CA2061990A1 - Porous semipermeable membrane resistant to chemicals and heat - Google Patents
Porous semipermeable membrane resistant to chemicals and heatInfo
- Publication number
- CA2061990A1 CA2061990A1 CA002061990A CA2061990A CA2061990A1 CA 2061990 A1 CA2061990 A1 CA 2061990A1 CA 002061990 A CA002061990 A CA 002061990A CA 2061990 A CA2061990 A CA 2061990A CA 2061990 A1 CA2061990 A1 CA 2061990A1
- Authority
- CA
- Canada
- Prior art keywords
- semipermeable membrane
- formula
- semipermeable
- membrane
- carrier material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 239000000126 substance Substances 0.000 title abstract description 8
- 229920001643 poly(ether ketone) Polymers 0.000 claims abstract description 26
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 24
- 239000012876 carrier material Substances 0.000 claims abstract description 22
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 14
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000002759 woven fabric Substances 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001471 micro-filtration Methods 0.000 claims abstract description 3
- 238000001728 nano-filtration Methods 0.000 claims abstract description 3
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000007872 degassing Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 210000004379 membrane Anatomy 0.000 description 55
- 239000007788 liquid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 description 1
- HGUYBLVGLMAUFF-UHFFFAOYSA-N 2-methoxybenzene-1,4-diamine Chemical compound COC1=CC(N)=CC=C1N HGUYBLVGLMAUFF-UHFFFAOYSA-N 0.000 description 1
- ZAMLGGRVTAXBHI-UHFFFAOYSA-N 3-(4-bromophenyl)-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(CC(O)=O)C1=CC=C(Br)C=C1 ZAMLGGRVTAXBHI-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- PDSULNVJASBMLP-UHFFFAOYSA-N furan-2,5-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)O1 PDSULNVJASBMLP-UHFFFAOYSA-N 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
-
- 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
- B01D71/5223—Polyphenylene oxide, phenyl ether polymers or polyphenylethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Abstract of the disclosure: HOE 91/F 064 Porous semipermeable membrane resistant to chemicals and heat A semipermeable membrane for micro-, nano- and ultra-filtration, comprising a carrier material and a semi-permeable layer adhering to this. The carrier material is a woven fabric or a non-woven based on a polyphenylene sulfide, a polyether ketone or a polyaramid. To produce the semipermeable membrane, the polymers are first dissolved in a solvent and the solution is filtered and degassed. In a subsequent step, a membrane is produced by the phase inversion process, H2SO4, CF3-SO3H, HF, Cl2HC-COOH or a mixture of Cl2HC-COOH and H2SO4 being employed as the solvent for polyether ketones and N-methylpyrrolidone, dimethylacetamide or dimethyl-formamide being employed as the solvent for polyaramids.
Description
~J ~
HOECH5T AKTIENGESELLSCHAFT HOE 91/F 064 DCh.SY/sch Description Porous semipermeable membrane resistant to chemicals and heat Since the introduction of asymmetric membranes of cellu-lose acetate by Loeb and Sourira~an (S. Sourira~an, Reverse Osmosis, Logos Press, London 1970) and of hydro-phobic polymers ~US-A-3,615,024), numerous membranes have been developed and proposed, in particular for separa-tions of low- and high- molecular-weight constituents dissolved in water, the structure and suitability of which are described in the literature (Desalination, 35 (1980), 5-20) and which have also been tested success-fully in industrial practice or for medical purposes.
Many of the membranes described have particularly advan-tageous properties for achieving specific ob~ects. As a result of their chemical and physical structure, the individual membranes can in each case have the optimum suitability only for quite specific separation problems.
This results in the fundamental re~uirement of the constant development of new membrane~ for new tasks.
An overview of the advantages and disadvantages of membranes which are already known is given in EP-A-0,082,433. There are thus, for example, hydrophilic, asymmetric membranes of cellulose acetate which have satisfactory anti-adsorptive properties but leave a great deal to be desired in recpect of their resistance to heat and chemicals. Although membranes of polysulfones or similar polymers have a ~ood resistance to heat and chemicals, they are sensitive to the action of organic solvents.
Hydrophilicity and a sLmultaneous resistance to solvents are found in membranes of regenerated cellulose, however, these can be hydrolyzed relatively easily in acid or alkaline media, and they are moreover rapidly attacked by microorganisms.
DE-A-3,321,860 describes chemically resistant membranes of partly sulfonated polyether ketone. Although these me~branes are not dissolved under the action of organic solvents~ such as acetone or tetrahydrofuran (THF), they swell severely and thereby change their membranes proper-ties irreversibly.
The membranes are absorbed onto woven fabrics or non-wovens in order to achieve an increased mechanical stabilization. The carrier materials generally used comprise polypropylene or polyethylene terephthalate.
Nevertheless, such carrier mem~ranes have the disad-vantage that, for example, the service temperatures are reduced considerably because of the inadeguate heat stability of the non-wovens or the woven fabrics. The action of organic solvents, acids and alkalis furthermore leads to the dissolution o. these carrier materials or to the detachment of the membrane.
~he invention i6 therefore based on the ob~ect of provid-ing semipermeable membranes which have a high stability, are resistant both to hydrolyzing agents and to oxidizing agents, have a high heat stability and are not attacked by organic solvents, even at elevated temperatures.
The object is achieved by a semipermeable membrane consisting of a carrier material and a layer adhering to this, the carrier material being a woven fabric or a non-woven based on a polyphenylene 6ulfide, a polyether ketone or a polyaramid. ~he membranes described here are particularly suitable for micro-, nano- and ultra-filtration.
In the membranes according to the invention, the semi-permeable layer on the carrier material can comprise either a polyether ketone or a polyaramid.
