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WO2010137974A1 - Composition polymère comprenant un mélange d'un élastomère thermoplastique multibloc et un polymère comprenant un métal du groupe 14 - Google Patents

Composition polymère comprenant un mélange d'un élastomère thermoplastique multibloc et un polymère comprenant un métal du groupe 14 Download PDF

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WO2010137974A1
WO2010137974A1 PCT/NL2010/050307 NL2010050307W WO2010137974A1 WO 2010137974 A1 WO2010137974 A1 WO 2010137974A1 NL 2010050307 W NL2010050307 W NL 2010050307W WO 2010137974 A1 WO2010137974 A1 WO 2010137974A1
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block
group
formula
blocks
membrane
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PCT/NL2010/050307
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English (en)
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Michel Henry Knoef
Sander Rogier Reijerkerk
Matthias Wessling
Dorothea Catharina Nijmeijer
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Universiteit Twente
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/521—Aliphatic polyethers
    • B01D71/5211—Polyethylene glycol or polyethyleneoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/701—Polydimethylsiloxane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/007—Separation by stereostructure, steric separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • Polymer composition comprising a blend of a multi-block thermoplastic elastomer and a polymer comprising a Group 14 metal
  • the present invention relates to a polymer composition
  • a polymer composition comprising a blend of a multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, and a polymer comprising a metal of Group 14 of the Periodic System of the Elements (IUPAC Version 22 June 2007), i.e. silicon, germanium, tin or lead.
  • the present invention further relates to membranes comprising said polymer composition and to the application of such membranes in separation processes, ion transport processes, ultrafiltration and nano filtration.
  • Multi-block polymers comprising hard polymeric blocks and soft polymeric blocks are well known in the art.
  • the hard polymeric blocks provide thermoplastic properties to the multi-block polymer whereas the soft blocks provide elastomeric properties to the multi-block polymer.
  • Such multi-block polymers are also known in the art as thermoplastic elastomers (cf. Kirk-Othmer, Encyclopedia of Chemical Technology, 3 rd Ed., Vol. 7, pages 368 - 370, 1993; Kirk-Othmer, Encyclopedia of Chemical Technology, 3 rd Ed., Vol. 9, pages 15 - 37, 1994).
  • Thermoplastic elastomers are used in a multitude of applications including membranes which are used in separation processes.
  • Thermoplastic elastomers are inter alia used in separation processes where they are applied in the form of membranes.
  • examples of commercially available thermoplastic elastomers used for this purpose include Pebax® grades, Pellethane® grades, Arnitel® grades and Hytrel® grades. All those grades have polyether blocks, amorphous polyester blocks or polysiloxane blocks as the soft blocks which implies that their major difference lies in the hard blocks.
  • Pebax® grades for example, are based on polyamide hard blocks.
  • Pellethane® grades are based on polyurethane hard blocks.
  • Arnitel® grades and Hytrel® grades are based on non-amorphous polyester blocks. Other hard blocks are based on imides.
  • US 4.963.165 discloses a membrane for gas separation which comprises a multi-block polyamide-polyether polymer.
  • US 5.130.017 discloses a membrane for separating aromatic compounds from non-aromatic compounds.
  • the membrane is manufactured from a multi-block polymer comprising an amide acid prepolymer which is chain- extended with a second prepolymer selected from the group of prepolymers comprising dianhydride, its corresponding tetra-acid or diacid-diester and an epoxy component, a diisocyanate component or a polyester component.
  • Silicon containing polymers have been used for manufacturing membranes which find application in separation processes.
  • JP A 61118412 and US 5.494.989 both incorporated by reference, disclose a copolymer suitable for gas separation, said copolymer being synthesized by copolymerizing e.g. a silylarylacetylene and another acetylene monomer in the presence of a Group 5 metal catalyst.
  • JP A 1194903 discloses a liquid separating membrane which can efficiently separate water-alcohol mixtures, wherein the separating membrane is based on a poly( 1 -trimethylsilyl-2-trialkylsilyl- 1 -propyne) .
