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WO2010137974A1 - Polymer composition comprising a blend of a multi-block thermoplastic elastomer and a polymer comprising a group 14 metal - Google Patents

Polymer composition comprising a blend of a multi-block thermoplastic elastomer and a polymer comprising a group 14 metal Download PDF

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Publication number
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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French (fr)
Inventor
Michel Henry Knoef
Sander Rogier Reijerkerk
Matthias Wessling
Dorothea Catharina Nijmeijer
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Universiteit Twente
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Publication of WO2010137974A1 publication Critical patent/WO2010137974A1/en

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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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Abstract

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. The present invention also relates to a membrane comprising said blend and its application in separation processes, ion transport processes, ultrafiltration and nanofiltration.

Description

Polymer composition comprising a blend of a multi-block thermoplastic elastomer and a polymer comprising a Group 14 metal
Field of the invention
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), 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.
Background of the invention
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, 3rd Ed., Vol. 7, pages 368 - 370, 1993; Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd 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, incorporated by reference, discloses a membrane for gas separation which comprises a multi-block polyamide-polyether polymer.
US 5.130.017, incorporated by reference, 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.
US 5.290.452, incorporated by reference, discloses polyester-polyamide based membranes for separating aromatic compounds from non-aromatic compounds.
DE 4237604 Al, incorporated by reference, discloses a membrane comprising a polyamide-polyether block copolymer which is used for ultrafiltration.
Silicon containing polymers have been used for manufacturing membranes which find application in separation processes. For example, 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.
US 5.707.423, incorporated by reference, discloses a separation membrane based on poly(l-dimethylphenylsilyl-l-propyne) for separating C2+ from natural gas.
US 4.567.245, incorporated by reference, discloses copolymer synthesised by copolymerising 1-trimethylsilyl-l-propyne and l-(r,r,3',3'-tetramethyl-l ',3'- disilabutyl)-l-propyne and a membrane made thereof having an outstandingly large oxygen permeation coefficient and a large separation factor between oxygen and nitrogen.
JP A 1009208, US 4.657.564 and US 5.373.073, all incorporated by reference, discloses membranes based on 1-alkenyldimethylsilyl-l-propyne.
JP A 1194903, incorporated by reference, 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) .
US 5.449.728, incorporated by reference, discloses a membrane based on 1- [dimethyl(10-pinanyl)silyl]-l -propyne which is used in resolving optically active compounds. RU 2206773 Cl , incorporated by reference, discloses the synthesis of poly(5- trimethylsilylnorborn-2-ene) and its use in membranes for gas separation.
T. C. Merkel et al, J. Membr. Sci. 191, 85 - 94, 2001, incorporated by reference, discloses membranes made of poly(dimethylsiloxane) and p o Iy(I -trimethylsily 1-1- propyne).
M. Ghisellini et al., Desalination 149, 441 - 445, 2002, incorporated by reference, discloses membranes made of pure poly(l-trimethylsilyl-l -propyne) and of copolymers of 1-trimethylsilyl-l -propyne and 1-trimethylsilyl-l-hexyne and the mass transport properties of n-pentane and n-hexane in these membranes. A. Car et al., J. Membr. Sci. 307, 88 - 95, and 110 - 117, 2008, incorporated by reference, discloses membranes made of a blend of the polyamide-po Iy ether block polymer Pebax® MH 1657 and polyethylene glycol having a Mn of 200 and their application in gas separation, in particular of carbon dioxide. Although the separation performance of these membranes was better than of normal polyamide-po Iy ether block polymer membranes, their is still a need in the art for membranes having an improved separation performance.
US 2002/0028156, incorporated by reference, discloses a blood oxygenator membrane comprising a polymeric matrix and a reinforcing fibre-based material, wherein the polymeric matrix comprises a thermoplastic elastomer. The 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, incorporated by reference, discloses 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.
Although the 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. In addition, it appears that 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.
Summary of the invention
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 nanofϊltration processes.
Detailed description of the invention
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. In addition, 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.