L t~
The semipermeable layer and if appropriate also the carrier layer i8 derived from a polyether ketone having the recurring units of the formula (Ia) ~ O ~ C ~ (Ia) in particular from a polyether ketone ha~ing the recur-ring units of the formula (Ib) ~ O ~ C ~ l~ ~ O A ~ (Ib) in which -A- is a radical ~ or ~ z in which R1, RZ, R3 and R4 can be identical or different and are hydrogen, a (Cl-C4)-alkyl, (C6-C14)-aryl or (C6-Cl4)-hydroxyaryl group or NO2, CN, NR52 (R5 = (Cl-C6)-alkyl) or halogen and -Z- is one of the groupings -O-,-S-,-CH2-,-CF2.,-C-, -C-, -SO2r or -CO-~he preparation of polyether ketones, for example by nucleophilic aromatic polycondensation, iR known and is described in EP-A-0,001,879 and GB-A-1,414,421. Polyether ketones such as are used for the membranes according to the invention are described, for example, in DE-A-3,936,997, which is of earlier priority and i5 not a prior publication.
In a further preferred embodiment, the semipermeable layer and if appropriate the carrier material comprises an aromatic homo- or copolyamide having at least one of the recurring structural unit~ of the formula (II) O O
-(C-E'-C-NH-E2-NH)- (II) in which -E1- and -E2- are identical or different and are selected from one or more of the grouping6 ~NH CO~
-Arl- or --A~ l--X--Ar2 in which -Arl- and -Ar2- are identical or different 1,2-phenylene, 1,3-phenylene, 1,4-phenylene radicals or (C6-C~4)-arylene radicals, which can be substituted by one or more (cl-c6)-alkyl~ (C~-C6)-alkoxy or CF3 groups or halogen, in particular fluorine, chlorine or bromine atoms, or are a heteroaromatic radical, for example a ~2,5]- or [3,4]-furano radical, and the radical -X-a) is a direct bond or i8 one of the following divalent radicals -O-, -C(CF3) 2- ~ -S2- ~ -CO- or -C(R6) 2- ~ in which R6 is hydrogen or a (Cl-C6)-alkyl or (C~-C4)-fluoroalkyl group, or b) is -Y-Arl-Y-, in which -Y- is the radical -O- or -C(CH3)2-~or c) is -O-Arl-Q-ArZ-0-, in which -Q- has the meaning given under Xa).
The pxeparation of the polyaramids which are suitable as carrier materials and as layer materials for ~he mem-branes according to the invention is described in DE-A-3,903,098 and DE-A-3,802,030.
Examples of suitable starting materials for their prepa-ration are a) dicarboxylic acid dichlorides of the formula (IV) Cl-C0-E2-C0-Cl (IV) in which El has the abovementioned meaning.
Examples of ~ompounds of the formula (IV~ are 4,4'-di-phenyl sulfone-dicarboxylic acid dichloride, 4,4'-diphenyl ether-dicarboxylic acid dichloride, 4,4'-di-phenyldicarboxylic acid dichloride, 2,6-naphthalene-dicarboxylic acid dichlGride, isophthalic acid dichloride and 2,5-furandicarboxylic acid dichloride, but in par-ticular terephthalic acid dichloride and substitutedt.erephthalic acid dichloride, for example 2-chlorotere-phthalic acid dichloride;
b) aromatized diamines of the formula (V) H2I~-E2--NH2 ~V) for example m-phenylenediamine or substituted phenylene-diamines, for example 2-chloro-, 2,5-dichloro- or 2-meth-oxy-p-phenylenediamine, in particular p-phenylenediamine, and substituted benzidine derivatives, for example 4,4'-di-aminobenzophenone, bis-[4-aminophenyl] sulfone, bis-[4-(4'-aminophenoxy)phenyl3 sulfone, 1,2-bis-[4'-aminophen-oxy]benzene, 1,4-bis-~(4~-aminophenyl)isopropyl]benzene and 2,2'-bis-t4-(4'-aminophenoxy~phenyl]propane, in par-ticular 1,4-bis-(4'-aminophenoxy)benzene, and mixtures ,J ~
of the diamines mentioned.
In the semipermeable membranes according to the inven-tion, both the carrier material and the semipermeable layer can comprise the same polyether ketone or different polyether ketones of the ~ormula (Ia) and tIb), or the same polyaramid or different polyaramids of the formula (II), or the carrier material and layer material can al~o comprise different materials.
It i~ particularly advantageous if the carrier material is derived from a polyphenylene sulfide having recurring structural units of the formula (III).
~ S ~ (III) The abovementioned polyaramids, polyether ketones and polyphenylene sulfides are employed in the form of non-woven~ or woven fabrics, preferably as non-wovens, for the membranes according to the invention.
To produce the membranes according to the invention, the polymer i6 first dissolved, filtered and degassed.
Suitable solvents for polyether ketones are, for e~ample, H2S04, CF3-S03H, HF, Cl2HC-COOH and in particular mixtures of Cl2HC-COOH and H2S04, and suitable solvents for poly-aramids are, in particular, N-methylpyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide and dimethylform-amide. A semipermeable membrane is produced from these solutions in a known manner by the phase inversion process (Robert E. Kesting, "Synthetic Polymeric Membranes", 2nd Edition, 1985, page 237 et se~.). For this purpo~e, the polymer solution is spread as a liquid layer on the carrier material. Precipitating liquid which is miscible with the solvent but in which the polymer~
dissolved in the polymer solution are insoluble and are precipitated as a semipermeable membrane i~ then allowed 2~ J
to act on the liquid layer. The precipitating liquid used is, for example, water.
When carrying out the process, the precipitating liquid is advantageously allowed to act on the membrane precipi-tated by this until practically the entire solvent fromthis has been replaced by precipitating liquid. The membrane formed i8 then freed from precipitating liquid, for example by drying the membrane directly in a stream of air or firæt treating it with a softening agent, such as glycerol, and then drying it.
~he thickness of the membranes according to the invention together with the carrier layer is in the range from 150 to 350 ~m, in particular from 200 to 300 ~m. The thickness of the semipermeable layer here is 20 to 150 ~m, preferably 50 to 100 ~m.