  • thermoplastic elastomer may be selected from a large group of homopolymers and copolymers. According to the examples, preferred thermoplastic elastomers are the polymers Tecoflex®, Hytrel® and Kraton®.
  • US 5.552.483 discloses a curable composition
  • a curable composition comprising a natural or synthetic rubber and a block polymer comprising alternating blocks of a polysiloxane and a copolymer of a 1,3-conjugated diene and a monovinyl aromatic compound.
  • the polysiloxane block is preferably an elastomeric linear polysiloxane.
  • membranes known from the prior art may have an acceptable performance
  • the present inventors have found that the addition of "smart" additives to the base polymeric constituent used for the manufacture of the membrane enhances its properties, in particular separation properties, ion transport processes, ultrafiltration and nano filtration.
  • membranes known from the prior art have widely different properties and that they can be used in very different separation processes, despite the fact that they are based on similar polymeric substances.
  • the present invention relates to a polymer composition comprising a blend of a multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, and a polymer comprising a metal of Group 14 of the Periodic System of the Elements (IUPAC Version 22 June 2007).
  • the present invention further relates to a membrane for separation processes, wherein said membrane comprises a polymer composition comprising a blend of a multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, and a polymer comprising a metal of Group 14 of the Periodic System of the Elements.
  • the present invention also relates to a gas separation process involving a membrane comprising a polymer composition comprising a blend of a multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, and a polymer comprising a metal of Group 14 of the Periodic System of the Elements.
  • the present invention relates in particular to a carbon dioxide gas separation process involving a membrane comprising a polymer composition comprising a blend of a multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, and a polymer comprising a metal of Group 14 of the Periodic System of the Elements.
  • the present invention further relates to ion transport processes which occur in e.g. ion exchange, electrochemical cells including batteries, and fuel cells.
  • the present invention also relates to ultrafiltration and nanof ⁇ ltration processes.
  • the verb "to comprise” as is used in this description and in the claims and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
  • reference to an element by the indefinite article “a” or “an” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there is one and only one of the elements.
  • the indefinite article “a” or “an” thus usually means “at least one”.
  • the multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks have the general formula -(A-B) n - wherein A represents a hard polymeric block and wherein B represents a soft polymer block and wherein n represents an integer of at least 2.
  • thermoplastic elastomer The multi-block thermoplastic elastomer
  • the multi-block thermoplastic elastomer comprises alternating hard polymeric blocks and soft polymeric blocks.
  • the polymeric hard blocks are selected from the group consisting of polyurethane blocks, polyamide blocks, non-amorphous polyester blocks, polyimide blocks, polysulfone blocks, polycarbonate blocks and mixtures thereof.
  • the soft polymeric blocks are selected from the group consisting of polyether blocks, amorphous polyester blocks and polysiloxane blocks.
  • the present invention therefore encompasses multi- block thermoplastic elastomers according to the general formula -(A-B) n - wherein A represents a hard polymeric block and wherein B represents a soft polymer block in the following combinations:
  • the soft blocks have a Tg of 0 0 C or lower.
  • the multi-block thermoplastic elastomer comprises a polyamide block as the hard block and a polyether block, an amorphous polyester block or a polysiloxane block as the soft block.
  • the multi-block thermoplastic elastomer comprises a polyamide block as the hard block and a polyether block as the soft block.
  • the multi-block thermoplastic elastomer comprising a polyamide block as the hard block and a polyether block as the soft block has preferably the following general Formula (VII):
  • P is a polyamide block
  • O is oxygen
  • Q is a polyether block
  • y indicates an integer such that the intrinsic viscosity ⁇ of the multi-block thermoplastic elastomer is in the range of about 0.5 to about 2.5, preferably about 0.7 to about 2.2, more preferably about 0.8 to about 2.05.
  • the polyamide block has preferably a number average molecular weight of about 100 to about 25000, more preferably about 100 to about 15000 and most preferably about 500 to about 10000.
  • the polyamide block is preferably an aliphatic polyamide block. Most preferably, the polyamide block is polyamide 6 (P A6).