The multi-block thermoplastic elastomer
According to the present invention, the multi-block thermoplastic elastomer comprises alternating hard polymeric blocks and soft polymeric blocks. Preferably, 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. Also preferably, 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:
A = a polyurethane block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof; A = a polyamide block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof;
A = non-amorphous polyester block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof;
A = a polyimide block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof; A = a polysulfone block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof; and
A = a polycarbonate block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof. According to the present invention, it is preferred that the soft blocks have a Tg of 00C or lower.
More preferably, 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. Most preferably, the multi-block thermoplastic elastomer comprises a polyamide block as the hard block and a polyether block as the soft block.
According to a first embodiment of the present invention, 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):
Figure imgf000007_0001
Formula (VII)
wherein P is a polyamide block, O is oxygen and Q is a polyether block whereas y indicates an integer such that the intrinsic viscosity η 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. Most preferably, 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.%.
The multi-block 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.
According to a second embodiment of the present invention, 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):
Figure imgf000008_0001
Formula (VIII)
wherein R5 and R6 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 Mn of about 300 to about 8000, PE is a residue of a polyoxyalkylene, preferably a polyoxyethylene, having a Mn 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. Such multi-block thermoplastic elastomers are disclosed in US 5.166.309, incorporated by reference. D may comprise a residue of a diacidic limiter such as dodecanedioic acid.
According to a third embodiment of the present invention, 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):
R5. -D- -O PE-O- -D- -NH-X NH- -R6
O O O O
Formula (IX) wherein R5 and R6 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 Mn of about 300 to about 3000, PE is a residue of a polyoxyalkylene, preferably a polyoxyethylene, having a Mn 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.
Additionally, 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.
According to the present invention, 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):
Figure imgf000010_0001
Formula (I)
wherein:
M is the Group 14 metal;
R1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R2 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):
Figure imgf000010_0002
Formula (II)
wherein:
M is the Group 14 metal;
R1 is selected from the group consisting of linear or branched Ci - Ci2 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R3 is R1 or a polyoxyalkylene chain;
R4 is hydrogen, a linear Ci - Ci2 alkyl group, a C6 - Ci2 aryl group, a (R1^M- CH2- group, a (R^2R3M-CH2- group, or a mixture thereof; and r is in the range of 100 - 20000; (c) a polyalkyne according to Formula (III):
Figure imgf000011_0001
Formula (III)
wherein:
M is the Group 14 metal;
R1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R3 is R1 or a polyoxyalkylene chain; (s/(s+t)) > 0.2; (t/(s+t)) > 0.05; (d) a polyalkyne according to Formula (IV):
Figure imgf000011_0002
Formula (IV)
wherein:
M is the Group 14 metal;
A is -(CR1 2)v- wherein v = 1 - 6;
R1 is selected from the group consisting of linear or branched Ci - Ci2 alkyl groups, Ce - Ci2 aryl groups and mixtures thereof;
R3 is R1 or a polyoxyalkylene chain;
R4 is hydrogen, a linear Ci - Ci2 alkyl group, a C6 - Ci2 aryl group, (R1^M-CH2- group, a (R^2R3M- group, or a mixture thereof; and u is in the range of 100 - 20000; (e) a polyalkyne according to Formula (V):
Figure imgf000012_0001
Formula (V)
wherein
M is the Group 14 metal; A is -(CR12)v- wherein v = 1 - 6;
R1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R3 is R1 or a polyoxyalkylene chain; (v/(v+w)) > 0.2; and (w/(v+w)) > 0.05; or (f) a polyalkene according to Formula (VI);
Figure imgf000012_0002
wherein R1 is selected from the group consisting of linear or branched Ci - Ci2 alkyl groups, C6 - Ci2 aryl groups and mixtures thereof;
R3 is R1 or a polyoxyalkylene chain; and x is in the range of 100 - 20000.
In the polymers (a) - (f) disclosed above, any one of the groups R1, R2, R3 and R4 may contain a chiral centre. In addition, the groups bonded to the metal M may be all different thereby rendering chirality to the metal M. In the polymers (a) - (f), any one of the groups R1, R2, R3 and R4 may be substituted with a substituent selected from the group of linear and branched Ci -C6 alkyl, halogen, OH, -OR1, M(R1 )3 or M(R1^R3.