The membranes according to the invention can be produced in the form of flat or tubular membranes, in particular in the form of flat membranes. Processes for the produc-tion of these membranes are known from the prior art.
The membranes according to the invention consist of a carrier material of polyether ketone, polyphenylene sulfide or polyaramid, preferably of polyphenylene sulfide, and of a semipermeable layer of a polyether ketone or a polyaramid, and are distinguished by their high resistance to chemicals, mechanical stresses and heat. Membranes with polyphenylene sulfide as the carrier material and polyether ketones as the semipermeable layer are thus resistant up to above 200C. Membranes with polyaramids as the semipermeable layer and as the carrier material or with polyphenylene sulfide as the carrier layer can preferably be employed in those areas where a particularly high resistance to aggressive media is required. Such membranes are thus not attacked by acids, alkalis or organic solvents, 8uch as chlorobenzene and methanol, or oxidizing agents, such as, for example, ~ 3 sodium hypochlorite, even at elevated temperatures. The separation efficiency of the membrane, its selectivity and also its mechanical stability are retained even after these extreme stresses. They are furthermore distin-guished by a high resistance to enzymatic and microbialattack, which means they are especially suitable for processing media from biotechnology. Another very promis-ing use of the membranes according to the invention is to be found in the removal of rhodium catalysts in Oxo syn-thesis (hydroformylation of olefins to give aldehydes).
The advantages of the membranes according to the inven-tion are illustrated further with the aid of the following embodiment examples.
Examples Polyaramid membranes Examples 1 to 7 For the membranes investigated in the Examples, the polyaramid IIA was prepared from:
>95 mol~ of terephthalic acid dichloride (TPC), 25 mol% of para-phenylenediamine (PPD), 50 mol% of 3,3'-dimethylbenzidine (DMB) and 25 mol% of 1,4-bis-(4-aminophenoxy)benzene (BAPOB) by a polycondensation reaction at 50C in N-methyl-pyrrolidone (NMP) as the solvent.
The polyaramid IIB is prepared from:
~95 mol% of TPC and 100 mol% of 2,2'-bis-[4-(4'-aminophenoxy)phenyl]propane in the same manner.
After neutralization with 100 mol% of CaO, the viscous solutions are filtered and degassed directly, or solid poly-N-vinylpyrrolidone is added, while stirring, and a polymer blend is thus prepared. The resulting clear solutions having various Staudinger indices and various / y~
concentrations are then applied to a carrier (a non-woven or a woven fabric) with a casting device. The membranes are precipitated in water at 5 to 20C. The membranes are then impregnated with a 40 to 50 % strength glycerol solution and dried at 50C. The membranes have a thick-ness of between 150 and 350 ~m, depending on the thickness of the carrier.
o- 2 . . .= _ . . _ tn ~? + h oo t51 ~ ~ ~ ~ .,1 ~
_I ~ ~ ,a ~ ~ N
c.) ~ o O O o ~ ~ ` Q~ ~ ~ ~ O ~
La 1~: U~ ~j O ~1 O X
u~ a) ~ ~ 1 _1 o ~1 ~ S~
c o ,a a~ a~ ~ A 1 a~ c~ _I ~ ~ P
~D 0 _1 ~ ., ~ ~ ~ ~ ~ X 0 oo n~-, o a~ 0 t) o ~ h C) ~ 1 ~ P o .. ~
o c ~ o~ ~D a~ ~:
~ .4 ~a ~ o ~:: _1 P1 1~ O t`~ ~a ~a ~
~ O Iq O O ~ 0 .,, ... ,, a ~ v ~o .,.~ ~Q O
_~ ~ ~1 ~ _1 ~ In O ~o .,1 ~ 0 ~ In d ~ ~ O ,1 ~1 ~ ~ a~ ~ o ~ ,1 ~ ~
_l O ~ ~ 1 ~ 1 ~a rl ~ t~ ~ O ~ 1~ a~
U~ ~ ~ ~: ~1 P ~ O ~ S.l ,1 1~ o P _l ~ ~ tQ ~
_1 ~,c ~ o u :~ ~a 3 t~ ~q ~ ~ O oo ~ O ~ O ~t u ,1 ~ O ~ ~
.,, P: ~ ~ ~ ~ a ~1 o ~i ~ O ~.) ~1 ~ Pl U~
a) ~ ~ .,, a~ tO .c ~ ~ ~
U ~ ~ ~ rl ~ ~ ~n O ~ ~ ~ _l ~ la O ~ _I t7' R ~ O O
tJl ~:: R 1-1 :1 ~ h t~ E~
o ~1 o _I ~n ~: a) u P1 L~ ~ o .r~ P1 O
~1 tn ~ tn ~n ~ ~1 ~ ~ ~ ~ ~ ~ ~ X~
~ t~ o P ~ ~ ~ ~ In w a E~ P
s~
~ s~
C ~ o O N O O Oq ~ O
11 C L .3 C _ ~ S
. ~ ~ ~ ~ ~ ~.
~E~ ~ O
. _0~ __ ~ ~ --~ s~
o o o o o o a .
