WO2018065526A1 - Porous article comprising a polymer and an additive, processes for their preparation and use thereof - Google Patents
Porous article comprising a polymer and an additive, processes for their preparation and use thereof Download PDFInfo
- Publication number
- WO2018065526A1 WO2018065526A1 PCT/EP2017/075370 EP2017075370W WO2018065526A1 WO 2018065526 A1 WO2018065526 A1 WO 2018065526A1 EP 2017075370 W EP2017075370 W EP 2017075370W WO 2018065526 A1 WO2018065526 A1 WO 2018065526A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- group
- additive
- mol
- polymer composition
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 151
- 239000000654 additive Substances 0.000 title claims abstract description 60
- 230000000996 additive effect Effects 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 93
- 239000012528 membrane Substances 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920006126 semicrystalline polymer Polymers 0.000 claims abstract description 16
- -1 poly(phenyl ether) Polymers 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229920006260 polyaryletherketone Polymers 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 13
- 239000004697 Polyetherimide Substances 0.000 claims description 12
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 229920002313 fluoropolymer Polymers 0.000 claims description 12
- 229920001601 polyetherimide Polymers 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000004811 fluoropolymer Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920005597 polymer membrane Polymers 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000412 polyarylene Polymers 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229940071104 xylenesulfonate Drugs 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 3
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 claims description 2
- RXXQCJSZVVTLJB-UHFFFAOYSA-N 5-methyl-2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=C(C)C=C1S(O)(=O)=O RXXQCJSZVVTLJB-UHFFFAOYSA-N 0.000 claims description 2
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 2
- 229940071118 cumenesulfonate Drugs 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 20
- 229920006125 amorphous polymer Polymers 0.000 abstract description 11
- 239000012510 hollow fiber Substances 0.000 abstract description 6
- 238000007493 shaping process Methods 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 description 32
- 239000011734 sodium Substances 0.000 description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 28
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 24
- 229920002530 polyetherether ketone Polymers 0.000 description 23
- 239000002253 acid Substances 0.000 description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 16
- 229920000069 polyphenylene sulfide Polymers 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 229920000491 Polyphenylsulfone Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920002492 poly(sulfone) Polymers 0.000 description 9
- 229920002312 polyamide-imide Polymers 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000005462 imide group Chemical group 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004962 Polyamide-imide Substances 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 150000003949 imides Chemical class 0.000 description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 0 C*C(*(C)(*)C(*NC)=O)=O Chemical compound C*C(*(C)(*)C(*NC)=O)=O 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- 150000003568 thioethers Chemical class 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 5
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 3
- 239000004954 Polyphthalamide Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012633 leachable Substances 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920006375 polyphtalamide Polymers 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- NFRRFEFZKGNYKS-UHFFFAOYSA-N 2-methylpropyl benzenesulfonate Chemical compound CC(C)COS(=O)(=O)C1=CC=CC=C1 NFRRFEFZKGNYKS-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DWNIQUIGFSGOFS-UHFFFAOYSA-N C(CCC)OC(C1=CC=CC=C1)=O.[K] Chemical compound C(CCC)OC(C1=CC=CC=C1)=O.[K] DWNIQUIGFSGOFS-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 2
- 239000004736 Ryton® Substances 0.000 description 2
- 239000004963 Torlon Substances 0.000 description 2
- 229920003997 Torlon® Polymers 0.000 description 2
- KMLAMNQCGDCOAI-UHFFFAOYSA-N [K].CCCCOS(=O)(=O)C1=CC=CC=C1 Chemical compound [K].CCCCOS(=O)(=O)C1=CC=CC=C1 KMLAMNQCGDCOAI-UHFFFAOYSA-N 0.000 description 2
- JNTLILSTWHVJAC-UHFFFAOYSA-N [K].CCOC(=O)C1=CC=CC=C1 Chemical compound [K].CCOC(=O)C1=CC=CC=C1 JNTLILSTWHVJAC-UHFFFAOYSA-N 0.000 description 2
- XRHRHTXIPOVCTD-UHFFFAOYSA-N [K].COC(=O)C1=CC=CC=C1 Chemical compound [K].COC(=O)C1=CC=CC=C1 XRHRHTXIPOVCTD-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- OBTFKRQJZSUBCQ-UHFFFAOYSA-L dipotassium;benzene-1,3-disulfonate Chemical compound [K+].[K+].[O-]S(=O)(=O)C1=CC=CC(S([O-])(=O)=O)=C1 OBTFKRQJZSUBCQ-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000001631 haemodialysis Methods 0.000 description 2
- 230000000322 hemodialysis Effects 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004300 potassium benzoate Substances 0.000 description 2
- 235000010235 potassium benzoate Nutrition 0.000 description 2
- 229940103091 potassium benzoate Drugs 0.000 description 2
- MYGBBCKCTXSGOB-UHFFFAOYSA-M potassium;2-propan-2-ylbenzenesulfonate Chemical compound [K+].CC(C)C1=CC=CC=C1S([O-])(=O)=O MYGBBCKCTXSGOB-UHFFFAOYSA-M 0.000 description 2
- GHKGUEZUGFJUEJ-UHFFFAOYSA-M potassium;4-methylbenzenesulfonate Chemical compound [K+].CC1=CC=C(S([O-])(=O)=O)C=C1 GHKGUEZUGFJUEJ-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000005649 substituted arylene group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- QBIAZVPERXOGAL-OWOJBTEDSA-N (e)-prop-1-ene-1,3-diamine Chemical compound NC\C=C\N QBIAZVPERXOGAL-OWOJBTEDSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical class FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 1
- RLEQVGMLDNITBW-UHFFFAOYSA-N 2,4,4-trimethylhexanedioic acid Chemical compound OC(=O)C(C)CC(C)(C)CC(O)=O RLEQVGMLDNITBW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RBQRPOWGQURLEU-UHFFFAOYSA-N 3-[(3-carboxyphenyl)methyl]benzoic acid Chemical compound OC(=O)C1=CC=CC(CC=2C=C(C=CC=2)C(O)=O)=C1 RBQRPOWGQURLEU-UHFFFAOYSA-N 0.000 description 1
- LJPXCZADJYRIMX-UHFFFAOYSA-N 3-[2-(3-carboxyphenoxy)phenoxy]benzoic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=CC=CC=2)OC=2C=C(C=CC=2)C(O)=O)=C1 LJPXCZADJYRIMX-UHFFFAOYSA-N 0.000 description 1
- CVPWXYQTHJVBDP-UHFFFAOYSA-N 3-[2-(3-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound OC(=O)C1=CC=CC(C(C=2C=C(C=CC=2)C(O)=O)(C(F)(F)F)C(F)(F)F)=C1 CVPWXYQTHJVBDP-UHFFFAOYSA-N 0.000 description 1
- BZVMGPSXJDFUPI-UHFFFAOYSA-N 3-[2-(3-carboxyphenyl)propan-2-yl]benzoic acid Chemical compound C=1C=CC(C(O)=O)=CC=1C(C)(C)C1=CC=CC(C(O)=O)=C1 BZVMGPSXJDFUPI-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- PHQYMDAUTAXXFZ-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C=C1 PHQYMDAUTAXXFZ-UHFFFAOYSA-N 0.000 description 1
- XKACUVXWRVMXOE-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)propan-2-yl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1C(C)(C)C1=CC=C(C(O)=O)C=C1 XKACUVXWRVMXOE-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- 239000004956 Amodel Substances 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920003295 Radel® Polymers 0.000 description 1
- 229920013632 Ryton Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 125000005362 aryl sulfone group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940050390 benzoate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000001601 blood-air barrier Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- MJIVRKPEXXHNJT-UHFFFAOYSA-N lutidinic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=C1 MJIVRKPEXXHNJT-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- BVEDCIGGRGVTKI-UHFFFAOYSA-M potassium 5-methyl-2-propan-2-ylbenzenesulfonate Chemical compound C=1(C(=CC(=CC=1)C)S(=O)(=O)[O-])C(C)C.[K+] BVEDCIGGRGVTKI-UHFFFAOYSA-M 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/002—Organic membrane manufacture from melts
-
- 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
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21827—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- Porous article comprising a polymer and an additive, processes for their preparation and use thereof
- the present invention relates to polymer compositions for the preparation of porous article, notably microporous membranes. More particularly, the present invention relates to a process of preparing a porous article from a blend of at least one semi-crystalline or amorphous polymer with an additive followed by a step of shaping the article and contacting the article with water to dissolve the additive and create an interconnected pore network within the shaped article.
- Porous polymeric membranes are used in a wide variety of applications. They can be prepared using different processes.
- phase inversion refers to a process of membrane formation where polymer solutions become set in a semi-solid gel phase by precipitation.
- NIPS Non- Solvent Induced Phase Separation
- a homogeneous polymeric solution also referred to as "dope solution”
- a suitable solvent and/or a co-solvent is typically processed by casting into a film and then brought to precipitation by contacting it with a non-solvent medium.
- TIPS Thermal Induced Phase Separation
- solvents such as N-Methyl-2-pyrrolidone (NMP), ⁇ , ⁇ -dimethyl formamide (DMF), diethyl phthalate (DEP), dibutyl phthalate (DBP) or dioctyl phthalate (DOP).
- NMP N-Methyl-2-pyrrolidone
- DMF diethyl phthalate
- DBP dibutyl phthalate
- DOP dioctyl phthalate
- Another method known as the temp late- leaching technique can be used to prepare porous membranes from polymers which do not dissolve in common organic solvents.
- a homogeneous film is prepared from a mixture of membrane matrix material and a leachable component.
- the leachable component can be a soluble low molecular weight substance or even a
- US 5,064,580 discloses a method for preparing a microporous membrane from poly(ether ether ketone) (PEEK) polymers and a plasticizer, which is capable of dissolving at least a portion of the PEEK polymer at the extrusion or casting temperature.
- the method comprises a step consisting in leaching the membranes to remove at least a portion of the plasticizer.
- US 6,887,408 discloses a process for the preparation of porous articles of PAEK.
- the process comprises forming the PEEK/PEI blend, forming the shaped article from the blend by extrusion, molding or casting, decomposing the PEI into low molecular weight fragments in the shaped article by chemical treatment, and removing the low molecular weight fragments from the article.
- Chemical reagents that removed the PEI fragments include for example ammonia, hydrazine, N-Methyl-2-pyrrolidone (NMP), ⁇ , ⁇ -dimethyl formamide (DMF), and the like.
- GB 920,229 relates to the production of microporous olefinic polymers (mainly polyethylene and polypropylene polymers) using a water-soluble anionic surfactant.
- porous articles made of amorphous or semi-crystalline polymers, prepared by an environmentally friendly process, which does not use solvents such as NMP or DMF, or does not involve any radiation source.
- Another object of the present invention is to provide a simple and cost-effective process for preparing these porous articles.
- An object of the present invention is to provide a polymer composition (C) suitable to prepare a porous polymer article, for example a membrane or hollow fibers.
- the article is made of a semi-crystalline polymer, for example a poly(ether ether ketone) (PEEK) or a poly(phenylene sulfide) (PPS), presenting valuable thermal properties, mechanical properties (i.e. stiffness to prevent pore collapse), chemical resistance and known to be insoluble in most common solvents.
- a semi-crystalline polymer for example a poly(ether ether ketone) (PEEK) or a poly(phenylene sulfide) (PPS)
- PEEK poly(ether ether ketone)
- PPS poly(phenylene sulfide)
- Another object of the present invention is to provide a simple and cost- effective process for the preparation of these porous articles, the process not using solvents such as NMP or DMF or not involving an irradiation source.
- this process comprises a step consisting in processing or shaping the polymer composition into an article, for example by extrusion, and a step consisting in contacting the article with water so as to dissolve one of the polymer composition components, herein called “additive", thereby creating a pore network within the shaped article.
- additives which are water-soluble, can be compounded homogeneously in various polymer compositions, notably semi-crystalline polymer compositions, withstanding harsh conditions that is to say notably not degrading at high temperatures (for example the ones used in the compounding).
- the homogeneous repartition of the additive within the polymer composition, along with an adjusted quantity of the same within the composition offer the possibility to create an interconnected pore network into the shaped article by a step consisting in dissolution into water.
- the polymer compositions (C) of the present invention comprise at least 28 wt. %, based on the total weight of the polymer composition (C), of the additive.
- the present invention relates to a polymer composition (C) comprising at least one polymer (P), which can be semi-crystalline or amorphous, and at least 28 wt. %, by weight of the polymer composition, of at least one additive.
- This composition is used to prepare porous articles, for example microporous membranes or hollow fibers, to be used in a wide application spectrum covering filtration in general (microfiltration and ultrafiltration), food and dairy industries, wastewater treatment, hemodialysis, battery separators and reverse osmosis pretreatment. More precisely, a homogenous article (e.g. a film or a membrane) is prepared from the mixture of the semi-crystalline and/or amorphous polymer and the additive. After the shaped article (e.g.
- a film or a membrane has been prepared, the additive, which is water-soluble by nature, is removed from the shaped article by immersion into water.
- a porous structure presenting an interconnected pore network is formed as a result (e.g. a porous film or a porous membrane).
- the shaped porous articles obtained with these components, according to this process, have been shown not only to present a high porosity but also good mechanical properties and chemical resistance.
- melting temperature (Tm) or “Tm” or “melting point” means the melting temperature measured by differential scanning calorimetry (DSC) according to
- halogen includes fluorine, chlorine, bromine, and iodine, unless indicated otherwise;
- aromatic denotes any mono- or polynuclear cyclic group (or moiety) having a number of ⁇ electrons equal to 4n+2, where n is 1 or any positive integer; an aromatic group (or moiety) can be an aryl and arylene group (or moiety).
- composition, articles and porous articles of this invention comprise at least one semi-crystalline or amorphous polymer.
- the polymer (P), which can be amorphous or semi-crystalline, is selected from the group consisting of a poly(aryl ether ketone) (PAEK), a poly(aryl ether sulfone) (PAES), a polyarylene sulfide (PAS), a polyetherimide (PEI), a poly(phenyl ether) (PPE), a polycarbonate (PC), a polyamide (PA), a polyphenylene (PP), a polyamideimide (PAI) and a
- the polymer is a PEAK
- it is preferably a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK
- the polymer is a PAES, it is preferably a polyphenylsulfone (PPSU), a polyethersulfone (PES) or a polysulfone (PSU).
- PPSU polyphenylsulfone
- PES polyethersulfone
- PSU polysulfone
- the polymer is a PAS, it is preferably a poly(/?ara-phenylene sulfide) (PPS).