  • the polyether block has preferably a number average molecular weight of about 100 to about 10000, more preferably about 200 to about 6000 and most preferably about 400 to about 3000.
  • the polyether block is preferably a polyoxyalkylene glycol block such as a polyoxy ethylene glycol block, a polyoxypropylene glycol block (which may be derived from 1,2-propene oxide, 1,3-propene oxide or mixtures thereof), a poly(oxyethylene-co-oxypropylene) glycol block, a polyoxytetramethylene glycol block (also known as po Iy-THF) or mixtures thereof.
  • the polyethylene glycol block is a polyoxy ethylene glycol block.
  • the weight proportions of the polyether block to the total weight of the multi- block thermoplastic elastomer having polyamide blocks as hard blocks is preferably about 5 to about 85 wt.%, more preferably about 20 wt.% to about 75 wt.%, most preferably about 40 wt.% to about 70 wt.%.
  • thermoplastic elastomers according to the first embodiment of the present invention and methods for their preparation are for example disclosed in US 4.230.838, US 4.331.786, US 4.332.920 and US 4.376.856, all incorporated by reference.
  • the multi-block thermoplastic elastomer comprising a polyamide block as the hard block and a polyether block as the soft block has preferably the following general Formula (VIII):
  • R 5 and R 6 are OH and/or H, a is a number 0.1 to 10, b is a number of 2 to 50, D is a residue of an oligoamidediacid having a M n of about 300 to about 8000, PE is a residue of a polyoxyalkylene, preferably a polyoxyethylene, having a M n of about 200 to about 5000, and X is a residue of a diacid comprising linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residues having 4 to 12 carbon atoms.
  • D may comprise a residue of a diacidic limiter such as dodecanedioic acid.
  • the multi-block thermoplastic elastomer comprising a polyamide block as the hard block and a polyether block as the soft block has preferably the following general Formula (IX):
  • R 5 and R 6 are OH and/or H, c is a number 1 to 4, d is a number of 2 to 50, D is a residue of an oligoamidediacid having a M n of about 300 to about 3000, PE is a residue of a polyoxyalkylene, preferably a polyoxyethylene, having a M n of about 200 to about 5000, and X is a residue of a diacid comprising linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residues having 4 to 20 carbon atoms.
  • Such multi-block thermoplastic elastomers are disclosed in US 5.213.891, incorporated by reference.
  • the multi-block thermoplastic elastomer according to the three embodiments mentioned above comprising a polyamide block as the hard block and a polyether block as the soft block may further comprise a polyol as is disclosed in US 2007/0106034, incorporated by reference, or a substituted polyoxyalkylene glycol block as is disclosed in US 6.300.463, incorporated by reference.
  • the multi-block thermoplastic elastomer comprising a polyamide block as the hard block and a polyether block as the soft block are most preferably selected from the PEBAX® grades 2533 SA 01, 2533 SD 01, 2533 SN 01, 3533 SA 01, 3533 SD 01, 3533 SN 01, 4033 SA 01, 4033 SD 01, 4033 SN 01, 5533 SA 01, 5533 SN 01, 5533 SP 01, 6633 SA 01, 6633 SP 01, 7033 SA 01, 7033 SP 01, 7233 SA 01, 7233 SP 01, MH 1657, MP 1878 SA 01, MV 1041 SA 01, MV 1074 SP 01 , MV 3000 SA 01 , MV 6100 SA 01 , MX 1205 SA 01 , MX 1205 SP 01 , MX 1717, RDG 277 and RDG 314.
  • the polymer comprising a metal of Group 14 of the Periodic System of the Elements
  • Group 14 of the Periodic System of the Elements contains the metals silicon, germanium, tin and lead. According to the present invention, it is preferred that the Group 14 metal is silicon (Si).