In the polymers (a) - (f) disclosed above, it is preferred that R1 a linear Ci - C6 alkyl group or phenyl, more preferably a Ci - C6 alkyl group, most preferably methyl. It is also preferred that R3 has the same meaning as R1.
In the polymers (a) - (f) disclosed above, it is furthermore preferred that the polyoxyalkylene chain (R2 and/or R3) is a polyoxy ethylene chain, said polyoxy ethylene chain preferably having the formula:
-(CH2CH2CH2O)-[-CH2CH2O-]p-CH3
wherein p is in such a range that the Mn 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. The minimum Mn is 117 (i.e. p = 1).
In the polymers (a) - (f) disclosed above, it is preferred that R4 is hydrogen, methyl or phenyl, most preferably methyl or phenyl.
In the polymers (a) - (f) disclosed above, it is furthermore preferred that the weight average molecular weight Mw of polymers (a) - (f), i.e. the polysiloxane according to Formula (I) (wherein R2 is the polyoxyalkylene chain), the polyalkynes according to Formula (II), (III), (IV) or (V), or the polyalkene according to Formula (VI) (i.e., that if R is a polyoxyalkylene chain) is determined by the polyoxyalkylene chain for about 60% to about 90%, more preferably about 70 wt.% to about 85 wt.%.
Furthermore, it is known in the prior art that poly(trialkylsilylalkynes) have generally a high molecular weight, i.e. a Mw over 106. Reference is made to US 4.808.679, incorporated by reference.
More specific preferred embodiments of polymers (b) - (f) are given below.
In polymer (b), R1 and R3 are most preferably methyl and R4 is most preferably a linear Ci - C4 alkyl group. Most preferably, R4 is methyl so that polymer (b) is poly(l- trimethylsilyl- 1 -propyne) (PTMSP) .
In polymer (c), R1 and R3 are most preferably methyl. It is furthermore preferred that the monomer bearing the -M(R1 )2R3 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).
In polymer (d), R1 and R3 are most preferably methyl and R4 is most preferably a linear Ci - C4 alkyl group. Most preferably, R4 is methyl. In polymer (e), v is preferably 1 and R1 and R3 are most preferably methyl.
In polymer (f), R1 and R3 are most preferably methyl.
The blend of the multi-block thermoplastic elastomer and the polymer comprising a metal of Group 14 of the Periodic System of the Elements
According to the present invention, it is preferred that 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. More preferably, 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. Yet even more preferably, 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
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:
A = a polyurethane block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof;
A = a polyamide block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof;
A = non-amorphous polyester block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof;
A = a polyimide block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof; A = a polysulfone block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof; and
A = a polycarbonate block and B = a polyether block, an amorphous polyester block, a polysiloxane block, or mixtures thereof.
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. When 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
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. Even more preferably, 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 CO2 gas permeability coefficient (determined at 35°C and 400 kPa pressure) of at least 120 Barrer, more preferably at least 140 Barrer, yet even more preferably at least 150 Barrer and most preferably at least 170 Barrer (Barrer = 10"10 cm3 (STP). cm/(cm2.s. cm Hg = 7.5-10"18 m3-m/m2-s-Pa). 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:
P = D X S
wherein D is the diffusivity (cm2/s = 1 - 10 4 m2/s) and S is the solubility (cm3 (STP)/(cm3.cm Hg = 7.5-10"4 m3/m3-Pa).
The membrane according to the present invention has preferably a selectivity α[P(CO2)/P(H2)] of at least about 9.0. The selectivity (X[P(CO2)ZP(N2)] is preferably at least about 30. As a consequence, the membrane according to the present invention provides a strongly enhanced permeability for CO2 gas in combination with an enhanced selectivity for CO2 gas over nitrogen gas and/or hydrogen gas.
According to the present invention, the selectivity α[P(CO2)/P(CH4)] of the membrane is preferably at least about 10. Additionally, the selectivity Ct[P(CO2)ZP(O2)] is preferably at least about 15 and the selectivity α[P(CO2)ZP(He)] is preferably at least about 15.
The selectivity α[P( A)ZP(B)] is herein defined as:
a[PWfFtB)] = %£L
wherein P(A) and P(B) represent the permeability coefficients of gases A and B, respectively.