- PPS poly(/?ara-phenylene sulfide)
- the polymer is a fluoropolymer
- it is preferably a polyvinylidene difluoride (PVDF), a polytetrafluoroethylene (PTFE) or a perfluoroalkoxy alkanes (PFA).
- PVDF polyvinylidene difluoride
- PTFE polytetrafluoroethylene
- PFA perfluoroalkoxy alkanes
- the polymers in the polymer composition may have a weight average molecular weight (Mw) ranging from 10,000 g/mol to 150,000 g/mol, preferably from 20,000 g/mol to 100,000 g/mol or from 40,000 to 95,000 g/mol.
- Mw weight average molecular weight
- the weight average molecular weight can be determined by gel permeation chromatography using ASTM D5296 with polystyrene standards.
- the polymer composition includes one, two, three, four, or more different polymers selected from those described herein.
- the recurring units (R PAEK ) may be selected from the group consisting of units of formulae (J- A) to (J-D) below:
- each of R' is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
- - j' is zero or an integer ranging from 1 to 4.
- the respective phenylene moieties may independently have 1,2-, 1,4- or 1,3-linkages to the other moieties different from R' in the recurring unit (R PAEK ).
- the phenylene moieties have 1 ,3- or 1 ,4- linkages, more preferably they have a 1 ,4-linkage.
- j' is preferably at each occurrence zero so that the phenylene moieties have no other substituents than those linking the main chain of the polymer.
- the PAEK is poly(ether ether ketone) (PEEK).
- PEEK poly(ether ether ketone)
- a poly(ether ether ketone) (PEEK) denotes any polymer comprising more than 50 mol. % of recurring units (R PAEK ) of formula (J' -A) :
- R PAEK recurring units
- the PAEK is poly(ether ketone ketone) (PEKK).
- PEKK poly(ether ketone ketone) denotes any polymer comprising more than 50 mol. % of recurring units (R PAEK ) of formula (J'-B) and formula (J"-B):
- R PAEK 95 mol. %, 99 mol. %, and most preferably all of recurring units (R PAEK ) are a combination of recurring units (J'-B) and (J"-B).
- the PAEK is poly(ether
- PEK poly(ether ketone)
- the PAEK is a PEEK-PEDEK copolymer.
- a PEEK-PEDEK copolymer denotes any polymer comprising more than 50 mol. % of recurring units (R PAEK ) of formula (J'-A) (PEEK recurring unit) and formula (J'-D) (poly(diphenyl ether ketone)(PEDEK) recurring unit) :
- the PEEK-PEDEK copolymer may include relative molar proportions of recurring units (J'-A) and (J'-D) (PEEK/PEDEK) ranging from 95/5 to 60/40.
- the sum of recurring units (J'-A) and (J'-D) represents at
- recurring units (J'-A) and (J'-D) represent all of the recurring units in the PAEK.
- the PAEK is PEEK or PEEK-PEDEK.
- KET ASPIRE ® PEEK is commercially available from Solvay Specialty Polymers USA, LLC. Excellent results were obtained when the polymer used to prepare porous membrane was PEEK or PEEK-PEDEK.
- PAES Poly(aryl ether sulfone)s
- PAES poly(aryl ether sulfone)
- each R is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium;
- each h equal to or different from each other, is an integer ranging from 0 to 4.
- T is selected from the group consisting of a bond, a sulfone group
- Rj and Rk are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl
- R j and R k are preferably methyl groups.
- the PAES is a polyphenylsulfone (PPSU).
- PPSU polyphenylsulfone
- PPSU can be prepared by known methods and is notably available as RADEL ® PPSU from Solvay Specialty Polymers USA, L.L.C.
- the PAES is a polyethersulfone (PES).
- PES polyethersulfone
- a polyethersulfone (PES) denotes any polymer comprising at least 50 mol. % of recurring units of formula (K'-B):
- PES can be prepared by known methods and is notably available as VERADEL ® PESU from Solvay Specialty Polymers USA, L.L.C.
- the PAES is a polysulfone (PSU).
- PSU polysulfone
- K'-C formula konvens %
- PSU can be prepared by known methods and is available as UDEL ® PSU from Solvay Specialty Polymers USA, L.L.C.
- PAS polyarylene sulfide
- R PAS recurring units of formula -(Ar'-S)-, where Ar' is an aromatic group.
- PAS include poly(2,4-toluene sulfide), poly(4,4'-biphenylene sulfide), poly(/?ara-phenylene sulfide) (PPS),
- the PAS is poly(/?ara-phenylene sulfide) (PPS).
- a poly(/?ara-phenylene sulfide) (PPS) denotes any polymer comprising at least 50 mol. % of recurring units (Rpps) of formula (L) :
- PPS recurring units
- a polyetherimide denotes any polymer comprising more than 50 mol. % of recurring units (R PEI ) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one ether group.
- R PEI recurring units
- Recurring units may optionally further comprise at least one amide group which is not included in the amic acid form of an imide group.
- R PEI The recurring units (R PEI ) are advantageously selected from the group consisting of following formulae (M), (N), (O), (P) and (Q), and mixtures thereof :
- Ar are tetravalent aromatic moieties and Ar' " are trivalent aromatic moieties independently selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; and
- R is a divalent radical of the general formula (S) :
- Y is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, in particular -C(CH 3 ) 2 ;
- R' ' is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
- p is independently 0, 1 , 2, 3 or 4; provided that at least one of Ar, Ar' ' ' and R comprise at least one ether group wherein the ether group is present in the polymer chain backbone.
- At least 50 mol. % of the recurring units (R PEI ) are recurring units selected from the group consisting of those of formula (T) in imide form, their corresponding amic acid forms of formulae (T'-A) and (T'-B), and mixtures thereof :
- At least 50 mol. % of the recurring units (R PEI ) are recurring units selected from the group consisting of those of formula (U) in imide form, their corresponding amic acid forms of
- 95 mol. %, 99 mol. %, and most preferably all of recurring units (R PEI ) are selected from the group consisting of those of formulae (T), (T'-A), (T'-B), and mixtures thereof or (U), (U'-A), (U'-B), and mixtures thereof.
- a poly(phenyl ether) denotes a polymer comprising more than 50 mol. % of recurring units (R PPE ) of formula (W) :
- A are independently selected from a CI- C30 alkyl groups
- (ii) q is O, 1, 2, 3 or 4.
- at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all recurring units in the PPE are recurring units (RPPE).
- A represents CH 3 and q is 2.
- the phenylene moieties in the PPE have 1,4-linkages.
- PC Polycarbonates
- the arylene group contained in the recurring units (Rpc) is preferably selected from optionally substituted phenylenes and naphthylenes and can substituted or unsubstituted.
- the optionally substituted arylene group of the aromatic diol (D) is preferably selected from optionally substituted phenylenes and optionally substituted naphthylenes.
- the aromatic diol (D) is preferably selected from aromatic diols complying with formulae (D-A) and (D-B) here below:
- - A is selected from C1-C8 alkylenes, C2-C8 alkylidenes, C5-C15
- - Z is selected from F, CI, Br, I, C1-C4 alkyls; if several Z radicals are
- - e denotes an integer from 0 to 1;
- - g denotes an integer from 0 to 1 ;
- - d denotes an integer from 0 to 4.
- - f denotes an integer from 0 to 3.
- aromatic diols (D) are selected in the group consisting of 2,2 bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2 bis (3,5 dimethyl 4 hydroxyphenyl) propane, 2,2,4-trimethyl cyclohexyl 1,1-diphenol and
- aromatic polycarbonates suitable in the practice of the invention as aromatic polycarbonates (PC) are included phenolphthalein-based polycarbonates, copolycarbonates and terpolycarbonates.
- the recurring units of the aromatic polycarbonate are recurring units (Rpc) obtained by the polycondensation reaction of a carbonic acid derivative with bisphenol A.
- the polyamide can have at least about 60 mol. %, at least about 70 mol. %, at least about 80 mol. %, at least about 90 mol. %, at least about 95 mol. %, at least about 99 mol. %, or at least about 99.9 mol. % of recurring units (R PA ).
- the recurring unit (R PA ) can be represented by formula (E) (E), where
- each Ri, R j , R k , and Ri on each carbon atom is independently selected from a hydrogen, a halogen, an alky, an alkenyl, an ether, a thioether, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, an quaternary ammonium, and any combination thereof;
- - m is an integer from 4 to 10;
- - n is an integer from 6 to 12.
- recurring units are obtained by the polycondensation reaction between at least one aliphatic diacid or derivative thereof (acid halogenides, especially chlorides, acid anhydrides, acid salts, acid amides) and at least one aromatic diamine.
- Non limitative examples of aromatic diamines are notably m-phenylene diamine (MPD), /?-phenylene diamine (PPD), 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diaminodiphenyl ether (4,4'-ODA), metaxylylenediamine (MXDA) :
- the aromatic diamine is preferably metaxylylenediamine (MXDA).
- Non limitative examples of aliphatic diacids are notably oxalic acid (HOOC-COOH), malonic acid (HOOC-CH 2 -COOH), succinic acid
- the aliphatic diacid is preferably adipic acid.
- Preferred polymers are PMXDA polymers consisting essentially of recurring units derived from the polycondensation reaction between adipic acid or derivative thereof and metaxylylenediamine.
- PMXDA polymers suitable for the purposes of the invention are notably available as IXEF ® PMXDAs from Solvay Specialty Polymers USA, LLC.
- recurring units (R PA ) are obtained by the polycondensation reaction between at least one aromatic diacid or derivative thereof and at least one aliphatic diamine.
- Non limitative examples of aliphatic diamines are notably
- Preferred aliphatic diamine is hexamethylenediamine (HMD A).
- Aromatic diacids and derivative thereof employed in the polycondensation reaction to yield such polymer are not particularly restricted.
- Non limitative examples of aromatic diacids are notably phthalic acids, including isophthalic acid (IP A), terephthalic acid (TP A) and (ortho)phthalic acid (PA),
- naphalendicarboxylic acids 2,5-pyridinedicarboxylic acid
- the polymer according to this fourth embodiment is a polyphthalamide, i.e. an aromatic polyamide comprising recurring units, more than 50 mole % of the recurring units being obtained by the poly condensation reaction between at least one phthalic acid, chosen among IPA, TPA and PA, or derivative thereof, and at least one aliphatic diamine.
- Suitable polyphthalamides are notably available as AMODEL ® polyphthalamides from Solvay Specialty Polymers USA, LLC.
- PAI Polyamideimide
- a polyamideimide or aromatic polyamide-imide polymer has at least 50 mol. % of recurring units (RPAI) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one amide group which is not included in the amic acid form of an imide group.
- RPAI recurring units
- recurring units are advantageously chosen among those of formula:
- - Ar is a trivalent aromatic group; typically Ar is selected from the group consisting of following structures : and corresponding optionally substituted structures, with X being -0-, -C(O)-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CF 2 ) q -, with q being an integer from 1 to 5 ; R is a divalent aromatic group; typically R is selected from the group consisting of following structures :
- Y being -0-, -S-, -S0 2 -, -CH 2 -, -C(O)-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CF 2 ) q , q being an integer from 1 to 5.
- the aromatic polyamide-imide comprises more than 50 % of recurring units (R PAI ) comprising an imide group in which the imide group is present as such, like in recurring units (RpAi-a), and/or in its amic acid form, like in recurring units (RpAi-b).
- R PAI recurring units
- the imide group is present as such, like in recurring units (RpAi-a), and/or in its amic acid form, like in recurring units (RpAi-b).
- Recurring units are preferably chosen from recurring units (1), (m) and (n), in their amide-imide (a) or amide-amic acid (b) forms :
- the polymer (PAI) comprises more than 90 mol. % of recurring units (R PAI ). Still more preferably, it contains no recurring unit other than recurring units (R PAI ).
- Polymers commercialized by Solvay Specialty Polymers USA, L.L.C. as TORLON ® polyamide-imides comply with this criterion.
- Torlon ® 4000T is an aromatic polyamide-imide polymer commercially available from Solvay Specialty Polymers USA, LLC.
- a polyphenylene polymer denotes any polymer comprising more than 50 mol. % of recurrig units (Rp) of formula (F) :
- R 2 , R 3 , and R 4 are each independently selected from the group consisting of a hydrogen, an alkyl, an aryl, an alkoxy, an aryloxy, an alkylketone, an arylketone, a fluoroalkyl, a fluoroaryl, a bromoalkyl, a bromoaryl, a chloroalkyl, a chloroaryl, an alkylsulfone, an arylsulfone, an alkylamide, an arylamide, an alkylester, an arylester, a fluorine, a chlorine, and a bromine.
- a polyphenylene polymer can have at least about 60 mol.
- R 1 , R 2 , R 3 , and R 4 can be independently represented by formula (F') :
- each R j , R k and Ri is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium and with j and 1, equal or different from each other are independently 0, 1, 2, 3, 4, or 5 and, k, equal or different from j or 1, is independently 0, 1, 2, 3 or 4;
- T is selected from the group consisting of -CH 2 -; -0-; -S0 2 -; -S-;
- each R a and R b independently of one another, is a hydrogen or a Cl-C12-alkyl, Cl-C12-alkoxy, or C6-C18-aryl group; -(CH 2 ) n - and - (CF 2 ) n - with n being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof.
- R 1 , R 2 , R 3 , and R 4 can be represented by formula (F") :
- Polyphenylene copolymers are commercially available from
- Solvay Advanced Polymers L.L.C. as PRIMOSPIRE ® PR-120 polyphenylene and PRIMOSPIRE ® SRP PR-250 polyphenylene.
- a fluoropolymer denotes a polymer comprising recurring units derived from at least one fluorinated monomer, that-is-to-say an ethylenically unsaturated monomer comprising at least one fluorine atom.
- the fluoropolymer may further comprise at least one hydrogenated monomer, that- is-to-say an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
- the fluoropolymer may be semi- crystalline or amorphous.
- the fluoropolymer (FP) is typically selected from the group consisting of :
- polymers (PF-1) comprising recurring units derived from at least one fluorinated monomer selected from tetrafluoroethylene (TFE) and
- chlorotrifluoroethylene and from at least one hydrogenated monomer selected from ethylene, propylene and isobutylene, optionally containing one or more additional comonomers, typically in amounts of from 0.01 % to 30 % by moles, based on the total amount of TFE and/or CTFE and the hydrogenated monomer(s);
- polymers (PF-2) comprising recurring units derived from vinylidene fluoride (VDF), and, optionally, from one or more fluorinated monomers different from VDF;
- polymers (PF-3) comprising recurring units derived from tetrafluoroethylene (TFE) and at least one fluorinated monomer different from TFE selected from the group consisting of :
- - perfluoro-oxyalkylvinylethers of formula CF 2 CFOXo wherein Xo is a C 1 -C 12 perfluorooxyalkyl group comprising one or more ether groups, such as perfluoro-2-propoxy-propyl group; C3-C8 perfluoroolefms, such as hexafluoropropene (HFP); and
- Ri, R 2 , R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a Ci-C 6 fluoroalkyl group, optionally comprising one or more oxygen atoms, and a Ci-C 6 fluoroalkoxy group, optionally comprising one or more oxygen atoms; and (4) polymers (PF-4) comprising recurring units derived from at least one cyclopolymerizable monomer of formula :
- each R 7 to Ri 6 independently of one another, is selected from -F and a C1-C3 fluoroalkyl group, a is 0 or 1, b is 0 or 1 with the proviso that b is 0 when a is 1.