  • the polymer comprising the metal of Group 14 of the Periodic System of the Elements can be selected from the group consisting of: (a) a polysiloxane according to Formula (I):
  • M is the Group 14 metal
  • R 1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C 12 aryl groups and mixtures thereof;
  • R 2 is a polyoxyalkylene chain; p is in the range of 5 to 5000; and q is in the range of 5 to 10000; (b) a polyalkyne according to Formula (II):
  • M is the Group 14 metal
  • R 1 is selected from the group consisting of linear or branched Ci - Ci 2 alkyl groups, Ce - C 12 aryl groups and mixtures thereof;
  • R 3 is R 1 or a polyoxyalkylene chain;
  • R 4 is hydrogen, a linear Ci - Ci 2 alkyl group, a C 6 - Ci 2 aryl group, a (R 1 ⁇ M- CH 2 - group, a (R ⁇ 2 R 3 M-CH 2 - group, or a mixture thereof; and r is in the range of 100 - 20000; (c) a polyalkyne according to Formula (III): Formula (III)
  • M is the Group 14 metal
  • R 1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C 12 aryl groups and mixtures thereof;
  • R 3 is R 1 or a polyoxyalkylene chain; (s/(s+t)) > 0.2; (t/(s+t)) > 0.05; (d) a polyalkyne according to Formula (IV):
  • M is the Group 14 metal
  • R 1 is selected from the group consisting of linear or branched Ci - Ci 2 alkyl groups, Ce - Ci 2 aryl groups and mixtures thereof;
  • R 3 is R 1 or a polyoxyalkylene chain
  • R 4 is hydrogen, a linear Ci - Ci 2 alkyl group, a C 6 - Ci 2 aryl group, (R 1 ⁇ M-CH 2 - group, a (R ⁇ 2 R 3 M- group, or a mixture thereof; and u is in the range of 100 - 20000; (e) a polyalkyne according to Formula (V):
  • M is the Group 14 metal;
  • R 1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C 12 aryl groups and mixtures thereof;
  • R 3 is R 1 or a polyoxyalkylene chain; (v/(v+w)) > 0.2; and (w/(v+w)) > 0.05; or (f) a polyalkene according to Formula (VI);
  • R 1 is selected from the group consisting of linear or branched Ci - Ci 2 alkyl groups, C 6 - Ci 2 aryl groups and mixtures thereof;
  • R 3 is R 1 or a polyoxyalkylene chain; and x is in the range of 100 - 20000.
  • any one of the groups R 1 , R 2 , R 3 and R 4 may contain a chiral centre.
  • the groups bonded to the metal M may be all different thereby rendering chirality to the metal M.
  • any one of the groups R 1 , R 2 , R 3 and R 4 may be substituted with a substituent selected from the group of linear and branched Ci -C 6 alkyl, halogen, OH, -OR 1 , M(R 1 ) 3 or M(R 1 ⁇ R 3 .
  • R 1 a linear Ci - C 6 alkyl group or phenyl, more preferably a Ci - C 6 alkyl group, most preferably methyl. It is also preferred that R 3 has the same meaning as R 1 .
  • the polyoxyalkylene chain (R 2 and/or R 3 ) is a polyoxy ethylene chain, said polyoxy ethylene chain preferably having the formula:
  • M n of the polyoxy ethylene chain is equal to about 1000 or less, more preferably equal to about 500 or less, and most preferably equal to about 250 or less.
  • R 4 is hydrogen, methyl or phenyl, most preferably methyl or phenyl.
  • poly(trialkylsilylalkynes) have generally a high molecular weight, i.e. a M w over 10 6 .
  • a M w over 10 6 Reference is made to US 4.808.679, incorporated by reference.
  • R 1 and R 3 are most preferably methyl and R 4 is most preferably a linear Ci - C 4 alkyl group. Most preferably, R 4 is methyl so that polymer (b) is poly(l- trimethylsilyl- 1 -propyne) (PTMSP) .
  • PTMSP poly(l- trimethylsilyl- 1 -propyne)
  • R 1 and R 3 are most preferably methyl. It is furthermore preferred that the monomer bearing the -M(R 1 ) 2 R 3 substituent is present in the final polymer (c) in an amount of about 5 wt.% to about 80 wt.%, based on the total weight of the polymer (c), and that the other monomer is present in an mount of about 20 wt.% to about 95 wt.%, based on the total weight of the final polymer (c).