~ ~------ - ~ -.,1 dP
al a _ o~ U~ l o o o U~ o U~ o 0~ ~ ~D U~ ~D ~r ~ ~r ~ ~ o P~ ~ _ o o ~
_ ~
_ _ _ __ __ __ ~ 11 O O O O O O O O O _I N
~1 ~_1 ~1 ~_1 ~)-1 1'~_1 ~ pO
~: ~ ~ E~ E~ E-~ K El K E-l K E~ ~ ~ --o o _ ~ O o O ~ t`~ CO ~O ~ Cl~ t` U~ O o _I O~ ' ~ O~ ~ l ~~0~ CO _I O~CD O j~O .~
_ U ,1 o ~
o~ ta 5!2 ~ O O l u~ O O O m h N tlr) O O~ O ~I O~ ~ O S-l--I ta ~ _~ _l ~_ o _l 1~
_l ~ Z ~ U ~ -a) 3~ _ _ _ R , . . _ _ _ S l 1 1 _ ~
O ~: O ~ ~q 0 ~ O
~3 a) ,~ P1 ~ u~
Q t~ . G~ dP o o .,1 1 r~ ~ t~ o u~ ~U~ U0--I
O O ~ _, _, ~ 1 O
P1 U ~ - ~ ~ ~
. _ _ _ . '1 ~
_ o~0~
~ o o o o o ~ X~' - - - - -- - ~ ~ p ~ w o ~ .C ~ O F
~ _ _ ~ w a~ w _1 ~ ~ 3 w~
~ E~ u~ q) o ~.q ~.q u~ ~-a w ~ 1:
h 0 ,1 1~3 Pl _~ _I ~ ~ Pl ~ ~ ~`C 0 0 1 P~ P~ ~ e~ P~ Pl P~ ~: 0 ~ ~ ~
o ~ In ~ m m ~ ~ h g~ 0 .4 R
0 0 0 H H 0 X 0 X H H H J-~ ~ O W ~ ~
U E3 H H _ ~ ~--~3 H H H 0 al 3 Ul la _ _ _ . . _ ~ W I
w h 1: ~ to ~--1 0 0 ~Q ~
h .~ h G~ w ~3 _i ~ ~ ~r n ~D t- O~
oo ,~
.. _ _ __ . __ _ _-- ~ + a ~ E~ K
J
Staudinger index t~] (limiting vi8c08ity, intrinsic viscosity) is understood as meaning the expression 17.p lim ---= [~1]
C2 ~ C2 in which ~8p = specific viscosity = ~
c2 = concentration of the dissolved substance = viscosity of the solution ~, = viscosity of the pure solvent Examples 8 to 10 Membranes of polyaramid IIA, polyether ketone ~Ia, b) or polyphenylene sulfide (III) as carrier materials can also be used in organic media. Thus, for example, noble metal catalysts can be removed from solutions which are pre-cipitated during the Oxo synthesis using the membranes according to the invention. The separations in this case are carried out in overflow cells of stainless steel.
_ Ex- Poly- Operating Permeate Cataly~t ample aramid/ tempera- flow retention ~ carrier ture (l/m2h) (%) __ 9 IIA~PPS 40 12 68 IIA/PPS ~ 110 32 ~ 55 * the polyaramid membrane on PET can be used up to 40C
~ the polyaramid membrane on PPS is stable far beyond Polyether ketone membranes Examples 11 to 15 To produce a polyether ketone membrane (PER as the semi-permeable layer), 120 g of a polyether ketone (Ib) are dissolved in 880 g of 96 ~ strength H2SO4 at about 30C
while stirring. After about 12 hours, the solution i~
filtered and degassed. Membranes are produced as des-cribed for polyaramid membranes in Examples 1 to 7.
10 ~ Ex- PEK (Ib)/ Water I Reten- Permeat~ ¦Thick ;
ample carrier flow tion flow nes 8 _ jmaterial (l/m2h) (%) (l/m2h) (~m) 11 PEK 200 97 (R 30) 36 360 12 PER 175 96 (R 30) 34 350 ~ (Ib)/PET _ 13 PER 120 97 (R 30) 38 230 (Ib)/PPS
14+~ ~as Ex- _ _ _ _ ample 11) .
15L (as Ex- 80 99 (R 30) 20 240 . ample 12) ~ PET non-woven dissolves, the membranes can no longer be employed A alkaline treatment: 24 hours in 2 % strength NaOH at
HOECH5T AKTIENGESELLSCHAFT HOE 91/F 064 DCh.SY/sch Description Porous semipermeable membrane resistant to chemicals and heat Since the introduction of asymmetric membranes of cellu-lose acetate by Loeb and Sourira~an (S. Sourira~an, Reverse Osmosis, Logos Press, London 1970) and of hydro-phobic polymers ~US-A-3,615,024), numerous membranes have been developed and proposed, in particular for separa-tions of low- and high- molecular-weight constituents dissolved in water, the structure and suitability of which are described in the literature (Desalination, 35 (1980), 5-20) and which have also been tested success-fully in industrial practice or for medical purposes.
Many of the membranes described have particularly advan-tageous properties for achieving specific ob~ects. As a result of their chemical and physical structure, the individual membranes can in each case have the optimum suitability only for quite specific separation problems.
This results in the fundamental re~uirement of the constant development of new membrane~ for new tasks.
An overview of the advantages and disadvantages of membranes which are already known is given in EP-A-0,082,433. There are thus, for example, hydrophilic, asymmetric membranes of cellulose acetate which have satisfactory anti-adsorptive properties but leave a great deal to be desired in recpect of their resistance to heat and chemicals. Although membranes of polysulfones or similar polymers have a ~ood resistance to heat and chemicals, they are sensitive to the action of organic solvents.
Hydrophilicity and a sLmultaneous resistance to solvents are found in membranes of regenerated cellulose, however, these can be hydrolyzed relatively easily in acid or alkaline media, and they are moreover rapidly attacked by microorganisms.
DE-A-3,321,860 describes chemically resistant membranes of partly sulfonated polyether ketone. Although these me~branes are not dissolved under the action of organic solvents~ such as acetone or tetrahydrofuran (THF), they swell severely and thereby change their membranes proper-ties irreversibly.
The membranes are absorbed onto woven fabrics or non-wovens in order to achieve an increased mechanical stabilization. The carrier materials generally used comprise polypropylene or polyethylene terephthalate.
Nevertheless, such carrier mem~ranes have the disad-vantage that, for example, the service temperatures are reduced considerably because of the inadeguate heat stability of the non-wovens or the woven fabrics. The action of organic solvents, acids and alkalis furthermore leads to the dissolution o. these carrier materials or to the detachment of the membrane.
~he invention i6 therefore based on the ob~ect of provid-ing semipermeable membranes which have a high stability, are resistant both to hydrolyzing agents and to oxidizing agents, have a high heat stability and are not attacked by organic solvents, even at elevated temperatures.