- the fluoropolymer is polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE) or perfluoroalkoxy alkanes (PFA).
- PVDF polyvinylidene difluoride
- PTFE polytetrafluoroethylene
- PFA perfluoroalkoxy alkanes
- Fluoropolymers are commercially available from Solvay Specialty
- the polymer composition (C) of the present invention also comprises an additive of formula (I) :
- Ar is an aromatic moiety and is selected from the group consisting of substituted or unsubstituted, aromatic monocyclic or polycyclic group having 5 to 18 carbon atoms,
- each of R is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8 cycloaliphatic group and a CI -CI 8 aromatic;
- - a is zero or an integer ranging from 1 to 5, preferably a is zero or 1;
- - X is (S0 3 ), (M p+ )i/ p or (COO " ), (M p+ )i /p in which M p+ is a metal cation of p valence;
- - b is an integer ranging from 1 to 4, preferably b is 1 or 2.
- One of the essential features of the present invention is to use an additive in the form of a salt of sulfonic acid or carboxylic acid, more precisely a sulfonate -SO3 " and/or a carboxylate -COO " .
- the additive may comprise 1 to 4 groups X, identical or different, where X is (S0 3 " ), (M p+ )i/ p or (COO " ), (M p+ )i /p in which M p+ is a metal cation of p valence.
- the additive of formula (I) is such that each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl and a C1-C3 aliphatic group (i.e. a methyl, an ethyl or a propyl).
- M is selected from the group consisting of sodium, potassium, calcium, lithium, magnesium, silver, aluminium, zinc, nickel, copper, palladium, iron, and cesium.
- M is sodium or potassium.
- M can alternatively be specifically chosen among alkali metals (IA of the periodic table) or alkaline earths metal (IIA of the periodic table).
- X is a sodium and/or a potassium salt of sulfonic acid and/or carboxylic acid.
- the additive used in the present invention is by nature water-soluble.
- the additive may also be said to be extractable, as defined below.
- the aromatic moiety of formula (I) can be selected from the group consisting of :
- Z is a divalent moiety and is selected from the group consisting of
- n an integer from 1 to 6, for example -CH 2 -
- the additive of formula (I) is such that each aromatic moiety of formula (I), for example (Ar-A) to (Ar-D) comprises 1,2 or 3 groups X, identical or different, where X is (S0 3 ), (M p+ )i/ p or (COO ) , (M p+ )i /p in which M p+ is a metal cation of p valence.
- the additive of formula (I) is such that each aromatic moiety of formula (I) comprises 1 or 2 groups X, identical or different, where X is (S0 3 ), (M p+ )i /p or (COO " ) , (M p+ )i /p in which
- M p+ is a metal cation of p valence.
- the additive is according to formula (II) :
- each of R is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8
- - a is zero or an integer ranging from 1 to 5;
- - b is each of either 1 or 2.
- the additive of formula (I) or (II) is such that a is 0, 1 or 2.
- a is zero so that the phenylene moieties have no other substituents than the sulfonate or carboxylate functions.
- the additive salt is benzoate, methylbenzoate, ethylbenzoate, propylbenzoate, benzene sulfonate, benzene disulfonate, p-toluene sulfonate, xylene sulfonate, cumene sulfonate, p-cymene sulfonate and dodecylbenzene sulfonate.
- the additive is selected from the group consisting of sodium or potassium benzoate, sodium or potassium methyl benzoate, sodium or potassium ethylbenzoate, sodium or potassium butylbenzoate, sodium or potassium benzene sulfonate, sodium or potassium benzene- 1,3-disulfonate, sodium or potassium p-toluene sulfonate, sodium or potassium xylenesulfonate, sodium or potassium cumene sulfonate, sodium or potassium /?ara-cymene sulfonate, sodium or potassium n-butyl benzene sulfonate, sodium or potassium iso-butyl benzene sulfonate, sodium or potassium tert-butyl benezene sulfonate and sodium or potassium dodecylbenzenesulfonate.
- the additive is present in the composition of the invention in a quantity of at least 28 wt. %, based on the total weight of the composition.
- the composition comprises between about 28 and about 80 wt. % of the additive, for example between about 30 and about 75 wt. % or between about 35 and about 70 wt. %.
- the additive has a melting temperature Tma (°C) of at least 150°C, for example of at least 170°C, at least 180°C, at least 190°C, or at least 200 °C, as for example measured by differential scanning calorimetry (DSC) according to ASTM D3418.
- Tma melting temperature
- the composition is such that the polymer (P) is semi-cristalline and the additive has a melting temperature Tma (°C) such that
- Tmp (°C) is the melting point of the semi-crystalline polymer, as for example measured by differential scanning calorimetry (DSC) according to ASTM D3418.
- the components of the composition are chosen according to their respective melting temperatures (°C) so as to fulfil equation (a).
- the components of the composition are chosen so as to fulfil any of the below equations (b) to (e) :
- Melting temperature of the components can notably be measured using differential scanning calorimetry according to ASTM D3418.
- the polymer composition (C) comprises:
- dodecylbenzenesulfonate preferably sodium or potassium benzene sulfonate.
- the polymer composition (C) includes titanium dioxide (Ti0 2 ).
- the amount of titanium dioxide preferably ranges from 0 pph to about 25 pph, for example from about 0.1 pph to about 25 pph, for example from about 5 pph to about 20 pph.
- the amount of titanium dioxide (Ti0 2 ) may be at most about 25 pph, preferably at most about 20 pph, preferably at most about 20 pph, preferably at most about 15 pph.
- the polymer composition (C) may further optionally comprise additional components such as ultraviolet light stabilizers, heat stabilizers, antioxidants, pigments, processing aids, lubricants, flame retardants, plasticizers and/or
- conductivity additive such as carbon black and carbon nanofibrils.
- the polymer composition (C) may further comprise water-soluble or dispersible polymer additives for benefit of processing and/or optimizing pore morphology and/or porosity.
- polymers include : sulfo- polyesters, polyvinyl alcohol, polyethylene oxide, polyethylene oxide/propylene oxide copolymers, polyethylene imine, polyethyloxazoline, and
- polyvinylpyrrolidone Such polymer additive are chosen to remain stable at the desired processing temperature and remain substantially extractable from the final articles by water.
- the polymer composition (C) may further comprise flame retardants such as halogen and halogen free flame retardants.
- article in the present context is thus to be understood broadly. It refers to any type of article of manufacture which can be formed from a polymeric material and covers (a) the intermediate articles (or intermediate shaped articles), which are non-porous, and result directly from the step consisting in shaping the polymer composition of the invention into shaped articles, for example by injection molding, extrusion molding or 3D printing, and (b) the final articles (or final shaped articles), which are porous, and obtained from the intermediate articles which have, for example been immersed into water to dissolve the additive and create the pores.
- the additive is said to be water-soluble and/or extractable.
- the polymer composition (C) may be used for thermal insulation or acoustic insulation, in variable shapes and sizes.
- the polymer article (A) comprising the polymer composition (C) of the present invention may be used as a filter or as a membrane (e.g. microfiltration or ultrafiltration).
- the article is preferably a membrane.
- membrane is used herein in its usual meaning, that is to say it refers to a discrete, generally thin, interface that moderates the permeation of chemical species in contact with it. This interface may be molecularly homogeneous, that is, completely uniform in structure (dense membrane), or it may be chemically or physically heterogeneous, for example containing voids, holes or pores of finite dimensions (porous membrane).
- Membranes can be in the form of a flat sheet or in the form of tubes.
- Tubular membranes are classified based on their dimensions in tubular membranes having a diameter greater than 3 mm; capillary membranes, having a diameter comprised between 0.5 mm and 3 mm; and hollow fine fibers having a diameter of less than 0.5 mm.
- Flat sheet membranes are generally preferred when high fluxes are required whereas hollow fibers are particularly advantageous in applications where compact modules with high surface areas are required.
- Porous membranes can be characterized by permeability measurements (volume of water which permeates through the membrane under given pressure conditions), porosity (ratio between the volume of voids and the total volume occupied by the membrane), pores features (average pore diameter, smallest pore diameter and largest pore diameter). They can also be characterized by their mechanical properties (tensile properties notably) and chemical resistance (after immersion in various solvents during a given amount of time).
- the articles may be used singularly or in bundle arrays and form, for example, filter systems.
- the articles may be, for example, microfiltration membranes, ultrafiltration membranes or support for reverse osmosis.
- Such articles can be used in the separation of various materials.
- the potential utility of such a membrane article depends upon the membrane material, its structure (which depends upon its method of preparation), and the mode in which it is operated.
- such articles can be used to permeate gases, e.g. oxygen or nitrogen, to separate solutes of suspended matter from solutions, e.g. soluble waste materials from blood (hemodialysis) or to separate dissolved molecules, colloids, and suspended solids from smaller molecules, e.g., in the manufacture of latex or cheese (ultrafiltration).
- the inventors have shown that the porous membranes of the present invention present an improved porous structure.
- the present invention also concerns the method of using the final shaped articles, for example porous membrane in filtration and purification processes, such as filtration of waste water, preparation of ultrapure water and in medical, pharmaceutical or food applications, including removal of
- the present invention concerns the use of the shaped articles for filtering or purifying liquids, such as filtering waste water, for preparing ultrapure water and in medical, pharmaceutical or food applications, including removal of microorganisms, dialyses and protein filtration.
- the porosity of the membrane may range from 3 to 90 %, preferably from 5 to 80 % or from 20 to 70 %.
- the membrane has a porosity of about 50 %, or about 60 %.
- the pores may have an average diameter of at least 0.001 ⁇ , of at least 0.005 ⁇ , of at least 0.01 ⁇ , of at least 0.1 ⁇ , of at least 1 ⁇ , of at least 10 ⁇ and of at most 50 ⁇ .
- the porous polymer article for example membrane, is used for filtering or purifying fluids, such as liquids or gas.
- the porous polymer article for example membrane
- batteries such as Li-ion batteries.
- the porous polymer article for example membrane, is used for as a diaphragm for electrolizer for the production of dihydrogen.
- the porous polymer article for example porous membrane according to the present invention, can be used for filtrating biologic solution (e.g. bioburden, virus, other large molecules) and/or buffer solutions (e.g. solutions that may contain small amount of solvents like DMSO or other polar aprotic solvents).
- biologic solution e.g. bioburden, virus, other large molecules
- buffer solutions e.g. solutions that may contain small amount of solvents like DMSO or other polar aprotic solvents.
- the polymer composition (C) is used as a support material in processes for manufacturing a three-dimensional object with an extrusion-based additive manufacturing system, otherwise known also as fused filament fabrication technique.
- the polymer composition (C) used as support material in these 3D manufacturing methods is provided under the form of a filament.
- the filament may have a cylindrical or substantially cylindrical geometry, or may have a non-cylindrical geometry, such as a ribbon filament geometry; further, filament may have a hollow geometry, or may have a core-shell geometry, with the support material of the present invention being used to form either the core or the shell.
- the present invention also relates to the method of making the polymer composition (C) as described above, the method comprising melt-mixing the semi-crystalline or amorphous polymer (P) and the additive.
- the polymer composition (C) can be manufactured by melt-mixing the at least one semi-crystalline or amorphous polymer (P), with at least 28 wt. %, by weight of the polymer composition, of the at least one additive of formula (I):
- Ar is an aromatic moiety and is selected from the group consisting of substituted or unsubstituted, aromatic monocyclic or polycyclic group having 5 to 18 carbon atoms,
- each of R is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8 cycloaliphatic group and a CI -CI 8 aromatic;
- - a is zero or an integer ranging from 1 to 5;
- - b is an integer ranging from 1 to 4.
- the polymer compositions (C) described herein are advantageously provided in the form of pellets, which may be used in injection molding or extrusion processes known in the art.
- the polymer composition (C) can be made by methods well known to the person of ordinary skill in the art.
- such methods include, but are not limited to, melt-mixing processes.
- Melt-mixing processes are typically carried out by heating the thermoplastic polymer above the melting temperature of the thermoplastic polymer thereby forming a melt of the thermoplastic polymer.
- Such a process may be carried out by heating the polymers above the melting temperature (Tm) of the semi- crystalline polymer to form a melt of the polymers and/or above the glass transition temperature (Tg) of the amorphous polymer.
- the processing temperature ranges from about 180-450°C, preferably from about 220-440°C, from about 260-430°C or from about 280-420°C.
- the processing temperature is at least 15°C, preferably at least 30°C, at least 50°C, at least 80°C or at least 100°C greater than the melting temperature (Tg) of the semi-crystalline polymer (or of the highest polymer Tm in the polymer composition if the composition comprises several semi-crystalline polymers).
- the processing temperature is at least 15°C, preferably at least 30°C or at least 50°C greater than the glass transition temperature (Tg) of the amorphous polymer (or of the highest polymer Tg in the polymer composition if the composition comprises several amorphous polymers).
- Tg glass transition temperature
- the melt-mixing process is carried out a temperature which the highest of the Tm or the Tg temperatures.
- the additive used in the context of the present invention is preferably in the form of a powder.
- the process for the preparation of the composition can be carried out in a melt-mixing apparatus, for which any melt-mixing apparatus known to the one skilled in the art of preparing polymer compositions by melt mixing can be used.
- Suitable melt-mixing apparatus are, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders.
- the constituting components for forming the composition are fed to the melt-mixing apparatus and melt-mixed in that apparatus.
- the constituting components may be fed simultaneously as a powder mixture or granule mixer, also known as dry-blend, or may be fed separately.
- the order of combining the components during melt-mixing is not particularly limited.
- the components can be mixed in a single batch, such that the desired amounts of each component are added together and subsequently mixed.
- a first sub-set of components can be initially mixed together and one or more of the remaining components can be added to the mixture for further mixing.
- the total desired amount of each component does not have to be mixed as a single quantity.
- a partial quantity can be initially added and mixed and, subsequently, some or all of the remainder can be added and mixed.