  • R 1 and R 3 are most preferably methyl and R 4 is most preferably a linear Ci - C 4 alkyl group. Most preferably, R 4 is methyl.
  • v is preferably 1 and R 1 and R 3 are most preferably methyl.
  • R 1 and R 3 are most preferably methyl.
  • the blend comprises about 0.1 wt.% to about 99 wt.% of the polymer comprising a metal of Group 14 of the Periodic System of the Elements, based on the total weight of the blend. It is furthermore preferred that the blend comprises about 1 wt.% to about 99.9 wt.% of the multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, based on the total weight of the blend.
  • the blend comprises about 0.1 wt.% to about 97 wt.% of the polymer comprising a metal of Group 14 of the Periodic System of the Elements and about 3 wt.% to about 99.9 wt.% of the multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks. Even more preferably, the blend comprises about 1 wt.% to about 97 wt.% of the polymer comprising a metal of Group 14 of the Periodic System of the Elements and about 3 wt.% to about 99 wt.% of the multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks.
  • the blend comprises about 10 wt.% to about 95 wt.% of the polymer comprising a metal of Group 14 of the Periodic System of the Elements and about 5 wt.% to about 90 wt.% of the multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks.
  • the polymer composition preferably comprises about 50 wt.% to about 100 wt.% of the blend of a multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks, and a polymer comprising a metal of Group 14 of the Periodic System of the Elements, based on the total weight of the polymer composition. More preferably, the polymer composition comprises about 70 wt. % to about 100 wt.% of said blend. Yet even more preferably, the polymer composition comprises about 90 wt.% to about 100 wt.% of said blend. Most preferably, the polymer composition consists essentially of said blend.
  • the polymer blend may comprise, as a further component, another thermoplastic elastomer, preferably a multi-block thermoplastic elastomer, in particular a multi-block thermoplastic elastomer selected from the group consisting of multi-block thermoplastic elastomers according to the general formula -(A-B) n - wherein A represents a hard polymeric block and wherein B represents a soft polymer block in the following combinations:
  • the amount of this other thermoplastic elastomer is preferably about 0 wt.% to about 50 wt.%, based on the total weight of the polymer composition. More preferably, this amount is about 0 wt.% to about 30 wt.%, even more preferably about 0 wt.% to about 10 wt.% and most preferably about 0 wt.%.
  • the polymer composition according to the present invention is in particular suitable for the manufacture of a membrane.
  • any of the polymers (a) - (f) comprise an unsaturated carbon carbon bond
  • these polymers are preferably crosslinked to provide additional mechanical strength to the membrane.
  • the membrane according to the present invention is preferably used in various applications which include separation processes, ion transport processes, in particular processes involving the transport of Li + , ultrafiltration processes and nano filtration processes. Additionally, since the polymers (a) - (f) may comprise a chiral centre, the membrane according to the present invention may be suitable for the separation of optical isomers, in particular enantiomers, as is for example disclosed in US 5.449.728, incorporated by reference.
  • the separation processes include gas/gas separation processes, gas/liquid separation processes and liquid/liquid separation processes. More preferably, the separation process is a gas/gas separation process, wherein most preferably carbon dioxide is separated from another gas or a mixture of gases.
  • the gas/gas separation process involves the separation of carbon dioxide from a light gas, wherein the molecular weight of the light gas is 44 or less (the molecular weight of propane is 44). Most preferably, the gas/gas separation process involves the separation of carbon dioxide from a gas which comprises hydrogen, nitrogen, methane or a mixture thereof, and wherein the molecular weight of the heaviest gas present in the mixture is 44 or less.
  • the membrane according to the present invention has preferably a hydrogen gas permeability coefficient (determined at 35°C and 400 kPa pressure) of less than 17 Barrer.
  • the membrane according to the present invention has preferably a nitrogen gas permeability coefficient (determined at 35°C and 400 kPa pressure) of less than 5 Barrer.
  • the membrane according to the present invention has preferably a methane gas permeability coefficient (determined at 35°C and 400 kPa pressure) of less than 12 Barrer.