The object is achieved by a semipermeable membrane consisting of a carrier material and a layer adhering to this, the carrier material being a woven fabric or a non-woven based on a polyphenylene 6ulfide, a polyether ketone or a polyaramid. ~he membranes described here are particularly suitable for micro-, nano- and ultra-filtration.
In the membranes according to the invention, the semi-permeable layer on the carrier material can comprise either a polyether ketone or a polyaramid.
L t~
The semipermeable layer and if appropriate also the carrier layer i8 derived from a polyether ketone having the recurring units of the formula (Ia) ~ O ~ C ~ (Ia) in particular from a polyether ketone ha~ing the recur-ring units of the formula (Ib) ~ O ~ C ~ l~ ~ O A ~ (Ib) in which -A- is a radical ~ or ~ z in which R1, RZ, R3 and R4 can be identical or different and are hydrogen, a (Cl-C4)-alkyl, (C6-C14)-aryl or (C6-Cl4)-hydroxyaryl group or NO2, CN, NR52 (R5 = (Cl-C6)-alkyl) or halogen and -Z- is one of the groupings -O-,-S-,-CH2-,-CF2.,-C-, -C-, -SO2r or -CO-~he preparation of polyether ketones, for example by nucleophilic aromatic polycondensation, iR known and is described in EP-A-0,001,879 and GB-A-1,414,421. Polyether ketones such as are used for the membranes according to the invention are described, for example, in DE-A-3,936,997, which is of earlier priority and i5 not a prior publication.
In a further preferred embodiment, the semipermeable layer and if appropriate the carrier material comprises an aromatic homo- or copolyamide having at least one of the recurring structural unit~ of the formula (II) O O
-(C-E'-C-NH-E2-NH)- (II) in which -E1- and -E2- are identical or different and are selected from one or more of the grouping6 ~NH CO~
-Arl- or --A~ l--X--Ar2 in which -Arl- and -Ar2- are identical or different 1,2-phenylene, 1,3-phenylene, 1,4-phenylene radicals or (C6-C~4)-arylene radicals, which can be substituted by one or more (cl-c6)-alkyl~ (C~-C6)-alkoxy or CF3 groups or halogen, in particular fluorine, chlorine or bromine atoms, or are a heteroaromatic radical, for example a ~2,5]- or [3,4]-furano radical, and the radical -X-a) is a direct bond or i8 one of the following divalent radicals -O-, -C(CF3) 2- ~ -S2- ~ -CO- or -C(R6) 2- ~ in which R6 is hydrogen or a (Cl-C6)-alkyl or (C~-C4)-fluoroalkyl group, or b) is -Y-Arl-Y-, in which -Y- is the radical -O- or -C(CH3)2-~or c) is -O-Arl-Q-ArZ-0-, in which -Q- has the meaning given under Xa).
The pxeparation of the polyaramids which are suitable as carrier materials and as layer materials for ~he mem-branes according to the invention is described in DE-A-3,903,098 and DE-A-3,802,030.
Examples of suitable starting materials for their prepa-ration are a) dicarboxylic acid dichlorides of the formula (IV) Cl-C0-E2-C0-Cl (IV) in which El has the abovementioned meaning.
Examples of ~ompounds of the formula (IV~ are 4,4'-di-phenyl sulfone-dicarboxylic acid dichloride, 4,4'-diphenyl ether-dicarboxylic acid dichloride, 4,4'-di-phenyldicarboxylic acid dichloride, 2,6-naphthalene-dicarboxylic acid dichlGride, isophthalic acid dichloride and 2,5-furandicarboxylic acid dichloride, but in par-ticular terephthalic acid dichloride and substitutedt.erephthalic acid dichloride, for example 2-chlorotere-phthalic acid dichloride;
b) aromatized diamines of the formula (V) H2I~-E2--NH2 ~V) for example m-phenylenediamine or substituted phenylene-diamines, for example 2-chloro-, 2,5-dichloro- or 2-meth-oxy-p-phenylenediamine, in particular p-phenylenediamine, and substituted benzidine derivatives, for example 4,4'-di-aminobenzophenone, bis-[4-aminophenyl] sulfone, bis-[4-(4'-aminophenoxy)phenyl3 sulfone, 1,2-bis-[4'-aminophen-oxy]benzene, 1,4-bis-~(4~-aminophenyl)isopropyl]benzene and 2,2'-bis-t4-(4'-aminophenoxy~phenyl]propane, in par-ticular 1,4-bis-(4'-aminophenoxy)benzene, and mixtures ,J ~
of the diamines mentioned.
In the semipermeable membranes according to the inven-tion, both the carrier material and the semipermeable layer can comprise the same polyether ketone or different polyether ketones of the ~ormula (Ia) and tIb), or the same polyaramid or different polyaramids of the formula (II), or the carrier material and layer material can al~o comprise different materials.
It i~ particularly advantageous if the carrier material is derived from a polyphenylene sulfide having recurring structural units of the formula (III).
~ S ~ (III) The abovementioned polyaramids, polyether ketones and polyphenylene sulfides are employed in the form of non-woven~ or woven fabrics, preferably as non-wovens, for the membranes according to the invention.
To produce the membranes according to the invention, the polymer i6 first dissolved, filtered and degassed.
Suitable solvents for polyether ketones are, for e~ample, H2S04, CF3-S03H, HF, Cl2HC-COOH and in particular mixtures of Cl2HC-COOH and H2S04, and suitable solvents for poly-aramids are, in particular, N-methylpyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide and dimethylform-amide. A semipermeable membrane is produced from these solutions in a known manner by the phase inversion process (Robert E. Kesting, "Synthetic Polymeric Membranes", 2nd Edition, 1985, page 237 et se~.). For this purpo~e, the polymer solution is spread as a liquid layer on the carrier material. Precipitating liquid which is miscible with the solvent but in which the polymer~
dissolved in the polymer solution are insoluble and are precipitated as a semipermeable membrane i~ then allowed 2~ J
to act on the liquid layer. The precipitating liquid used is, for example, water.