Preferably, the membrane according to the present invention further comprises a support for providing mechanical strength. Such supports 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
Example 1
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 Mn 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 Mn 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 800C 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 300C to remove residual solvent. Thermal properties of the films were determined by DSC (Perkin Elmer DSC 7).
The glass transition temperature Tg is defined as the midpoint of the heat capacity transition of the heating scan and the melting temperature from the onset of melting.
The melting enthalpies ΔHm of the hard and soft blocks were determined from the endothermic peak areas. Samples were heated from -800C to 2500C at a rate of 20°C/min. Subsequently, a cooling scan from 2500C to -800C at a rate of 20°C/min followed by a second heating scan under the same conditions as the firs heating scan was performed. Results are shown in Table 1. Table 1
Figure imgf000019_0001
From the date shown in Table 1, it can be concluded that PDMS-PEG has only a minor influence on ΔHm(PA-6). The Tg of the blends is about constant (~ -51°C).
Example 2
Gas permeabilities of flat membrane films were determined with different gas- permeation set-ups. Low pressure gas (N2, O2, He, H2, CH4 and CO2) 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
Technology, 14(1-3), 27 - 39, 1998). Results are shown in Table 2. Table 2
Figure imgf000020_0001
The data shown in Table 2 show that the permeability increases significantly with increasing amount of PDMS-PEG.
Example 3
The pure gas permeability selectivities of CO2 over several light gases are presented in Table 3 (determined with LPGS set-up).
Table 3
Figure imgf000020_0002
Since an increase in permeability is more desirable, even a slightly decreasing selectivity is acceptable. The data of Tables 2 and 3 demonstrate that the permeability of CO2 can be increased significantly without significantly deteriorating the selectivity OfCO2 over light gases.
Comparative Examples 1 - 5
The CO2 permeability of a membrane made from a blend of 50 wt.% Pebax® MH 1657 and 50 wt.% PEG 200 is 172 Barrer. The α(PCO2/ PH2) is 10.5, the α(PCO2/ PN2) is 50.5 and the α(PCO2/ PCH4) is 15.7 (determined with LPGS set-up). Hence, 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 α(PCO2/ PHe) and α(PCO2/ PO2). The data are summarized in Table 4.
Table 4
Figure imgf000021_0001

Claims

Claims
1. 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.
2. The membrane according to Claim 1, wherein the hard polymeric 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.
3. The membrane according to Claim 1 or Claim 2, wherein the soft polymeric blocks are selected from the group consisting of poly ether blocks, amorphous polyester blocks and polysiloxane blocks. 4. The membrane according to any one of Claims 1 - 3, wherein the multi-block thermoplastic elastomer is a polyamide-po Iy ether multi-block copolymer. 5. The membrane according to Claim 4, wherein the polyamide-poly ether multi- block copolymer is selected from the group consisting of:
(a) a 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):
Figure imgf000022_0001
Formula (VII)
wherein P is a polyamide block, O is oxygen and Q is a polyether block whereas n indicates an integer such that the intrinsic viscosity η of the multi-block thermoplastic elastomer is in the range of about 0.5 to about 2.5; (b) a 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):
R5- -D- O PE-O- -X- -O PE- 0-- R6
O O O O
Formula (VIII)
wherein R5 and R6 are OH and/or H, a is a number 0.1 to 10, b is a number of2 to 50, D is a residue of an oligoamidediacid or a diacid having a Mn of about 300 to about 8000, PE is a residue of a polyoxyalkylene, preferably a polyoxyethylene, having a Mn of about 200 to about 5000, and X is a residue of a diacid comprising linear or branched aliphatic, eye Io aliphatic or aromatic hydrocarbon residues having 4 to 12 carbon atoms; and (c) 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):
R5. -D- -O PE-O- -D- -NH-X NH- -R6
O O O O
Formula (IX)