- the method of manufacturing the polymer composition (C) may comprise if needed several successive steps of melt-mixing or extrusion under different conditions.
- the process itself, or each step of the process if relevant, may also comprise a step consisting in a cooling of the molten mixture.
- the intermediate non-porous article (e.g. the shaped non-porous membrane or the shaped porous film) and the final porous article (e.g. the porous membrane or the porous film) according to the present invention are made from the polymer composition (C) using any suitable melt-processing method. In particular, they are made by injection molding, extrusion molding or 3D printing.
- any standard molding technique can be used; standard techniques including shaping the polymer compositions in a molten/softened form can be advantageously applied, and include notably compression molding, extrusion molding, injection molding, transfer molding and the like. Dies may be used to shape the articles, for example a die having an annular orifice if the article is a hollow fiber membrane.
- the method of forming the polymer articles comprises a step consisting in printing layers of a three-dimensional object from the provided polymer composition (C).
- the polymer article is in fact formed with an extrusion-based additive manufacturing system, otherwise known also as fused filament fabrication technique.
- the method of forming the polymer articles comprises at least the step consisting in extruding the polymer composition (C) above described.
- the method of forming the porous polymer articles comprises additionally the step consisting in contacting the intermediate non porous article with water, for example by immersion into water or in a solution containing water.
- the water used to dissolve the water-soluble additive can be at a temperature varying for example between room temperature and 95°C.
- the time period needed to dissolve the polymer is variable. As an example, the time period can vary between 1 second and 2 hours, or from 5 seconds to 1 hour.
- the additive can be said to be extractable, that-is-to-say able to be substantially extracted from the intermediate product by contact with water, for example immersion into water, the water being possibly heated up to 95°C, for a period of time up to 2 hours.
- substantially in this context means that at least 80 wt. % of the additive is extracted from the intermediate product, for example at least 85 wt. %, at least 90 wt. % or at least 95 wt. %, so as to obtained the final shaped porous article.
- the present invention also concerns a method of forming a porous polymer membrane M), comprising:
- the method of forming a porous polymer membrane (M) can comprise one or several optional steps.
- One optional step consists in stretching the membrane.
- This optional step can notably take place during step (iii).
- Another optional step consists in drying the membrane, for example in an oven.
- the present invention is also directed to the porous polymer article (e.g. membrane or hollow tube) obtainable by this method.
- the porous polymer article e.g. membrane or hollow tube
- the porous polymer article may contain up to 20 wt. % of the additive, for example up to 15 wt. % of the additive, up to 10 wt. % of the additive, up to
- the additive contains less than 1 wt. % of the additive.
- the articles according to the present invention may be coated or further treated.
- the method may additionally comprise at least one additional step comprising coating at least one metal onto at least a part of the surface of the said part.
- PPS polymer Ryton ® QC 160N from Solvay Specialty Polymers USA, LLC .
- PEEK polymer KetaSpire ® KT-880P from Solvay Specialty Polymers USA, LLC. This grade has a melt viscosity in the range 120-180 Pa-s as measured at 400 °C and 1000 1/s according to ASTM D-3835;
- Tm Melting temperatures of the various components were measured using differential scanning calorimetry according to ASTM D3418 employing a heating and cooling rate of 20 °C/min. Three scans were used for each DSC test : a first heat up to 400 °C, followed by a first cool down to 50 °C, followed by a second heat up to 400 °C. The Tm was determined from the second heat up as the peak temperature on the melting endotherm.
- the melting temperatures for the four components used in the examples and comparative examples are tabulated in Table 1.
- Membrane #1 Blend PEEK/ NaBzS 60/40
- Comparative membrane #1 Blend PPS/NaAc 50/50
- Selected polymer and additives were pre-dried in oven to eliminate moisture.
- the combined constituents were added to an Eries Magnetics FT-26 vibratory feeder and fed directly into a Leistritz Micl8Gl/30D twin screw co- rotating compounder with screw speed set to 200 rpm and barrel settings adjusted such that the melt temperature was about 320°C for PPS and 380°C for PEEK.
- the material was then cooled into strands and pelletized.
- the pellets were then fed into a gravity hopper mounted to a DSM Xplore MCI 5 compounder with 15mL barrel capacity and 1" width film die.
- the barrel temperatures were adjusted such that the melt temperature was > 320°C for PPS, and 380°C for PEEK with screw speed set to force control.
- Membranes were collected on a DSM Xplore film winder with roll settings (speed, torque) adjusted to target a 100-200 ⁇ thickness.
- the membrane #2 was dried in vacuum and weighed. The membrane was then immersed in an excess of hot water (about 90°C) for 2 hours. The membrane was then dried in vacuum and re-weighed to determine extraction efficiency.
- Water flux J expressed in l/(m 2 xh)
- the water flux is calculated by the following equation :
- Membrane porosity (£m) was determined according to the gravimetric method. Porosity is defined as the ratio between the volume of voids and the total volume occupied by the membrane. Perfectly dry membrane pieces were weighed and impregnated in isopropylic alcohol (IP A) for 24h; after this time, the excess of the liquid was removed with tissue paper, and membranes weight was measured again. Finally, from the dry and the wet weight of the sample, it is possible to evaluate the porosity of the membrane using the following formula :
- - pp is the polymer density (1.35 for PPS and 1.3 for PEEK).
- Membranes bubble points, smallest pore size and pore size distribution were determined following ASTM F316 method, using a capillary flow porometer PoroluxTM 1000 (Porometer-Belgium). For each test, membranes samples were initially fully wetted using Fluorinert ® FC 43 (fluorinated fluid with a surface tension of 16 dyn/cm). Nitrogen (inert gas) was used. Results are presented in Table 3 below.
- the porous membranes #1 and #2 present good mechanical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to polymer compositions (C) for the preparation of porous article, notably microporous membranes or hollow fibers. More particularly, the present invention relates to a process of preparing a porous article from a blend of at least one semi-crystalline or amorphous polymer (P) with an additive followed by a step of shaping the article and contacting the article with water to dissolve the additive and create an interconnected pore network within the shaped article.
Description
Porous article comprising a polymer and an additive, processes for their preparation and use thereof
RELATED APPLICATIONS
This application claims priority to U.S. provisional application No.
62/404,934, filed October 6, 2016 and to European patent application No.
17153832.5 filed January 30, 2017, the whole content of each of these applications being incorporated herein by reference for all purposes.
FIELD OF THE INVENTION
The present invention relates to polymer compositions for the preparation of porous article, notably microporous membranes. More particularly, the present invention relates to a process of preparing a porous article from a blend of at least one semi-crystalline or amorphous polymer with an additive followed by a step of shaping the article and contacting the article with water to dissolve the additive and create an interconnected pore network within the shaped article. BACKGROUND
Porous polymeric membranes are used in a wide variety of applications. They can be prepared using different processes.
The phase inversion methods are currently the most commonly used ones. Phase inversion refers to a process of membrane formation where polymer solutions become set in a semi-solid gel phase by precipitation. In the Non- Solvent Induced Phase Separation (NIPS) process, a homogeneous polymeric solution (also referred to as "dope solution") containing a polymer, a suitable solvent and/or a co-solvent is typically processed by casting into a film and then brought to precipitation by contacting it with a non-solvent medium. In the Thermal Induced Phase Separation (TIPS) process, precipitation is obtained by decreasing the temperature of the polymeric solution. These methods use solvents, such as N-Methyl-2-pyrrolidone (NMP), Ν,Ν-dimethyl formamide (DMF), diethyl phthalate (DEP), dibutyl phthalate (DBP) or dioctyl phthalate (DOP). The use of solvents generates substantial environmental and disposal problems. There have been many active research efforts to replace the use of solvents with environmentally friendly alternatives.
Another method known as the temp late- leaching technique can be used to prepare porous membranes from polymers which do not dissolve in common
organic solvents. In this technique, a homogeneous film is prepared from a mixture of membrane matrix material and a leachable component. The leachable component can be a soluble low molecular weight substance or even a
macro molecular material such as poly( vinyl alcohol) (PVA) or poly(ethylene glycol) (PEG). After the film has been prepared, the leachable component is removed by a suitable chemical treatment, and a porous structure is formed as a result. One drawback of this method is the low thermal stability of PEG and PVA that degrades at temperatures above 300°C.
US 5,064,580 discloses a method for preparing a microporous membrane from poly(ether ether ketone) (PEEK) polymers and a plasticizer, which is capable of dissolving at least a portion of the PEEK polymer at the extrusion or casting temperature. The method comprises a step consisting in leaching the membranes to remove at least a portion of the plasticizer.
US 6,887,408 discloses a process for the preparation of porous articles of PAEK. The process comprises forming the PEEK/PEI blend, forming the shaped article from the blend by extrusion, molding or casting, decomposing the PEI into low molecular weight fragments in the shaped article by chemical treatment, and removing the low molecular weight fragments from the article. Chemical reagents that removed the PEI fragments include for example ammonia, hydrazine, N-Methyl-2-pyrrolidone (NMP), Ν,Ν-dimethyl formamide (DMF), and the like.
GB 920,229 relates to the production of microporous olefinic polymers (mainly polyethylene and polypropylene polymers) using a water-soluble anionic surfactant.
There is still a need to provide porous articles, made of amorphous or semi-crystalline polymers, prepared by an environmentally friendly process, which does not use solvents such as NMP or DMF, or does not involve any radiation source. Another object of the present invention is to provide a simple and cost-effective process for preparing these porous articles.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a polymer composition (C) suitable to prepare a porous polymer article, for example a membrane or hollow fibers.
According to one embodiment, the article is made of a semi-crystalline polymer, for example a poly(ether ether ketone) (PEEK) or a poly(phenylene sulfide) (PPS), presenting valuable thermal properties, mechanical properties (i.e.
stiffness to prevent pore collapse), chemical resistance and known to be insoluble in most common solvents.
Another object of the present invention is to provide a simple and cost- effective process for the preparation of these porous articles, the process not using solvents such as NMP or DMF or not involving an irradiation source.
According to one embodiment of the invention, this process comprises a step consisting in processing or shaping the polymer composition into an article, for example by extrusion, and a step consisting in contacting the article with water so as to dissolve one of the polymer composition components, herein called "additive", thereby creating a pore network within the shaped article. The inventors have surprisingly found that certain additives, which are water-soluble, can be compounded homogeneously in various polymer compositions, notably semi-crystalline polymer compositions, withstanding harsh conditions that is to say notably not degrading at high temperatures (for example the ones used in the compounding). The homogeneous repartition of the additive within the polymer composition, along with an adjusted quantity of the same within the composition, offer the possibility to create an interconnected pore network into the shaped article by a step consisting in dissolution into water.
According to the invention, the polymer compositions (C) of the present invention comprise at least 28 wt. %, based on the total weight of the polymer composition (C), of the additive.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to a polymer composition (C) comprising at least one polymer (P), which can be semi-crystalline or amorphous, and at least 28 wt. %, by weight of the polymer composition, of at least one additive. This composition is used to prepare porous articles, for example microporous membranes or hollow fibers, to be used in a wide application spectrum covering filtration in general (microfiltration and ultrafiltration), food and dairy industries, wastewater treatment, hemodialysis, battery separators and reverse osmosis pretreatment. More precisely, a homogenous article (e.g. a film or a membrane) is prepared from the mixture of the semi-crystalline and/or amorphous polymer and the additive. After the shaped article (e.g. a film or a membrane) has been prepared, the additive, which is water-soluble by nature, is removed from the shaped article by immersion into water. A porous structure presenting an interconnected pore network is formed as a result (e.g. a porous film or a porous membrane). The shaped porous articles obtained with these components,
according to this process, have been shown not only to present a high porosity but also good mechanical properties and chemical resistance.
For the sake of clarity, throughout the present application :
- "melting temperature (Tm)" or "Tm" or "melting point" means the melting temperature measured by differential scanning calorimetry (DSC) according to
ASTM D3418 at 20°C/min as described in details in the examples;
- the term "halogen" includes fluorine, chlorine, bromine, and iodine, unless indicated otherwise;
- the adjective "aromatic" denotes any mono- or polynuclear cyclic group (or moiety) having a number of π electrons equal to 4n+2, where n is 1 or any positive integer; an aromatic group (or moiety) can be an aryl and arylene group (or moiety).
The composition, articles and porous articles of this invention comprise at least one semi-crystalline or amorphous polymer.
According to the invention, the polymer (P), which can be amorphous or semi-crystalline, is selected from the group consisting of a poly(aryl ether ketone) (PAEK), a poly(aryl ether sulfone) (PAES), a polyarylene sulfide (PAS), a polyetherimide (PEI), a poly(phenyl ether) (PPE), a polycarbonate (PC), a polyamide (PA), a polyphenylene (PP), a polyamideimide (PAI) and a
fluorinated polymer.
When the polymer is a PEAK, it is preferably a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK
copolymer).
When the polymer is a PAES, it is preferably a polyphenylsulfone (PPSU), a polyethersulfone (PES) or a polysulfone (PSU).
When the polymer is a PAS, it is preferably a poly(/?ara-phenylene sulfide) (PPS).
When the polymer is a fluoropolymer, it is preferably a polyvinylidene difluoride (PVDF), a polytetrafluoroethylene (PTFE) or a perfluoroalkoxy alkanes (PFA).
Generally, the polymers in the polymer composition may have a weight average molecular weight (Mw) ranging from 10,000 g/mol to 150,000 g/mol, preferably from 20,000 g/mol to 100,000 g/mol or from 40,000 to 95,000 g/mol. The weight average molecular weight can be determined by gel permeation chromatography using ASTM D5296 with polystyrene standards.
In some embodiments, the polymer composition includes one, two, three, four, or more different polymers selected from those described herein.
Poly(aryl ether ketone)s (PAEK)
As used herein, a poly(aryl ether ketone) (PAEK) denotes any polymer comprising more than 50 mol. % of recurring units (RPAEK) comprising a Ar'-C(=0)-Ar* group, where Ar' and Ar*, equal to or different from each other, are aromatic groups. The recurring units (RPAEK) may be selected from the group consisting of units of formulae (J- A) to (J-D) below:
where
- each of R', equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
- j' is zero or an integer ranging from 1 to 4.
In recurring unit (RPAEK), the respective phenylene moieties may independently have 1,2-, 1,4- or 1,3-linkages to the other moieties different
from R' in the recurring unit (RPAEK). Preferably, the phenylene moieties have 1 ,3- or 1 ,4- linkages, more preferably they have a 1 ,4-linkage.
In recurring units (RPAEK), j' is preferably at each occurrence zero so that the phenylene moieties have no other substituents than those linking the main chain of the polymer.