When carrying out the process, the precipitating liquid is advantageously allowed to act on the membrane precipi-tated by this until practically the entire solvent fromthis has been replaced by precipitating liquid. The membrane formed i8 then freed from precipitating liquid, for example by drying the membrane directly in a stream of air or firæt treating it with a softening agent, such as glycerol, and then drying it.
~he thickness of the membranes according to the invention together with the carrier layer is in the range from 150 to 350 ~m, in particular from 200 to 300 ~m. The thickness of the semipermeable layer here is 20 to 150 ~m, preferably 50 to 100 ~m.
The membranes according to the invention can be produced in the form of flat or tubular membranes, in particular in the form of flat membranes. Processes for the produc-tion of these membranes are known from the prior art.
The membranes according to the invention consist of a carrier material of polyether ketone, polyphenylene sulfide or polyaramid, preferably of polyphenylene sulfide, and of a semipermeable layer of a polyether ketone or a polyaramid, and are distinguished by their high resistance to chemicals, mechanical stresses and heat. Membranes with polyphenylene sulfide as the carrier material and polyether ketones as the semipermeable layer are thus resistant up to above 200C. Membranes with polyaramids as the semipermeable layer and as the carrier material or with polyphenylene sulfide as the carrier layer can preferably be employed in those areas where a particularly high resistance to aggressive media is required. Such membranes are thus not attacked by acids, alkalis or organic solvents, 8uch as chlorobenzene and methanol, or oxidizing agents, such as, for example, ~ 3 sodium hypochlorite, even at elevated temperatures. The separation efficiency of the membrane, its selectivity and also its mechanical stability are retained even after these extreme stresses. They are furthermore distin-guished by a high resistance to enzymatic and microbialattack, which means they are especially suitable for processing media from biotechnology. Another very promis-ing use of the membranes according to the invention is to be found in the removal of rhodium catalysts in Oxo syn-thesis (hydroformylation of olefins to give aldehydes).
The advantages of the membranes according to the inven-tion are illustrated further with the aid of the following embodiment examples.
Examples Polyaramid membranes Examples 1 to 7 For the membranes investigated in the Examples, the polyaramid IIA was prepared from:
>95 mol~ of terephthalic acid dichloride (TPC), 25 mol% of para-phenylenediamine (PPD), 50 mol% of 3,3'-dimethylbenzidine (DMB) and 25 mol% of 1,4-bis-(4-aminophenoxy)benzene (BAPOB) by a polycondensation reaction at 50C in N-methyl-pyrrolidone (NMP) as the solvent.
The polyaramid IIB is prepared from:
~95 mol% of TPC and 100 mol% of 2,2'-bis-[4-(4'-aminophenoxy)phenyl]propane in the same manner.
After neutralization with 100 mol% of CaO, the viscous solutions are filtered and degassed directly, or solid poly-N-vinylpyrrolidone is added, while stirring, and a polymer blend is thus prepared. The resulting clear solutions having various Staudinger indices and various / y~
concentrations are then applied to a carrier (a non-woven or a woven fabric) with a casting device. The membranes are precipitated in water at 5 to 20C. The membranes are then impregnated with a 40 to 50 % strength glycerol solution and dried at 50C. The membranes have a thick-ness of between 150 and 350 ~m, depending on the thickness of the carrier.
o- 2 . . .= _ . . _ tn ~? + h oo t51 ~ ~ ~ ~ .,1 ~
_I ~ ~ ,a ~ ~ N
c.) ~ o O O o ~ ~ ` Q~ ~ ~ ~ O ~
La 1~: U~ ~j O ~1 O X
u~ a) ~ ~ 1 _1 o ~1 ~ S~
c o ,a a~ a~ ~ A 1 a~ c~ _I ~ ~ P
~D 0 _1 ~ ., ~ ~ ~ ~ ~ X 0 oo n~-, o a~ 0 t) o ~ h C) ~ 1 ~ P o .. ~
o c ~ o~ ~D a~ ~:
~ .4 ~a ~ o ~:: _1 P1 1~ O t`~ ~a ~a ~
~ O Iq O O ~ 0 .,, ... ,, a ~ v ~o .,.~ ~Q O
_~ ~ ~1 ~ _1 ~ In O ~o .,1 ~ 0 ~ In d ~ ~ O ,1 ~1 ~ ~ a~ ~ o ~ ,1 ~ ~
_l O ~ ~ 1 ~ 1 ~a rl ~ t~ ~ O ~ 1~ a~
U~ ~ ~ ~: ~1 P ~ O ~ S.l ,1 1~ o P _l ~ ~ tQ ~
_1 ~,c ~ o u :~ ~a 3 t~ ~q ~ ~ O oo ~ O ~ O ~t u ,1 ~ O ~ ~
.,, P: ~ ~ ~ ~ a ~1 o ~i ~ O ~.) ~1 ~ Pl U~
a) ~ ~ .,, a~ tO .c ~ ~ ~
U ~ ~ ~ rl ~ ~ ~n O ~ ~ ~ _l ~ la O ~ _I t7' R ~ O O
tJl ~:: R 1-1 :1 ~ h t~ E~
o ~1 o _I ~n ~: a) u P1 L~ ~ o .r~ P1 O
~1 tn ~ tn ~n ~ ~1 ~ ~ ~ ~ ~ ~ ~ X~
~ t~ o P ~ ~ ~ ~ In w a E~ P
s~
~ s~
C ~ o O N O O Oq ~ O
11 C L .3 C _ ~ S
. ~ ~ ~ ~ ~ ~.
~E~ ~ O
. _0~ __ ~ ~ --~ s~
o o o o o o a .