  • the permeability coefficient P is herein defined as:
  • the membrane according to the present invention has preferably a selectivity ⁇ [P(CO 2 )/P(H 2 )] of at least about 9.0.
  • the selectivity (X[P(CO 2 )ZP(N 2 )] is preferably at least about 30.
  • the membrane according to the present invention provides a strongly enhanced permeability for CO 2 gas in combination with an enhanced selectivity for CO 2 gas over nitrogen gas and/or hydrogen gas.
  • the selectivity ⁇ [P(CO 2 )/P(CH 4 )] of the membrane is preferably at least about 10. Additionally, the selectivity Ct[P(CO 2 )ZP(O 2 )] is preferably at least about 15 and the selectivity ⁇ [P(CO 2 )ZP(He)] is preferably at least about 15.
  • P(A) and P(B) represent the permeability coefficients of gases A and B, respectively.
  • the membrane according to the present invention further comprises a support for providing mechanical strength.
  • a support for providing mechanical strength are known in the art and are generally highly permeable and occur in the form of flat sheets, hollow fibers or hollow tubes.
  • the support may be constituted of porous glass, porous metal, porous ceramics, polymers having a high permeability and the like.
  • the membrane according to the present invention may be applied on one surface or on both surfaces of the support.
  • the present invention also relates to the use of the membrane according to the present invention in separation processes and ion transport processes, in particular processes involving the transport of Li + , ultrafiltration processes and nanofiltration processes. Examples
  • Pebax® MH 1657 was obtained from Arkema.
  • This thermoplastic elastomer is a block polymer containing about 60 wt.% PEO and about 40 wt.% PA-6.
  • the M n of the PEO block is about 1500 which means that the copolymer consists of about 35 repeating ethylene oxide monomers and about 9 repeating PA-6 monomers.
  • the additive poly(dimethylsiloxane-gra/t-ethyleneglycol) (PDMS-PEG) was obtained from Aldrich and contains about 80 wt.% of PEG; the M n is about 3800.
  • Membranes were prepared by the following general procedure. A solution of 3 wt.% Pebax® MH 1657 in a mixture of ethano I/water (70/30 w/w) was prepared under reflux at 80 0 C under continuous stirring (about two hours). After complete dissolution of the polymer, the solution was cooled to ambient temperature. Subsequently, different amounts of PDMS-PEG were added and the solution was stirred for one more hour. Membrane films were prepared by solution casting: the solution was poured in a petri dish and placed under a nitrogen atmosphere at ambient temperature to evaporate the solvent. The obtained films were dried in a vacuum oven at 30 0 C to remove residual solvent. Thermal properties of the films were determined by DSC (Perkin Elmer DSC 7).
  • the glass transition temperature T g is defined as the midpoint of the heat capacity transition of the heating scan and the melting temperature from the onset of melting.
  • Gas permeabilities of flat membrane films were determined with different gas- permeation set-ups.
  • Low pressure gas (N 2 , O 2 , He, H 2 , CH 4 and CO 2 ) permeabilities were determined with a low pressure gas separation (LPGS) set-up at 400 kPa feed pressure at 35°C.
  • High pressure pure and mixed gas permeabilities were determined with a high pressure gas separation (HPGS) set-up for pressure up to 2500 kPa at 35°C.
  • Bot set-ups measured the steady-state pressure increase in time in a calibrated volme at the permeation side of the membrane film (start: vacuum ⁇ 10 kPa) following the constant volume variable pressure method (A. Bos et ah, Separation and Purification
  • the CO 2 permeability of a membrane made from a blend of 50 wt.% Pebax® MH 1657 and 50 wt.% PEG 200 is 172 Barrer.
  • the ⁇ (PCO 2 / PH 2 ) is 10.5, the ⁇ (PCO 2 / PN 2 ) is 50.5 and the ⁇ (PCO 2 / PCH 4 ) is 15.7 (determined with LPGS set-up).
  • PEG200 is a far less effective additive in increasing the permeability of Pebax® MH 1657 membranes.