wherein R5 and R6 are OH and/or H, c is a number 1 to 4, b is a number of 2 to 50, D is a residue of an oligoamidediacid having a Mn of about 300 to about 3000, PE is a residue of a polyoxyalkylene, preferably a polyoxyethylene, having a Mn of about 200 to about 5000, and X is a residue of a diacid comprising linear or branched aliphatic, eye Io aliphatic or aromatic hydrocarbon residues having 4 to 20 carbon atoms. The membrane according to any one of Claims 1 - 6, wherein the polymer comprising a metal of Group 14 of the Periodic System of the Elements is selected from the group consisting of: (a) a polysiloxane according to Formula (I):
Figure imgf000024_0001
Formula (I)
wherein:
M is the Group 14 metal;
R1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R2 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):
Figure imgf000024_0002
Formula (II)
wherein:
M is the Group 14 metal;
R1 is selected from the group consisting of linear or branched C1 - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof;
R3 is R1 or a polyoxyalkylene chain;
R4 is hydrogen, a linear Ci - Ci2 alkyl group, a (R^)3M-CH2- group, a
(R^2R3M- group, or a mixture thereof; and r is in the range of 100 - 20000; (c) a polyalkyne according to Formula (III):
Figure imgf000025_0001
Formula (III)
wherein:
M is the Group 14 metal;
R1 is selected from the group consisting of linear or branched Ci - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R3 is R1 or a polyoxyalkylene chain; (s/(s+t)) > 0.2; and (t/(s+t)) > 0.05; (d) a polyalkyne according to Formula (IV):
Figure imgf000025_0002
Formula (IV)
wherein:
M is the Group 14 metal;
A is -(CR1 2)v- wherein v = 1 - 6;
R1 is selected from the group consisting of linear or branched C1 - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof;
R3 is R1 or a polyoxyalkylene chain; R4 is hydrogen, a linear Ci - C12 alkyl group, a (R^)3M-CH2- group, a (R^2R3M- group, or a mixture thereof; and u is in the range of 100 - 20000; (e) a polyalkyne according to Formula (V):
Figure imgf000026_0001
Formula (V)
wherein
M is the Group 14 metal; A is -(CR1 2)v- wherein v = 1 - 6;
R1 is selected from the group consisting of linear or branched C1 - C12 alkyl groups, Ce - C12 aryl groups and mixtures thereof; R3 is R1 or a polyoxyalkylene chain; (v/(v+w)) > 0.2; and (w/(v+w)) > 0.05; and (f) a polyalkene according to Formula (VI);
Figure imgf000026_0002
wherein R1 is selected from the group consisting of linear or branched Ci C12 alkyl groups, C6 - Ci2 aryl groups and mixtures thereof; R3 is R1 or a polyoxyalkylene chain; and x is in the range of 100 - 20000. 7. The membrane according to Claim 6, wherein the polyoxyalkylene chain is a polyoxy ethylene chain. 8. The membrane according to Claim 6 or Claim 7, wherein the weight average molecular weight Mw of the polysiloxane according to Formula (I), the polyalkynes according to Formula (II), (III), (IV) or (V) or the polyalkene according to Formula (VI) is determined by the polyoxyethylene chain for about 60% to about 90%. 9. The membrane according to any one of Claims 6 - 8, wherein the polyoxyethylene chain has the formula
Figure imgf000027_0001
wherein p is in such a range that the Mn of the polyoxyethylene chain is equal to about 1000 or less.
10. The membrane according to any one of Claims 1 - 9, wherein the membrane 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 membrane.
11. The membrane according to any one of Claims 1 - 10, wherein the membrane comprises about 1 wt.% to about 99.9 wt.% of the multi-block thermoplastic elastomer comprising alternating hard polymeric blocks and soft polymeric blocks.
12. The membrane according to any one of Claims 1 - 11, wherein the membrane has a CO2 gas permeability coefficient of at least of at least 120 Barrer.
13. The membrane according to any one of Claims 1 - 12, wherein the membrane comprises a support.
14. Use of a membrane according to any one of Claims 1 - 13 for separation processes.
15. Use according to Claim 14, wherein the separation process is a gas/gas separation process. 16. Use according to Claim 15, wherein CO2 is separated from a light gas, wherein the molecular weight of the light gas is 44 or less.
17. Use according to Claim 16, wherein the light gas comprises hydrogen, nitrogen, methane or a mixture thereof.
18. Use of a membrane according to any one of Claims 1 - 13 in ion transport processes.
19. Use of a membrane according to any one of Claims 1 - 13 in ultrafiltration processes and/or nanofiltration processes.
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