~ ~------ - ~ -.,1 dP
al a _ o~ U~ l o o o U~ o U~ o 0~ ~ ~D U~ ~D ~r ~ ~r ~ ~ o P~ ~ _ o o ~
_ ~
_ _ _ __ __ __ ~ 11 O O O O O O O O O _I N
~1 ~_1 ~1 ~_1 ~)-1 1'~_1 ~ pO
~: ~ ~ E~ E~ E-~ K El K E-l K E~ ~ ~ --o o _ ~ O o O ~ t`~ CO ~O ~ Cl~ t` U~ O o _I O~ ' ~ O~ ~ l ~~0~ CO _I O~CD O j~O .~
_ U ,1 o ~
o~ ta 5!2 ~ O O l u~ O O O m h N tlr) O O~ O ~I O~ ~ O S-l--I ta ~ _~ _l ~_ o _l 1~
_l ~ Z ~ U ~ -a) 3~ _ _ _ R , . . _ _ _ S l 1 1 _ ~
O ~: O ~ ~q 0 ~ O
~3 a) ,~ P1 ~ u~
Q t~ . G~ dP o o .,1 1 r~ ~ t~ o u~ ~U~ U0--I
O O ~ _, _, ~ 1 O
P1 U ~ - ~ ~ ~
. _ _ _ . '1 ~
_ o~0~
~ o o o o o ~ X~' - - - - -- - ~ ~ p ~ w o ~ .C ~ O F
~ _ _ ~ w a~ w _1 ~ ~ 3 w~
~ E~ u~ q) o ~.q ~.q u~ ~-a w ~ 1:
h 0 ,1 1~3 Pl _~ _I ~ ~ Pl ~ ~ ~`C 0 0 1 P~ P~ ~ e~ P~ Pl P~ ~: 0 ~ ~ ~
o ~ In ~ m m ~ ~ h g~ 0 .4 R
0 0 0 H H 0 X 0 X H H H J-~ ~ O W ~ ~
U E3 H H _ ~ ~--~3 H H H 0 al 3 Ul la _ _ _ . . _ ~ W I
w h 1: ~ to ~--1 0 0 ~Q ~
h .~ h G~ w ~3 _i ~ ~ ~r n ~D t- O~
oo ,~
.. _ _ __ . __ _ _-- ~ + a ~ E~ K
J
Staudinger index t~] (limiting vi8c08ity, intrinsic viscosity) is understood as meaning the expression 17.p lim ---= [~1]
C2 ~ C2 in which ~8p = specific viscosity = ~
c2 = concentration of the dissolved substance = viscosity of the solution ~, = viscosity of the pure solvent Examples 8 to 10 Membranes of polyaramid IIA, polyether ketone ~Ia, b) or polyphenylene sulfide (III) as carrier materials can also be used in organic media. Thus, for example, noble metal catalysts can be removed from solutions which are pre-cipitated during the Oxo synthesis using the membranes according to the invention. The separations in this case are carried out in overflow cells of stainless steel.
_ Ex- Poly- Operating Permeate Cataly~t ample aramid/ tempera- flow retention ~ carrier ture (l/m2h) (%) __ 9 IIA~PPS 40 12 68 IIA/PPS ~ 110 32 ~ 55 * the polyaramid membrane on PET can be used up to 40C
~ the polyaramid membrane on PPS is stable far beyond Polyether ketone membranes Examples 11 to 15 To produce a polyether ketone membrane (PER as the semi-permeable layer), 120 g of a polyether ketone (Ib) are dissolved in 880 g of 96 ~ strength H2SO4 at about 30C
while stirring. After about 12 hours, the solution i~
filtered and degassed. Membranes are produced as des-cribed for polyaramid membranes in Examples 1 to 7.
10 ~ Ex- PEK (Ib)/ Water I Reten- Permeat~ ¦Thick ;
ample carrier flow tion flow nes 8 _ jmaterial (l/m2h) (%) (l/m2h) (~m) 11 PEK 200 97 (R 30) 36 360 12 PER 175 96 (R 30) 34 350 ~ (Ib)/PET _ 13 PER 120 97 (R 30) 38 230 (Ib)/PPS
14+~ ~as Ex- _ _ _ _ ample 11) .
15L (as Ex- 80 99 (R 30) 20 240 . ample 12) ~ PET non-woven dissolves, the membranes can no longer be employed A alkaline treatment: 24 hours in 2 % strength NaOH at
Claims (9)
1. A semipermeable membrane for micro-, nano- and ultrafiltration, comprising a carrier material and a semipermeable layer adhering to this, wherein the carrier material is a woven fabric or a non-woven based on a polyphenylene sulfide, a polyether ketone or a polyaramid.
2. A semipermeable membrane as claimed in claim 1, wherein the semipermeable layer comprises a poly-ether ketone having the following recurring units of the formula (Ia) (Ia)
3. A semipermeable membrane as claimed in claim 1, wherein the semipermeable layer comprises a poly-ether ketone having the following recurring units of the formula (Ib):
(Ib) in which -A- is or R1, R2, R3 and R4 can be identical or different and are hydrogen, a (C1-C4)-alkyl, (C6-C14)-aryl or (C6-C14)-hydroxyaryl group or _ 15 -NO2, CN, NR52 (R5 = (C1-C6)-alkyl) or halogen and -Z- is one of the groupings or -CO-
(Ib) in which -A- is or R1, R2, R3 and R4 can be identical or different and are hydrogen, a (C1-C4)-alkyl, (C6-C14)-aryl or (C6-C14)-hydroxyaryl group or _ 15 -NO2, CN, NR52 (R5 = (C1-C6)-alkyl) or halogen and -Z- is one of the groupings or -CO-
4. A semipermeable membrane as claimed in claim 1, wherein the semipermeable layer comprises an aro-matic homo- or copolyamide having at least one of the recurring structural units of the formula (II) (II) in which -E1- and -E2- are identical or different and are selected from one or more of the groupings -Ar1-or -Ar1-X-Ar2-, in which -Ar1- and -Ar2- are identical or different 1,2-phenylene, 1,3-phenylene, 1,4-phenylene radicals or (C6-C14)-arylene radicals, which can be substitu-ted by one or more (C1-C6)-alkyl, (C1-C6)-alkoxy or CF3 groups or halogen, in particular fluorine, chlorine or bromine, or are a heteroaromatic radical, and the radical X
a) is a direct bond or is one of the following divalent radicals -O-, -C(CF3)2-, -SO2-, -CO- or -C(R6)2-, in which R6 is hydrogen or a (C1-C6)-alkyl or (C1-C4)-fluoroalkyl group, or b) is -Y-Ar1-Y-, in which -Y- is the radical -O- or -C(CH3)2-, or c) is -O-Ar1-Q-Ar2-O-, in which Q has the meaning given under Xa).