  • This test was performed with several blends and included also testing of the ⁇ (PCO 2 / PHe) and ⁇ (PCO 2 / PO 2 ). The data are summarized in Table 4.

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une composition polymère comprenant un mélange d'un élastomère thermoplastique multibloc comprenant l'alternance de blocs polymères durs et de blocs polymères mous, et un polymère comprenant un métal du groupe 14 du tableau périodique des éléments. L'invention concerne également une membrane comprenant ledit mélange et son application dans des procédés de séparation, des procédés de transport d'ions, d'ultrafiltration et de nanofiltration.
PCT/NL2010/050307 2009-05-25 2010-05-21 Composition polymère comprenant un mélange d'un élastomère thermoplastique multibloc et un polymère comprenant un métal du groupe 14 WO2010137974A1 (fr)

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US10221278B2 (en) 2011-05-13 2019-03-05 Novomer, Inc. Catalytic carbonylation catalysts and methods
WO2013118148A1 (fr) * 2012-02-06 2013-08-15 Council Of Scientific & Industrial Research Membrane sélective d'énantiomères l pour la résolution optique d'acides alpha-aminés et son procédé de préparation
WO2015085295A3 (fr) * 2013-12-07 2015-10-29 Novomer, Inc. Membranes de nanofiltration et procédés d'utilisation
US10245559B2 (en) 2013-12-07 2019-04-02 Novomer, Inc. Nanofiltration membranes and methods of use
US11027242B2 (en) 2013-12-07 2021-06-08 Novomer, Inc. Nanofiltration membranes and methods of use
US11667617B2 (en) 2014-05-05 2023-06-06 Novomer, Inc. Catalyst recycle methods
US10858329B2 (en) 2014-05-05 2020-12-08 Novomer, Inc. Catalyst recycle methods
US10597294B2 (en) 2014-05-30 2020-03-24 Novomer, Inc. Integrated methods for chemical synthesis
US10829372B2 (en) 2014-05-30 2020-11-10 Novomer, Inc. Integrated methods for chemical synthesis
CN104208748A (zh) * 2014-07-24 2014-12-17 苏州大学 具有梯度弹性模量的生物可降解聚氨酯及其制备的组织工程纤维支架
US10974234B2 (en) 2014-07-25 2021-04-13 Novomer, Inc. Synthesis of metal complexes and uses thereof
US10792620B2 (en) 2014-11-20 2020-10-06 Entegris, Inc. Grafted ultra high molecular weight polyethylene microporous membranes
CN107106997B (zh) * 2014-11-20 2021-10-26 恩特格里斯公司 接枝的超高分子量聚乙烯微孔膜
CN107106997A (zh) * 2014-11-20 2017-08-29 恩特格里斯公司 接枝的超高分子量聚乙烯微孔膜
US10626073B2 (en) 2015-02-13 2020-04-21 Novomer, Inc. Process for production of acrylic acid
US10738022B2 (en) 2015-02-13 2020-08-11 Novomer, Inc. Continuous carbonylation processes
US10717695B2 (en) 2015-02-13 2020-07-21 Novomer, Inc. Distillation process for production of acrylic acid
US10927091B2 (en) 2015-02-13 2021-02-23 Novomer, Inc. Continuous carbonylation processes
US10221150B2 (en) 2015-02-13 2019-03-05 Novomer, Inc. Continuous carbonylation processes
US11078172B2 (en) 2015-02-13 2021-08-03 Novomer, Inc. Integrated methods for chemical synthesis
US10099988B2 (en) 2015-02-13 2018-10-16 Novomer, Inc. Process for production of acrylic acid
US11155511B2 (en) 2015-02-13 2021-10-26 Novomer, Inc. Distillation process for production of acrylic acid
US10099989B2 (en) 2015-02-13 2018-10-16 Novomer, Inc. Distillation process for production of acrylic acid
US11807613B2 (en) 2015-02-13 2023-11-07 Novomer, Inc. Integrated methods for chemical synthesis
CN110639375A (zh) * 2019-09-27 2020-01-03 南京工业大学 一种高稳定性血液透析膜及其制备方法

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