In some embodiments, the PAEK is poly(ether ether ketone) (PEEK). As used herein, a poly(ether ether ketone) (PEEK) denotes any polymer comprising more than 50 mol. % of recurring units (RPAEK) of formula (J' -A) :
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of recurring units (RPAEK) are recurring units (J'- A).
In another preferred embodiment, the PAEK is poly(ether ketone ketone) (PEKK). As used herein, a poly(ether ketone ketone) (PEKK) denotes any polymer comprising more than 50 mol. % of recurring units (RPAEK) of formula (J'-B) and formula (J"-B):
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of recurring units (RPAEK) are a combination of recurring units (J'-B) and (J"-B).
In yet another preferred embodiment, the PAEK is poly(ether
ketone) (PEK). As used herein, a poly(ether ketone) (PEK) denotes any polymer comprising more tha of formula (J'-C) :
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of recurring units (RPAEK) are recurring units (J'-C).
In some embodiments, the PAEK is a PEEK-PEDEK copolymer. As used herein, a PEEK-PEDEK copolymer denotes any polymer comprising more than 50 mol. % of recurring units (RPAEK) of formula (J'-A) (PEEK recurring unit) and formula (J'-D) (poly(diphenyl ether ketone)(PEDEK) recurring unit) :
The PEEK-PEDEK copolymer may include relative molar proportions of recurring units (J'-A) and (J'-D) (PEEK/PEDEK) ranging from 95/5 to 60/40. Preferably the sum of recurring units (J'-A) and (J'-D) represents at
least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, of recurring units in the PAEK. In some aspects, recurring units (J'-A) and (J'-D) represent all of the recurring units in the PAEK.
Most preferably, the PAEK is PEEK or PEEK-PEDEK. KET ASPIRE® PEEK is commercially available from Solvay Specialty Polymers USA, LLC. Excellent results were obtained when the polymer used to prepare porous membrane was PEEK or PEEK-PEDEK.
Poly(aryl ether sulfone)s (PAES)
For the purpose of the present invention, a poly(aryl ether sulfone) (PAES) denotes any polymer comprising at least 50 mol. % of recurring units (RPAES) of formula (K) :
where
(i) each R, equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium;
(ii) each h, equal to or different from each other, is an integer ranging from 0 to 4; and
(iii) T is selected from the group consisting of a bond, a sulfone group
[-S(=0)2-], and a group -C(Rj)(Rk)-, where Rj and Rk, equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an
alkenyl, an alkynyl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl
phosphonate, an amine, and a quaternary ammonium. Rj and Rk are preferably methyl groups.
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of recurring units in the PAES are recurring units (RPAES).
In one embodiment, the PAES is a polyphenylsulfone (PPSU). As used herein, a polyphenylsulfone (PPSU) denotes any polymer comprising more than
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PPSU are recurring units of formula (K'-A).
PPSU can be prepared by known methods and is notably available as RADEL® PPSU from Solvay Specialty Polymers USA, L.L.C.
In some embodiments, the PAES is a polyethersulfone (PES). As used herein, a polyethersulfone (PES) denotes any polymer comprising at least 50 mol. % of recurring units of formula (K'-B):
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PES are recurring units of formula (K'-B).
PES can be prepared by known methods and is notably available as VERADEL® PESU from Solvay Specialty Polymers USA, L.L.C.
In some embodiments, the PAES is a polysulfone (PSU). As used herein, a polysulfone (PSU) denotes any polymer comprising at least 50 mol. % of recurring units of formula (K'-C):
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PSU are recurring units of formula (K'-C).
PSU can be prepared by known methods and is available as UDEL® PSU from Solvay Specialty Polymers USA, L.L.C.
Polyarylene Sulfide (PAS)
For the purpose of the present invention, the expression "polyarylene sulfide (PAS)" is intended to denote any polymer comprising more
than 50 mol. % of recurring units (RPAS) of formula -(Ar'-S)-, where Ar' is an aromatic group.
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PAS are recurring units (RPAS).
Nonlimiting examples of PAS include poly(2,4-toluene sulfide), poly(4,4'-biphenylene sulfide), poly(/?ara-phenylene sulfide) (PPS),
poly(ort/zo-phenylene sulfide), poly(meto-phenylene sulfide), poly(xylene sulfide), poly(ethylisopropylphenylene sulfide), poly(tetramethylphenylene sulfide), poly(butylcyclohexylphenylene sulfide), poly(hexyldodecylphenylene sulfide), poly(octadecylphenylene sulfide), poly(phenylphenylene sulfide), poly-(tolylphenylene sulfide), poly(benzylphenylene sulfide),
poly[octyl-4-(3-methylcyclopentyl)phenylene sulfide], and any combination thereof.
Preferably, the PAS is poly(/?ara-phenylene sulfide) (PPS). As used herein, a poly(/?ara-phenylene sulfide) (PPS) denotes any polymer comprising at least 50 mol. % of recurring units (Rpps) of formula (L) :
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PPS are recurring units (Rpps).
PPS is manufactured and sold under the trade name Ryton PPS by Solvay Specialty Polymers USA, LLC. Excellent results were obtained when the polymer used to prepare porous membrane was PPS.
Polyetherimide (PEI)
For the purpose of the present invention, a polyetherimide (PEI) denotes any polymer comprising more than 50 mol. % of recurring units (RPEI) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one ether group. Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of recurring units of the PEI are recurring units (RPEI).
Recurring units (RPEI) may optionally further comprise at least one amide group which is not included in the amic acid form of an imide group.
The recurring units (RPEI) are advantageously selected from the group consisting of following formulae (M), (N), (O), (P) and (Q), and mixtures thereof :
formula (M) formula (N) formula (O);
formula (P) formula (Q)
where in formulae (M)-(Q) :
Ar are tetravalent aromatic moieties and Ar' " are trivalent aromatic moieties independently selected from the group consisting of a substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic group having 5 to 50 carbon atoms; and
where (i) Y is selected from the group consisting of alkylenes of 1 to 6 carbon atoms, in particular -C(CH3)2; (ii) R' ' is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and (iii) p is independently 0, 1 , 2, 3 or 4; provided that at least one of Ar, Ar' ' ' and R comprise at least one ether group wherein the ether group is present in the polymer chain backbone.
In a preferred embodiment, at least 50 mol. % of the recurring units (RPEI) are recurring units selected from the group consisting of those of formula (T) in imide form, their corresponding amic acid forms of formulae (T'-A) and (T'-B), and mixtures thereof :
where in formulae (T'-A) and (T'-B) the "→" denotes isomerism so that in any recurring unit the groups to which the arrows point may exist as shown or in an interchanged position.
In a another preferred embodiment, at least 50 mol. % of the recurring units (RPEI) are recurring units selected from the group consisting of those of
formula (U) in imide form, their corresponding amic acid forms of
formulae (LP -A) and (U'-B), and mixtures thereof :
wherein in formulae (LP -A) and (U'-B) the "→" denotes isomerism so that in any recurring unit the groups to which the arrows point may exist as shown or in an interchanged position.
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %,
95 mol. %, 99 mol. %, and most preferably all of recurring units (RPEI) are selected from the group consisting of those of formulae (T), (T'-A), (T'-B), and mixtures thereof or (U), (U'-A), (U'-B), and mixtures thereof.
Poly(phenyl ether) (PPE)
For the purpose of the present invention, a poly(phenyl ether) (PPE denotes a polymer comprising more than 50 mol. % of recurring units (RPPE) of formula (W) :
where
(i) A are independently selected from a CI- C30 alkyl groups, and
(ii) q is O, 1, 2, 3 or 4.
Preferably at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all recurring units in the PPE are recurring units (RPPE).
Preferably, A represents CH3 and q is 2.
Preferably the phenylene moieties in the PPE have 1,4-linkages.
Polycarbonates (PC)
For the purpose of the present invention, a polycarbonate (PC) denotes a polymer comprising more than 50 wt. % of the recurring units (Rpc) comprising at least one optionally substituted arylene group and at least one carbonate group (-0-C(=0)-0).
The arylene group contained in the recurring units (Rpc) is preferably selected from optionally substituted phenylenes and naphthylenes and can substituted or unsubstituted.
The recurring units (Rpc) can be selected from those obtainable by the polycondensation reaction of a carbonic acid derivative, typically diphenyl carbonate Ph-0-C(=0)-0-Ph, wherein Ph is phenyl, or phosgene C1-C(=0)-C1, and at least one optionally substituted aromatic diol (D) HO-R-OH in which R is a C6-C50 divalent radical comprising at least one arylene group.
The optionally substituted arylene group of the aromatic diol (D) is preferably selected from optionally substituted phenylenes and optionally substituted naphthylenes.
The aromatic diol (D) is preferably selected from aromatic diols complying with formulae (D-A) and (D-B) here below:
cycloalkylenes, C5-C15 cycloalkylidenes, carbonyl atom, oxygen atom, sulfur atom, SO, SO2- and radicals complying with formula (D'-A) here below :
- Z is selected from F, CI, Br, I, C1-C4 alkyls; if several Z radicals are
substituents, they may be identical or different from one another;
- e denotes an integer from 0 to 1;
- g denotes an integer from 0 to 1 ;
- d denotes an integer from 0 to 4; and
- f denotes an integer from 0 to 3.
Preferably, aromatic diols (D) are selected in the group consisting of 2,2 bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2 bis (3,5 dimethyl 4 hydroxyphenyl) propane, 2,2,4-trimethyl cyclohexyl 1,1-diphenol and
1 , 1 -bis-(4-hydroxy-phenyl)-cyclohexane.
Among the aromatic polycarbonates suitable in the practice of the invention as aromatic polycarbonates (PC) are included phenolphthalein-based polycarbonates, copolycarbonates and terpolycarbonates.
Preferably more than 75 wt. %, more preferably more than 90 wt. % and more preferably 100 wt. % of the recurring units of the aromatic polycarbonate are recurring units (Rpc).
According to a particularly preferred embodiment, essentially all, if not all, the recurring units of the aromatic polycarbonate are recurring units (Rpc) obtained by the polycondensation reaction of a carbonic acid derivative with bisphenol A.
Polyamides (PA)
As used herein, a polyamide has at least about 50 mol. % recurring units (RPA) including at least one amide group (-C(=0)N(H)-). In some embodiments, the polyamide can have at least about 60 mol. %, at least about 70 mol. %, at least about 80 mol. %, at least about 90 mol. %, at least about 95 mol. %, at least about 99 mol. %, or at least about 99.9 mol. % of recurring units (RPA).
According to a first embodiment, the recurring unit (RPA) can be represented by formula (E)
(E),
where
- each Ri, Rj, Rk, and Ri on each carbon atom is independently selected from a hydrogen, a halogen, an alky, an alkenyl, an ether, a thioether, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, an quaternary ammonium, and any combination thereof;
- m is an integer from 4 to 10;
- n is an integer from 6 to 12.
According to a second embodiment, recurring units (RPA) are obtained from lactam or aminoacids having the structure NH2-(CH2)n-COOH with n=3 to 12, preferentially covering n=5, n=10, n=l 1 (PA6, PA1 1 , PA12).
According to a third embodiment, recurring units (RPA) are obtained by the polycondensation reaction between at least one aliphatic diacid or derivative thereof (acid halogenides, especially chlorides, acid anhydrides, acid salts, acid amides) and at least one aromatic diamine.
Non limitative examples of aromatic diamines are notably m-phenylene diamine (MPD), /?-phenylene diamine (PPD), 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diaminodiphenyl ether (4,4'-ODA), metaxylylenediamine (MXDA) :
(4,4'-ODA) (3,4' -ODA)
The aromatic diamine is preferably metaxylylenediamine (MXDA).
Non limitative examples of aliphatic diacids are notably oxalic acid (HOOC-COOH), malonic acid (HOOC-CH2-COOH), succinic acid
[HOOC-(CH2)2-COOH], glutaric acid [HOOC-(CH2)3-COOH],
2,2-dimethyl-glutaric acid [HOOC-C(CH3)2-(CH2)2-COOH], adipic acid
[HOOC-(CH2)4-COOH], 2,4,4-trimethyl-adipic acid
[HOOC-CH(CH3)-CH2-C(CH3)2- CH2-COOH], pimelic acid
[HOOC-(CH2)5_COOH], suberic acid [HOOC-(CH2)6-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid [HOOC-(CH2)8-COOH], undecanedioic acid [HOOC-(CH2)9-COOH], dodecandioic acid [HOOC-(CH2)i0-COOH], tetradecandioic acid [HOOC-(CH2)„-COOH].
The aliphatic diacid is preferably adipic acid.
As above mentioned, such aliphatic diacids can be used in the
polycondensation reaction notably under the form of free acid and acid chloride.
Preferred polymers are PMXDA polymers consisting essentially of recurring units derived from the polycondensation reaction between adipic acid or derivative thereof and metaxylylenediamine.
PMXDA polymers suitable for the purposes of the invention are notably available as IXEF® PMXDAs from Solvay Specialty Polymers USA, LLC.
According to a fourth embodiment, recurring units (RPA) are obtained by the polycondensation reaction between at least one aromatic diacid or derivative thereof and at least one aliphatic diamine.
Non limitative examples of aliphatic diamines are notably
1 ,2-diaminoethane, 1 ,2-diaminopropane, propylene- 1 ,3-diamine,
1 ,3-diamino butane, 1 , 4-diamino butane (putrescine), 1 ,5-diaminopentane (cadaverine), 1 ,6-hexanediamine or hexamethylenediamine (HMD A),
1 ,8-diaminooctane, 1 , 10-diaminodecane, 1 , 12-diaminododecane,
1 -amino-3 -N-methyl-N-(3 -aminopropyl)-aminopropane) .
Preferred aliphatic diamine is hexamethylenediamine (HMD A).
Aromatic diacids and derivative thereof employed in the polycondensation reaction to yield such polymer are not particularly restricted. Non limitative examples of aromatic diacids are notably phthalic acids, including isophthalic acid (IP A), terephthalic acid (TP A) and (ortho)phthalic acid (PA),
naphalendicarboxylic acids, 2,5-pyridinedicarboxylic acid,
2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid,
2,2-bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)methane,
2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, bis(3-carboxyphenyl)methane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene.
Preferably, the polymer according to this fourth embodiment is a polyphthalamide, i.e. an aromatic polyamide comprising recurring units, more than 50 mole % of the recurring units being obtained by the poly condensation reaction between at least one phthalic acid, chosen among IPA, TPA and PA, or derivative thereof, and at least one aliphatic diamine.
(IPA) (TPA) (PA)
Suitable polyphthalamides are notably available as AMODEL® polyphthalamides from Solvay Specialty Polymers USA, LLC.
