B2 (en) 2014-05-30 2014-05-30 Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb)
US (1) US9592476B2 (en)
EP (1) EP2949382A1 (en)
JP (1) JP5967503B2 (en)
KR (1) KR101697562B1 (en)
CN (1) CN105175660B (en)
CA (1) CA2889445C (en)
SG (1) SG10201503011PA (en)
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CA2886291A1 (en) 2014-05-30 2015-11-30 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (ib)
CA2889441A1 (en) 2014-05-30 2015-11-30 Khaled Abdel-Hakim Helmy Aamer Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (iia)
CA2886210A1 (en) 2014-05-30 2015-11-30 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (ia)
2014-05-30 US US14/292,446 patent/US9592476B2/en active Active
2015-04-14 EP EP15163452.4A patent/EP2949382A1/en not_active Withdrawn
2015-04-16 JP JP2015084284A patent/JP5967503B2/en active Active
2015-04-16 SG SG10201503011PA patent/SG10201503011PA/en unknown
2015-04-23 KR KR1020150057196A patent/KR101697562B1/en active IP Right Grant
2015-04-24 CA CA2889445A patent/CA2889445C/en active Active
2015-04-30 CN CN201510423982.XA patent/CN105175660B/en active IP Right Grant
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CN105175660B (en) 2018-04-06
SG10201503011PA (en) 2015-12-30
US20150343395A1 (en) 2015-12-03
CA2889445A1 (en) 2015-11-30
JP5967503B2 (en) 2016-08-10
CN105175660A (en) 2015-12-23
JP2015227442A (en) 2015-12-17
KR20150137997A (en) 2015-12-09
CA2889445C (en) 2018-01-23
EP2949382A1 (en) 2015-12-02
KR101697562B1 (en) 2017-01-18
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