Polyamideimide (PAI)
As used herein, a polyamideimide or aromatic polyamide-imide polymer (PAI) has at least 50 mol. % of recurring units (RPAI) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one amide group which is not included in the amic acid form of an imide group.
The recurring units (RPAI) are advantageously chosen among those of formula:
(amic acid form)
(imide form)
wherein :
- Ar is a trivalent aromatic group; typically Ar is selected from the group consisting of following structures :
and corresponding optionally substituted structures, with X being -0-, -C(O)-, -CH2-, -C(CH3)2-, -C(CF3)2-, -(CF2)q-, with q being an integer from 1 to 5 ; R is a divalent aromatic group; typically R is selected from the group consisting of following structures :
and corresponding optionally substituted structures, with Y being -0-, -S-, -S02-, -CH2-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -(CF2)q, q being an integer from 1 to 5.
Preferably, the aromatic polyamide-imide comprises more than 50 % of recurring units (RPAI) comprising an imide group in which the imide group is present as such, like in recurring units (RpAi-a), and/or in its amic acid form, like in recurring units (RpAi-b).
Recurring units (RPAI) are preferably chosen from recurring units (1), (m) and (n), in their amide-imide (a) or amide-amic acid (b) forms :
wherein the attachment of the two amide groups to the aromatic ring as shown in (1-b) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations ;
wherein the attachment of the two amide groups to the aromatic ring as shown in (m-b) will be understood to represent the 1 ,3 and the 1 ,4 polyamide-amic acid configurations ; and
wherein the attachment of the two amide groups to the aromatic ring as shown in (n-b) will be understood to represent the 1 ,3 and the 1 ,4 polyamide-amic acid configurations.
More preferably, the polymer (PAI) comprises more than 90 mol. % of recurring units (RPAI). Still more preferably, it contains no recurring unit other than recurring units (RPAI). Polymers commercialized by Solvay Specialty Polymers USA, L.L.C. as TORLON® polyamide-imides comply with this criterion.
Torlon® 4000T is an aromatic polyamide-imide polymer commercially available from Solvay Specialty Polymers USA, LLC.
Polyp henylenes (PP)
As used herein, a polyphenylene polymer denotes any polymer comprising more than 50 mol. % of recurrig units (Rp) of formula (F) :
where
- R2, R3, and R4 are each independently selected from the group consisting of a hydrogen, an alkyl, an aryl, an alkoxy, an aryloxy, an alkylketone, an
arylketone, a fluoroalkyl, a fluoroaryl, a bromoalkyl, a bromoaryl, a chloroalkyl, a chloroaryl, an alkylsulfone, an arylsulfone, an alkylamide, an arylamide, an alkylester, an arylester, a fluorine, a chlorine, and a bromine. In some embodiments, a polyphenylene polymer can have at least about 60 mol. %, at least about 70 mol. %, at least about 80 mol. %, at least about 90 mol. %, at least about 95 mol. %, at least about 99 mol. % or at least about 99.9 mol. % repeat units (Rp).
In some embodiments, one or more of R1, R2, R3, and R4 can be independently represented by formula (F') :
Ar - T - (F')
wherein :
- Ar is represented by a formula selected from the following group of formulae
- with each Rj, Rk and Ri is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium and with j and 1, equal or different from each other are independently 0, 1, 2, 3, 4, or 5 and, k, equal or different from j or 1, is independently 0, 1, 2, 3 or 4;
- where the dashed lined indicates a bond to T.
- where T is selected from the group consisting of -CH2-; -0-; -S02-; -S-;
-C(O)-; -C(CH3)2-; -C(CF3)2-; -C(=CC12)-; -C(CH3)(CH2CH2COOH)-; -N=N-; -RaC=CRb-, where each Ra and Rb, independently of one another, is a hydrogen or a Cl-C12-alkyl, Cl-C12-alkoxy, or C6-C18-aryl group; -(CH2)n- and - (CF2)n- with n being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof.
where, in formula (F' '), the dashed bond indicates the bond to the benzyl moiety of repeat unit (Rp).
Polyphenylene copolymers are commercially available from
Solvay Advanced Polymers, L.L.C. as PRIMOSPIRE® PR-120 polyphenylene and PRIMOSPIRE® SRP PR-250 polyphenylene.
Fluoropolymer (FP)
As used herein, a fluoropolymer denotes a polymer comprising recurring units derived from at least one fluorinated monomer, that-is-to-say an ethylenically unsaturated monomer comprising at least one fluorine atom. The fluoropolymer may further comprise at least one hydrogenated monomer, that- is-to-say an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms. The fluoropolymer may be semi- crystalline or amorphous.
The fluoropolymer (FP) is typically selected from the group consisting of :
(1) polymers (PF-1) comprising recurring units derived from at least one fluorinated monomer selected from tetrafluoroethylene (TFE) and
chlorotrifluoroethylene (CTFE), and from at least one hydrogenated monomer selected from ethylene, propylene and isobutylene, optionally containing one or more additional comonomers, typically in amounts of from 0.01 % to 30 % by moles, based on the total amount of TFE and/or CTFE and the hydrogenated monomer(s);
(2) polymers (PF-2) comprising recurring units derived from vinylidene fluoride (VDF), and, optionally, from one or more fluorinated monomers different from VDF;
(3) polymers (PF-3) comprising recurring units derived from tetrafluoroethylene (TFE) and at least one fluorinated monomer different from TFE selected from the group consisting of :
- perfluoroalkylvinylethers of formula CF2=CFORfi wherein Rn - is a Ci-C6 perfluoroalkyl group;
- perfluoro-oxyalkylvinylethers of formula CF2=CFOXo wherein Xo is a C1-C12 perfluorooxyalkyl group comprising one or more ether groups, such as perfluoro-2-propoxy-propyl group;
C3-C8 perfluoroolefms, such as hexafluoropropene (HFP); and
perfluorodioxoles of formula :
wherein Ri, R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a Ci-C6 fluoroalkyl group, optionally comprising one or more oxygen atoms, and a Ci-C6 fluoroalkoxy group, optionally comprising one or more oxygen atoms; and (4) polymers (PF-4) comprising recurring units derived from at least one cyclopolymerizable monomer of formula :
wherein each R7 to Ri6, independently of one another, is selected from -F and a C1-C3 fluoroalkyl group, a is 0 or 1, b is 0 or 1 with the proviso that b is 0 when a is 1.
Preferably, the fluoropolymer is polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE) or perfluoroalkoxy alkanes (PFA).
Fluoropolymers are commercially available from Solvay Specialty
Polymers Italy S.p.A under the trademark name HYFLON® PFA P and M series, HYFLON® MFA and HYFLON® AD.
Additive
The polymer composition (C) of the present invention also comprises an additive of formula (I) :
Ra - Ar - Xb (I)
where
- Ar is an aromatic moiety and is selected from the group consisting of substituted or unsubstituted, aromatic monocyclic or polycyclic group having 5 to 18 carbon atoms,
- each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8 cycloaliphatic group and a CI -CI 8 aromatic;
- a is zero or an integer ranging from 1 to 5, preferably a is zero or 1;
- X is (S03 ), (Mp+)i/p or (COO"), (Mp+)i/p in which Mp+ is a metal cation of p valence;
- b is an integer ranging from 1 to 4, preferably b is 1 or 2.
One of the essential features of the present invention is to use an additive in the form of a salt of sulfonic acid or carboxylic acid, more precisely a sulfonate -SO3" and/or a carboxylate -COO". The additive may comprise 1 to 4 groups X, identical or different, where X is (S03 "), (Mp+)i/p or (COO"), (Mp+)i/p in which Mp+ is a metal cation of p valence.
According to an embodiment, the additive of formula (I) is such that each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl and a C1-C3 aliphatic group (i.e. a methyl, an ethyl or a propyl).
According to an embodiment, M is selected from the group consisting of sodium, potassium, calcium, lithium, magnesium, silver, aluminium, zinc, nickel, copper, palladium, iron, and cesium. Preferably M is sodium or potassium.
M can alternatively be specifically chosen among alkali metals (IA of the periodic table) or alkaline earths metal (IIA of the periodic table).
According to an embodiment, X is a sodium and/or a potassium salt of sulfonic acid and/or carboxylic acid.
The additive used in the present invention is by nature water-soluble.
The additive may also be said to be extractable, as defined below.
According to one embodiment of the invention, the aromatic moiety of formula (I) can be selected from the group consisting of :
r-B)
-SO2-, -CO- and alkylenes of 1 to 6 carbon atoms. Z can in particular be
According to one embodiment of the invention, the additive of formula (I) is such that each aromatic moiety of formula (I), for example (Ar-A) to (Ar-D) comprises 1,2 or 3 groups X, identical or different, where X is (S03 ), (Mp+)i/p or (COO ), (Mp+)i/p in which Mp+ is a metal cation of p valence.
According to one embodiment of the invention, the additive of formula (I) is such that each aromatic moiety of formula (I) comprises 1 or 2 groups X, identical or different, where X is (S03 ), (Mp+)i/p or (COO"), (Mp+)i/p in which
Mp+ is a metal cation of p valence.
wherein :
- each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8
cycloaliphatic group and a CI -CI 8 aromatic;
- a is zero or an integer ranging from 1 to 5;
- X is (S03 ), (Mp+)i/p or (COO"), (Mp+)i/p in which Mp+ is a metal cation of p valence;
- b is each of either 1 or 2.
According to one further embodiment of the invention, the additive of formula (I) or (II) is such that a is 0, 1 or 2.
According to another embodiment, a is zero so that the phenylene moieties have no other substituents than the sulfonate or carboxylate functions.
According to another embodiment of the invention, the additive salt is benzoate, methylbenzoate, ethylbenzoate, propylbenzoate, benzene sulfonate, benzene disulfonate, p-toluene sulfonate, xylene sulfonate, cumene sulfonate, p-cymene sulfonate and dodecylbenzene sulfonate.
According to another embodiment of the invention, the additive is selected from the group consisting of sodium or potassium benzoate, sodium or potassium methyl benzoate, sodium or potassium ethylbenzoate, sodium or potassium butylbenzoate, sodium or potassium benzene sulfonate, sodium or potassium benzene- 1,3-disulfonate,
sodium or potassium p-toluene sulfonate, sodium or potassium xylenesulfonate, sodium or potassium cumene sulfonate, sodium or potassium /?ara-cymene sulfonate, sodium or potassium n-butyl benzene sulfonate, sodium or potassium iso-butyl benzene sulfonate, sodium or potassium tert-butyl benezene sulfonate and sodium or potassium dodecylbenzenesulfonate.
The additive is present in the composition of the invention in a quantity of at least 28 wt. %, based on the total weight of the composition.
According to another embodiment of the invention, the composition comprises between about 28 and about 80 wt. % of the additive, for example between about 30 and about 75 wt. % or between about 35 and about 70 wt. %.
According to an embodiment of the present invention, the additive has a melting temperature Tma (°C) of at least 150°C, for example of at least 170°C, at least 180°C, at least 190°C, or at least 200 °C, as for example measured by differential scanning calorimetry (DSC) according to ASTM D3418.
According to another embodiment of the invention, the composition is such that the polymer (P) is semi-cristalline and the additive has a melting temperature Tma (°C) such that
Tmp - 50 < Tma < Tmp + 50 (a)
wherein Tmp (°C) is the melting point of the semi-crystalline polymer, as for example measured by differential scanning calorimetry (DSC) according to ASTM D3418.
According to this embodiment, the components of the composition are chosen according to their respective melting temperatures (°C) so as to fulfil equation (a). Preferably, the components of the composition are chosen so as to fulfil any of the below equations (b) to (e) :
Tmp - 45 < Tma < Tmp + 45 (b),
Tmp - 40 < Tma < Tmp + 40 (c)
Tmp - 35 < Tma < Tmp + 35 (d)
Tmp - 30 < Tma < Tmp + 30 (e)
Melting temperature of the components can notably be measured using differential scanning calorimetry according to ASTM D3418.
According to an embodiment of the invention, the polymer composition (C) comprises:
- at least one semi-crystalline polymer (P) selected in the group consisting of PAEK and PPS, and
- at least 28 wt. %, by weight of the polymer composition (C), of at least one additive as described above, for example selected in the group consisting of sodium or potassium benzoate, sodium or potassium methyl benzoate, sodium or potassium ethylbenzoate, sodium or potassium butylbenzoate, sodium or potassium benzene sulfonate, sodium or potassium benzene- 1 ,3-disulfonate, sodium or potassium p- toluene sulfonate, sodium or potassium xylenesulfonate, sodium or potassium cumene sulfonate, sodium or potassium p-cymene sulfonate, sodium or potassium n- butyl benzene sulfonate, sodium or potassium iso-butyl benzene sulfonate, sodium or potassium tert-butyl benezene sulfonate and sodium or potassium
dodecylbenzenesulfonate, preferably sodium or potassium benzene sulfonate.
Optional Components
In some embodiments, the polymer composition (C) includes titanium dioxide (Ti02). The amount of titanium dioxide preferably ranges from 0 pph to about 25 pph, for example from about 0.1 pph to about 25 pph, for example from about 5 pph to about 20 pph. The amount of titanium dioxide (Ti02) may be at most about 25 pph, preferably at most about 20 pph, preferably at most about 20 pph, preferably at most about 15 pph.
The polymer composition (C) may further optionally comprise additional components such as ultraviolet light stabilizers, heat stabilizers, antioxidants, pigments, processing aids, lubricants, flame retardants, plasticizers and/or
conductivity additive such as carbon black and carbon nanofibrils.
The polymer composition (C) may further comprise water-soluble or dispersible polymer additives for benefit of processing and/or optimizing pore morphology and/or porosity. Examples of such polymers include : sulfo- polyesters, polyvinyl alcohol, polyethylene oxide, polyethylene oxide/propylene oxide copolymers, polyethylene imine, polyethyloxazoline, and
polyvinylpyrrolidone, Such polymer additive are chosen to remain stable at the desired processing temperature and remain substantially extractable from the final articles by water.
The polymer composition (C) may further comprise flame retardants such as halogen and halogen free flame retardants.
Articles (A) Comprising the Polymer Composition (C) and Applications
The polymer compositions (C) described herein can be used for the
manufacture of a wide variety of formed articles. The term "article" in the present context is thus to be understood broadly. It refers to any type of article of manufacture which can be formed from a polymeric material and covers (a)
the intermediate articles (or intermediate shaped articles), which are non-porous, and result directly from the step consisting in shaping the polymer composition of the invention into shaped articles, for example by injection molding, extrusion molding or 3D printing, and (b) the final articles (or final shaped articles), which are porous, and obtained from the intermediate articles which have, for example been immersed into water to dissolve the additive and create the pores. In this context, the additive is said to be water-soluble and/or extractable.
The polymer composition (C) may be used for thermal insulation or acoustic insulation, in variable shapes and sizes.
The polymer article (A) comprising the polymer composition (C) of the present invention may be used as a filter or as a membrane (e.g. microfiltration or ultrafiltration).
The article is preferably a membrane. Indeed, the polymer compositions described herein are very well suited for the production of membranes of this type. The term "membrane" is used herein in its usual meaning, that is to say it refers to a discrete, generally thin, interface that moderates the permeation of chemical species in contact with it. This interface may be molecularly homogeneous, that is, completely uniform in structure (dense membrane), or it may be chemically or physically heterogeneous, for example containing voids, holes or pores of finite dimensions (porous membrane). Membranes can be in the form of a flat sheet or in the form of tubes. Tubular membranes are classified based on their dimensions in tubular membranes having a diameter greater than 3 mm; capillary membranes, having a diameter comprised between 0.5 mm and 3 mm; and hollow fine fibers having a diameter of less than 0.5 mm. Flat sheet membranes are generally preferred when high fluxes are required whereas hollow fibers are particularly advantageous in applications where compact modules with high surface areas are required.
Porous membranes can be characterized by permeability measurements (volume of water which permeates through the membrane under given pressure conditions), porosity (ratio between the volume of voids and the total volume occupied by the membrane), pores features (average pore diameter, smallest pore diameter and largest pore diameter). They can also be characterized by their mechanical properties (tensile properties notably) and chemical resistance (after immersion in various solvents during a given amount of time).
The articles may be used singularly or in bundle arrays and form, for example, filter systems. The articles may be, for example, microfiltration
membranes, ultrafiltration membranes or support for reverse osmosis.
These articles can be used in the separation of various materials. The potential utility of such a membrane article depends upon the membrane material, its structure (which depends upon its method of preparation), and the mode in which it is operated. For example, such articles can be used to permeate gases, e.g. oxygen or nitrogen, to separate solutes of suspended matter from solutions, e.g. soluble waste materials from blood (hemodialysis) or to separate dissolved molecules, colloids, and suspended solids from smaller molecules, e.g., in the manufacture of latex or cheese (ultrafiltration).
The inventors have shown that the porous membranes of the present invention present an improved porous structure.
Accordingly, the present invention also concerns the method of using the final shaped articles, for example porous membrane in filtration and purification processes, such as filtration of waste water, preparation of ultrapure water and in medical, pharmaceutical or food applications, including removal of
microorganisms, dialyses and protein filtration.
In other words, the present invention concerns the use of the shaped articles for filtering or purifying liquids, such as filtering waste water, for preparing ultrapure water and in medical, pharmaceutical or food applications, including removal of microorganisms, dialyses and protein filtration.
The porosity of the membrane may range from 3 to 90 %, preferably from 5 to 80 % or from 20 to 70 %. For example, the membrane has a porosity of about 50 %, or about 60 %.
The pores may have an average diameter of at least 0.001 μιη, of at least 0.005 μιη, of at least 0.01 μιη, of at least 0.1 μιη, of at least 1 μιη, of at least 10 μιη and of at most 50 μιη.
According to an embodiment, the porous polymer article, for example membrane, is used for filtering or purifying fluids, such as liquids or gas.
According to another embodiment, the porous polymer article, for example membrane, is used as a separator in batteries, such as Li-ion batteries.
According to another embodiment, the porous polymer article, for example membrane, is used for as a diaphragm for electrolizer for the production of dihydrogen.
According to another embodiment, the porous polymer article, for example porous membrane according to the present invention, can be used for filtrating biologic solution (e.g. bioburden, virus, other large molecules) and/or buffer
solutions (e.g. solutions that may contain small amount of solvents like DMSO or other polar aprotic solvents).
According to another embodiment of the present invention, the polymer composition (C) is used as a support material in processes for manufacturing a three-dimensional object with an extrusion-based additive manufacturing system, otherwise known also as fused filament fabrication technique. The polymer composition (C) used as support material in these 3D manufacturing methods is provided under the form of a filament. The filament may have a cylindrical or substantially cylindrical geometry, or may have a non-cylindrical geometry, such as a ribbon filament geometry; further, filament may have a hollow geometry, or may have a core-shell geometry, with the support material of the present invention being used to form either the core or the shell.
Method of Manufacturing the Polymer Compositions (C), Articles (A) and Porous articles
The present invention also relates to the method of making the polymer composition (C) as described above, the method comprising melt-mixing the semi-crystalline or amorphous polymer (P) and the additive.
More precisely, the polymer composition (C) can be manufactured by melt-mixing the at least one semi-crystalline or amorphous polymer (P), with at least 28 wt. %, by weight of the polymer composition, of the at least one additive of formula (I):
F - Ar - Xb (I)
where
- Ar is an aromatic moiety and is selected from the group consisting of substituted or unsubstituted, aromatic monocyclic or polycyclic group having 5 to 18 carbon atoms,
- each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8 cycloaliphatic group and a CI -CI 8 aromatic;
- a is zero or an integer ranging from 1 to 5;
- X is (S03 ~), (Mp+)i/p or (COO"), (Mp+)i/p in which Mp+ is a metal cation of p valence;
- b is an integer ranging from 1 to 4.
to provide a molten mixture.
The polymer compositions (C) described herein are advantageously provided in the form of pellets, which may be used in injection molding or extrusion processes known in the art.
The polymer composition (C) can be made by methods well known to the person of ordinary skill in the art. For example, such methods include, but are not limited to, melt-mixing processes. Melt-mixing processes are typically carried out by heating the thermoplastic polymer above the melting temperature of the thermoplastic polymer thereby forming a melt of the thermoplastic polymer. Such a process may be carried out by heating the polymers above the melting temperature (Tm) of the semi- crystalline polymer to form a melt of the polymers and/or above the glass transition temperature (Tg) of the amorphous polymer. In some embodiments, the processing temperature ranges from about 180-450°C, preferably from about 220-440°C, from about 260-430°C or from about 280-420°C. Preferably, the processing temperature is at least 15°C, preferably at least 30°C, at least 50°C, at least 80°C or at least 100°C greater than the melting temperature (Tg) of the semi-crystalline polymer (or of the highest polymer Tm in the polymer composition if the composition comprises several semi-crystalline polymers). Preferably, the processing temperature is at least 15°C, preferably at least 30°C or at least 50°C greater than the glass transition temperature (Tg) of the amorphous polymer (or of the highest polymer Tg in the polymer composition if the composition comprises several amorphous polymers). In case of a blend of an amorphous polymer and a semi-crystalline polymer, the melt-mixing process is carried out a temperature which the highest of the Tm or the Tg temperatures.
The additive used in the context of the present invention is preferably in the form of a powder.
The process for the preparation of the composition can be carried out in a melt-mixing apparatus, for which any melt-mixing apparatus known to the one skilled in the art of preparing polymer compositions by melt mixing can be used. Suitable melt-mixing apparatus are, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders. Preferably, use is made of an extruder fitted with means for dosing all the desired components to the extruder, either to the extruder's throat or to the melt. In the process for the preparation of the polymer composition the constituting components for forming the composition are fed to the melt-mixing apparatus and melt-mixed in that
apparatus. The constituting components may be fed simultaneously as a powder mixture or granule mixer, also known as dry-blend, or may be fed separately.
The order of combining the components during melt-mixing is not particularly limited. In one embodiment, the components can be mixed in a single batch, such that the desired amounts of each component are added together and subsequently mixed. In other embodiments, a first sub-set of components can be initially mixed together and one or more of the remaining components can be added to the mixture for further mixing. For clarity, the total desired amount of each component does not have to be mixed as a single quantity. For example, for one or more of the components, a partial quantity can be initially added and mixed and, subsequently, some or all of the remainder can be added and mixed.
The method of manufacturing the polymer composition (C) may comprise if needed several successive steps of melt-mixing or extrusion under different conditions.
The process itself, or each step of the process if relevant, may also comprise a step consisting in a cooling of the molten mixture.
The intermediate non-porous article (e.g. the shaped non-porous membrane or the shaped porous film) and the final porous article (e.g. the porous membrane or the porous film) according to the present invention are made from the polymer composition (C) using any suitable melt-processing method. In particular, they are made by injection molding, extrusion molding or 3D printing.
For this purpose, any standard molding technique can be used; standard techniques including shaping the polymer compositions in a molten/softened form can be advantageously applied, and include notably compression molding, extrusion molding, injection molding, transfer molding and the like. Dies may be used to shape the articles, for example a die having an annular orifice if the article is a hollow fiber membrane.
According to an embodiment of the present invention, the method of forming the polymer articles (intermediate non porous ones or final porous ones) comprises a step consisting in printing layers of a three-dimensional object from the provided polymer composition (C). According to this embodiment, the polymer article is in fact formed with an extrusion-based additive manufacturing system, otherwise known also as fused filament fabrication technique.
According to an embodiment of the present invention, the method of forming the polymer articles (intermediate non porous ones or final porous ones)
comprises at least the step consisting in extruding the polymer composition (C) above described.
According to an embodiment of the present invention, the method of forming the porous polymer articles (e.g. porous membrane or porous hollow fiber) comprises additionally the step consisting in contacting the intermediate non porous article with water, for example by immersion into water or in a solution containing water. The water used to dissolve the water-soluble additive can be at a temperature varying for example between room temperature and 95°C. The time period needed to dissolve the polymer is variable. As an example, the time period can vary between 1 second and 2 hours, or from 5 seconds to 1 hour.
According to this embodiment, the additive can be said to be extractable, that-is-to-say able to be substantially extracted from the intermediate product by contact with water, for example immersion into water, the water being possibly heated up to 95°C, for a period of time up to 2 hours. "Substantially" in this context means that at least 80 wt. % of the additive is extracted from the intermediate product, for example at least 85 wt. %, at least 90 wt. % or at least 95 wt. %, so as to obtained the final shaped porous article.
Accordingly the present invention also concerns a method of forming a porous polymer membrane M), comprising:
(i) preparing a polymer composition (C) as described above,
(ii) processing the polymer composition (C) into a membrane, for example extruding the polymer composition (C) into a flat membrane,
(iii) immersing the membrane into water.
The method of forming a porous polymer membrane (M) can comprise one or several optional steps. One optional step consists in stretching the membrane.
This optional step can notably take place during step (iii). Another optional step consists in drying the membrane, for example in an oven.
The present invention is also directed to the porous polymer article (e.g. membrane or hollow tube) obtainable by this method.
The porous polymer article may contain up to 20 wt. % of the additive, for example up to 15 wt. % of the additive, up to 10 wt. % of the additive, up to
5 wt. % of the additive or less. According to an embodiment, it contains less than 1 wt. % of the additive.
The articles according to the present invention may be coated or further treated.
Hence, the method, as above detailed, may additionally comprise at least one additional step comprising coating at least one metal onto at least a part of the surface of the said part.
Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
The invention will be herein after illustrated in greater detail in the following section by means of non-limiting examples.
EXAMPLES
Two working examples and three corresponding comparative examples are provided. All the compositions prepared and evaluated are shown below in Table 3.
Raw materials
1 ) PPS polymer : Ryton® QC 160N from Solvay Specialty Polymers USA, LLC .
2) PEEK polymer : KetaSpire® KT-880P from Solvay Specialty Polymers USA, LLC. This grade has a melt viscosity in the range 120-180 Pa-s as measured at 400 °C and 1000 1/s according to ASTM D-3835;
3) Sodium benzenesulfonate, RIA International (NaBzS)
4) Sodium acetate, Fisher Scientific (NaAc)
Melting temperature of the components
Melting temperatures (Tm) of the various components were measured using differential scanning calorimetry according to ASTM D3418 employing a heating and cooling rate of 20 °C/min. Three scans were used for each DSC test : a first heat up to 400 °C, followed by a first cool down to 50 °C, followed by a second heat up to 400 °C. The Tm was determined from the second heat up as the peak temperature on the melting endotherm. The melting temperatures for the four components used in the examples and comparative examples are tabulated in Table 1.
Table 1
Procedure for the preparation of the membranes
Three different polymer compositions were tested :
Membrane #1 : Blend PEEK/ NaBzS 60/40
Membrane #2 : Blend PPS/NaBzS 50/50
Comparative membrane #1 : Blend PPS/NaAc 50/50
The following process took place for membrane #1 and membrane #2 :
Selected polymer and additives were pre-dried in oven to eliminate moisture. The combined constituents were added to an Eries Magnetics FT-26 vibratory feeder and fed directly into a Leistritz Micl8Gl/30D twin screw co- rotating compounder with screw speed set to 200 rpm and barrel settings adjusted such that the melt temperature was about 320°C for PPS and 380°C for PEEK. The material was then cooled into strands and pelletized.
The pellets were then fed into a gravity hopper mounted to a DSM Xplore MCI 5 compounder with 15mL barrel capacity and 1" width film die. The barrel temperatures were adjusted such that the melt temperature was > 320°C for PPS, and 380°C for PEEK with screw speed set to force control. Membranes were collected on a DSM Xplore film winder with roll settings (speed, torque) adjusted to target a 100-200 μιη thickness.
For comparative membrane #1, the compounding step led to a phase separation of the components and extruding continuous strands for making pellets was not possible.
Aqueous extraction of additive after shaping
The membrane #2 was dried in vacuum and weighed. The membrane was then immersed in an excess of hot water (about 90°C) for 2 hours. The membrane was then dried in vacuum and re-weighed to determine extraction efficiency.
Table 2
These results show that more than 99 % of the additive has been dissolved during the step of immersion into the hot water, thereby creating pores into the membrane.
Permeability measurements
Water flux (J expressed in l/(m2xh)) through each membrane at given pressure, is defined as the volume which permeates per unit area and per unit time. The water flux is calculated by the following equation :
J = V
A At
wherein :
- J (l/(m2xh)) is the water flux,
- V (1) is the volume of permeate,
- A (m2) is the membrane area, and
- At (h) is the operation time.
Water flux measurements were conducted at room temperature using a dead-end configuration under a constant nitrogen pressure of 1 bar. Membrane discs with an effective area of 11.3 cm2 were cut from the items stored in water and placed on a metal plate. For each material, flux is the average of at least five different discs.
Porosity
Membrane porosity (£m) was determined according to the gravimetric method. Porosity is defined as the ratio between the volume of voids and the total volume occupied by the membrane. Perfectly dry membrane pieces were weighed and impregnated in isopropylic alcohol (IP A) for 24h; after this time, the excess of the liquid was removed with tissue paper, and membranes weight was measured again. Finally, from the dry and the wet weight of the sample, it is possible to evaluate the porosity of the membrane using the following formula :
(Ww - Wd)/pw
£m ww - wd | wd
Pw Pp
wherein :
- Ww is the weight of the wet membrane,
- Wd is the weight of the dry membrane,
- pw is the IP A density (0.785) and
- pp is the polymer density (1.35 for PPS and 1.3 for PEEK).
For all membranes types, at least three measurements were performed; then, average values and corresponding standard deviations were calculated.
Bubble point and pore size determination
Membranes bubble points, smallest pore size and pore size distribution were determined following ASTM F316 method, using a capillary flow porometer Porolux™ 1000 (Porometer-Belgium). For each test, membranes samples were initially fully wetted using Fluorinert® FC 43 (fluorinated fluid with a surface tension of 16 dyn/cm). Nitrogen (inert gas) was used.
Results are presented in Table 3 below.
Table 3
* Sm. P : smallest pore
** Av. P : average pore
The porous membranes #1 and #2 present good mechanical properties
(tensile properties according to ASTM D-638) and good chemical resistance (results not shown).
Claims
1. A polymer composition (C) comprising:
- at least one polymer (P) selected from the group consisting of a poly(aryl ether ketone) (PAEK), a poly(aryl ether sulfone) (PAES), a polyarylene sulfide (PAS), a polyetherimide (PEI), a poly(phenyl ether) (PPE), a polycarbonate (PC), a polyamide (PA), a polyphenylene (PP) and a fluoropolymer, and
- at least 28 wt. %, based on the total weight of the polymer composition (C), of at least one additive of formula (I):
Ra - Ar - Xb (I) where
- Ar is an aromatic moiety and is selected from the group consisting of substituted or unsubstituted, aromatic monocyclic or polycyclic group having 5 to 18 carbon atoms,
- each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8 cycloaliphatic group and a CI -CI 8 aromatic;
- a is zero or an integer ranging from 1 to 5;
- X is (S03 ~), (Mp+)i/p or (COO"), (Mp+)i/p in which Mp+ is a metal cation of p valence;
- b is an integer ranging from 1 to 4.
2. The polymer composition of claim 1, wherein the additive of formula (I) such that each of R, identical or different from each other, is selected from e group consisting of a halogen, an hydroxyl and a C1-C3 aliphatic group.
3. The polymer composition (C) of any one of claims 1 and 2, wherein Ar in formula (I) is selected from the group consisting of:
4. The polymer composition (C) of any one of claims 1 to 3, wherein the additive is such that a is 0, 1 or 2.
5. The polymer composition (C) of any one of claims 1 to 4, wherein the additive has a melting point Tma (°C) of at least 150°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
6. The polymer composition (C) of any one of claims 1 to 5, wherein the polymer (P) is semi-crystalline and the additive has a melting point Tma (°C) such that
Tmp - 50 < Tma < Tmp + 50 wherein Tmp (°C) is the melting point of the semi-crystalline polymer, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
7. The polymer composition (C) of any one of claims 1 to 6, wherein the additive is according to formula (II):
where
- each of R, identical or different from each other, is selected from the group consisting of a halogen, an hydroxyl, a CI -CI 8 aliphatic group, a CI -CI 8 cycloaliphatic group and a CI -CI 8 aromatic;
- a is zero or an integer ranging from 1 to 5;
- X is (S03 ~), (Mp+)i/p or (COO"), (Mp+)i/p in which Mp+ is a metal cation of p valence;
- b is each of either 1 or 2.
8. The polymer composition (C) of any one of claims 1 to 7, wherein the additive salt is selected from the group consisting of benzoate, methylbenzoate, ethylbenzoate, propylbenzoate, benzene sulfonate, benzene disulfonate, p-toluene sulfonate, xylene sulfonate, cumene sulfonate, p-cymene sulfonate and dodecylbenzene sulfonate.
9. The polymer composition (C) of any one of claims 1 to 8, comprising between 30 wt. % and 70 wt. % of the additive.
10. A polymer article (A) comprising the polymer composition (C) of any one of claims 1 to 9.
11. A method of forming a porous polymer membrane (M), comprising:
(i) preparing a polymer composition (C) according to any one of claims 1 to 9,
(ii) processing the polymer composition (C) into a membrane,
(iii) immersing the membrane into water.
12. A porous polymer membrane (M) obtainable by the process of claim
11.
13. Use of the porous polymer membrane (M) of claim 12 for filtering or purifying fluids, such as liquids or gas.
14. Use of the porous polymer membrane (M) of claim 12 as a separator in batteries, such as Li-ion batteries.
15. Use of the porous polymer membrane (M) of claim 12 as a diaphragm for electrolizer for the production of dihydrogen.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201780061901.3A CN109843997B (en) | 2016-10-06 | 2017-10-05 | Porous article comprising a polymer and an additive, method for the production thereof and use thereof |
US16/339,550 US20190241712A1 (en) | 2016-10-06 | 2017-10-05 | Porous article comprising a polymer and an additive, processes for their preparation and use thereof |
EP17786862.7A EP3523365B1 (en) | 2016-10-06 | 2017-10-05 | Porous article comprising a polymer and an additive, processes for their preparation and use thereof |
JP2019517414A JP7208893B2 (en) | 2016-10-06 | 2017-10-05 | Porous Articles Containing Polymers and Additives, Their Preparation and Their Use |
EP21162506.6A EP3872123A1 (en) | 2016-10-06 | 2017-10-05 | Porous article comprising a polymer and an additive, processes for their preparation and use thereof |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662404934P | 2016-10-06 | 2016-10-06 | |
US62/404,934 | 2016-10-06 | ||
EP17153832.5 | 2017-01-30 | ||
EP17153832 | 2017-01-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018065526A1 true WO2018065526A1 (en) | 2018-04-12 |
Family
ID=58016542
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2017/075370 WO2018065526A1 (en) | 2016-10-06 | 2017-10-05 | Porous article comprising a polymer and an additive, processes for their preparation and use thereof |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2018065526A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020127454A1 (en) | 2018-12-20 | 2020-06-25 | Solvay Specialty Polymers Usa, Llc | Porous membranes for high pressure filtration |
WO2021018868A1 (en) | 2019-07-30 | 2021-02-04 | Solvay Specialty Polymers Usa, Llc | Membrane comprising a blend of polyarylethersulfone and polyaryletherketone and method for manufacturing thereof |
WO2021048286A1 (en) | 2019-09-10 | 2021-03-18 | Solvay Specialty Polymers Usa, Llc | Porous articles, processes for their preparation and uses thereof |
CN112993488A (en) * | 2021-02-08 | 2021-06-18 | 哈尔滨工业大学 | Lithium ion battery diaphragm material and preparation method thereof |
JP2022515734A (en) * | 2018-12-20 | 2022-02-22 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | Porous membrane for high pressure filtration |
WO2022096373A1 (en) * | 2020-11-04 | 2022-05-12 | Solvay Specialty Polymers Usa, Llc | Microporous articles and corresponding formation methods |
DE102020130603A1 (en) | 2020-11-19 | 2022-05-19 | Audi Aktiengesellschaft | Process for producing a membrane for a humidifier and for producing a humidifier |
WO2022122769A1 (en) | 2020-12-07 | 2022-06-16 | Solvay Specialty Polymers Usa, Llc | Polymer composition and method for manufacturing membranes therefrom |
WO2024068332A1 (en) | 2022-09-29 | 2024-04-04 | Solvay Specialty Polymers Usa, Llc | Membrane for alkaline water electrolysis |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB920229A (en) | 1960-02-10 | 1963-03-06 | Standard Telephones Cables Ltd | Improvements in bistable circuits employing negative resistance devices |
GB980229A (en) * | 1961-12-20 | 1965-01-13 | Gen Electric | Production of microporous hydrocarbon polymers |
US3956020A (en) * | 1968-10-31 | 1976-05-11 | General Electric Company | Ultrafine porous polymer articles |
US4196070A (en) * | 1977-12-12 | 1980-04-01 | Nuclepore Corporation | Method for forming microporous fluorocarbon polymer sheet and product |
US5064580A (en) | 1988-03-31 | 1991-11-12 | The Dow Chemical Company | Process for making microporous membranes from poly(etheretherketone)-type polymers |
US6887408B2 (en) | 2003-05-05 | 2005-05-03 | Porogen Llc | Porous poly(aryl ether ketone) membranes, processes for their preparation and use thereof |
EP1746125A1 (en) * | 2004-04-23 | 2007-01-24 | Ntn Corporation | Porous resin article and method for production thereof |
US20070232502A1 (en) * | 2004-06-10 | 2007-10-04 | Hideyuki Tsutsui | Sliding Material and Sliding Bearing |
-
2017
- 2017-10-05 WO PCT/EP2017/075370 patent/WO2018065526A1/en unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB920229A (en) | 1960-02-10 | 1963-03-06 | Standard Telephones Cables Ltd | Improvements in bistable circuits employing negative resistance devices |
GB980229A (en) * | 1961-12-20 | 1965-01-13 | Gen Electric | Production of microporous hydrocarbon polymers |
US3956020A (en) * | 1968-10-31 | 1976-05-11 | General Electric Company | Ultrafine porous polymer articles |
US4196070A (en) * | 1977-12-12 | 1980-04-01 | Nuclepore Corporation | Method for forming microporous fluorocarbon polymer sheet and product |
US5064580A (en) | 1988-03-31 | 1991-11-12 | The Dow Chemical Company | Process for making microporous membranes from poly(etheretherketone)-type polymers |
US6887408B2 (en) | 2003-05-05 | 2005-05-03 | Porogen Llc | Porous poly(aryl ether ketone) membranes, processes for their preparation and use thereof |
EP1746125A1 (en) * | 2004-04-23 | 2007-01-24 | Ntn Corporation | Porous resin article and method for production thereof |
US20070232502A1 (en) * | 2004-06-10 | 2007-10-04 | Hideyuki Tsutsui | Sliding Material and Sliding Bearing |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7511558B2 (en) | 2018-12-20 | 2024-07-05 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | Porous membranes for high pressure filtration |
US12064731B2 (en) | 2018-12-20 | 2024-08-20 | Solvay Specialty Polymers Usa, Llc | Porous membranes for high pressure filtration |
CN113195082A (en) * | 2018-12-20 | 2021-07-30 | 索尔维特殊聚合物美国有限责任公司 | Porous membranes for high pressure filtration |
JP2022514036A (en) * | 2018-12-20 | 2022-02-09 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | Porous membrane for high pressure filtration |
JP2022515734A (en) * | 2018-12-20 | 2022-02-22 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | Porous membrane for high pressure filtration |
WO2020127454A1 (en) | 2018-12-20 | 2020-06-25 | Solvay Specialty Polymers Usa, Llc | Porous membranes for high pressure filtration |
JP7516382B2 (en) | 2018-12-20 | 2024-07-16 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | Porous membranes for high pressure filtration |
WO2021018868A1 (en) | 2019-07-30 | 2021-02-04 | Solvay Specialty Polymers Usa, Llc | Membrane comprising a blend of polyarylethersulfone and polyaryletherketone and method for manufacturing thereof |
WO2021048286A1 (en) | 2019-09-10 | 2021-03-18 | Solvay Specialty Polymers Usa, Llc | Porous articles, processes for their preparation and uses thereof |
WO2022096373A1 (en) * | 2020-11-04 | 2022-05-12 | Solvay Specialty Polymers Usa, Llc | Microporous articles and corresponding formation methods |
DE102020130603A1 (en) | 2020-11-19 | 2022-05-19 | Audi Aktiengesellschaft | Process for producing a membrane for a humidifier and for producing a humidifier |
WO2022122769A1 (en) | 2020-12-07 | 2022-06-16 | Solvay Specialty Polymers Usa, Llc | Polymer composition and method for manufacturing membranes therefrom |
CN112993488A (en) * | 2021-02-08 | 2021-06-18 | 哈尔滨工业大学 | Lithium ion battery diaphragm material and preparation method thereof |
WO2024068332A1 (en) | 2022-09-29 | 2024-04-04 | Solvay Specialty Polymers Usa, Llc | Membrane for alkaline water electrolysis |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018065526A1 (en) | Porous article comprising a polymer and an additive, processes for their preparation and use thereof | |
EP3523365A1 (en) | Porous article comprising a polymer and an additive, processes for their preparation and use thereof | |
Peyravi et al. | Thin film composite membranes with modified polysulfone supports for organic solvent nanofiltration | |
JP6211059B2 (en) | Ultrafiltration membranes made from sulfonated polyphenylene sulfone | |
KR102626465B1 (en) | Method for preparing membranes using lactamide based solvents | |
KR20150036007A (en) | Composite membranes comprising a sulfonated polyphenylenesulfone and their use in forward osmosis processes | |
Gao et al. | Phenolphthalein‐based cardo poly (arylene ether sulfone): Preparation and application to separation membranes | |
CN109641182B (en) | Multilayer hollow fiber membrane | |
Aristizábal et al. | Solvent and thermally stable polymeric membranes for liquid molecular separations: Recent advances, challenges, and perspectives | |
US20130206694A1 (en) | Membrane for water purification | |
KR102573508B1 (en) | Gas separation membrane, gas separation membrane element, and gas separation method | |
Mashhadikhan et al. | Breaking temperature barrier: Highly thermally heat resistant polymeric membranes for sustainable water and wastewater treatment | |
WO2019016179A1 (en) | Membranes comprising fluorinated polymers and use thereof | |
US8752714B2 (en) | Sulfonated poly (aryl ether) membrane including blend with phenyl amine compound | |
KR102309225B1 (en) | Composite semi-permeable membrane | |
JP7511558B2 (en) | Porous membranes for high pressure filtration | |
US20220267587A1 (en) | Membrane comprising a blend of polyarylethersulfone and polyaryletherketone and method for manufacturing thereof | |
CN114364726A (en) | Porous article, method for its preparation and use thereof | |
CA2081260A1 (en) | Semipermeable, porous, asymmetric polyether amide membranes | |
EP3431170A1 (en) | Membranes comprising fluorinated polymers and use thereof | |
JP6937502B2 (en) | Porous Composite Film and Method for Producing Porous Composite Film | |
JPH054031A (en) | Hydrophilic separation membrane | |
KR20240102144A (en) | Porous membrane by blending perfluoroalkoxy alkane (pfa) and inorganic material, and manufacturing method thereof | |
CN116761667A (en) | Polymer composition and method for producing film therefrom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17786862 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019517414 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2017786862 Country of ref document: EP Effective date: 20190506 |