a) is a direct bond or is one of the following divalent radicals -O-, -C(CF3)2-, -SO2-, -CO- or -C(R6)2-, in which R6 is hydrogen or a (C1-C6)-alkyl or (C1-C4)-fluoroalkyl group, or b) is -Y-Ar1-Y-, in which -Y- is the radical -O- or -C(CH3)2-, or c) is -O-Ar1-Q-Ar2-O-, in which Q has the meaning given under Xa).
5. A semipermeable membrane as claimed in claim 2 or 3, wherein the carrier material and the semipermeable layer both comprise the same polyether ketone or different polyether ketones having the recurring units of the formula (Ia) or (Ib), or comprise the same polyaramid or comprise different polyaramids of the formula (II).
6. A semipermeable membrane as claimed in claim 1, wherein the carrier material is a non-woven or a woven fabric based on a polymer having the recurring units of the formula (Ia) or (Ib) or of the formula (II).
7. A semipermeable membrane as claimed in claim 1, wherein the carrier material is a polyphenylene sulfide having the recurring structural units of the formula (III) ( III )
8. A process for the production of a semipermeable membrane as claimed in claim 1, which comprises first dissolving the polymer in a solvent and filtering and degassing the solution, and, in a subsequent step, producing a membrane by the phase inversion process, and employing H2SO4, CF3-SO3H, HF, Cl2HC-COOH or a mixture of Cl2HC-COOH and H2SO4 as the solvent for a polyether ketone and N-methyl-pyrrolidone, dimethylacetamide or dimethylformamide as the solvent for a polyaramid.
9. A semipermeable membrane as claimed in claim 1, which is a flat or tubular membrane.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4106234 | 1991-02-28 | ||
DEP4106234.5 | 1991-02-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2061990A1 true CA2061990A1 (en) | 1992-08-29 |
Family
ID=6426040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002061990A Abandoned CA2061990A1 (en) | 1991-02-28 | 1992-02-27 | Porous semipermeable membrane resistant to chemicals and heat |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0501425A1 (en) |
JP (1) | JPH04317733A (en) |
KR (1) | KR920016135A (en) |
CA (1) | CA2061990A1 (en) |
MX (1) | MX9200822A (en) |
TW (1) | TW205513B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5562826A (en) * | 1991-10-26 | 1996-10-08 | Hoechst Aktiengesellschaft | Semipermeable, porous, asymmetric polyether amide membranes |
DE59208013D1 (en) * | 1991-10-26 | 1997-03-20 | Hoechst Ag | Semipermeable, porous, asymmetrical polyether amide membranes |
DE4338196A1 (en) * | 1993-11-09 | 1995-05-11 | Bayer Ag | Process for cleaning organic synthesis products |
DE4418843A1 (en) | 1994-05-30 | 1995-12-07 | Hoechst Ag | Porous membrane made from aromatic polyamide |
DE19549001A1 (en) * | 1995-12-28 | 1997-07-03 | Hoechst Ag | Process for the preparation of polyether amide solutions, steam-sterilizable dialysis membranes obtainable using the polyether amide solutions, and process for the production of these membranes |
DE19729456C1 (en) * | 1997-07-10 | 1998-10-22 | Sartorius Gmbh | Porous organic polymer membrane used for micro-filtration and ultrafiltration |
JP2009202076A (en) * | 2008-02-27 | 2009-09-10 | Toray Ind Inc | Separative membrane |
JP2010043372A (en) * | 2008-08-12 | 2010-02-25 | Toyobo Co Ltd | Polyphenylene sulfide nonwoven fabric with smoothness, method for producing the same, and textile material using the same |
CN105032218B (en) * | 2015-07-20 | 2017-11-03 | 四川大学 | A kind of enhanced solvent resistant polyaryl thioether sulfone hollow-fibre membrane and preparation method thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES516206A0 (en) * | 1981-10-21 | 1983-10-01 | Du Pont | "IMPROVEMENTS INTRODUCED IN A PROCEDURE FOR THE PREPARATION OF A REVERSE OSMOSIS MEMBRANE". |
KR960004612B1 (en) * | 1988-09-29 | 1996-04-09 | 도레이 가부시키가이샤 | Porous membrane and the manufacturing process thereof |
GB8901672D0 (en) * | 1989-01-26 | 1989-03-15 | Ici Plc | Membranes |
DE3903098A1 (en) * | 1989-02-02 | 1990-08-16 | Hoechst Ag | SEMIPERMEABLE MEMBRANE MADE OF A HOMOGENOUSLY MIXABLE POLYMER ALLOY |
US4908134A (en) * | 1989-02-16 | 1990-03-13 | Exxon Research And Engineering Company | Ultrafiltration polyamide membrane and its use for recovery of dewaxing aid (OP-3454) |
DE3928934C2 (en) * | 1989-08-31 | 1999-04-29 | Sartorius Gmbh | Textile reinforced microporous membrane filter, process for its preparation and its use |
DE3936997A1 (en) * | 1989-11-07 | 1991-05-08 | Hoechst Ag | SEMIPERMEABLE MEMBRANE MADE OF POLYETHERKETONES |
-
1992
- 1992-02-17 TW TW081101120A patent/TW205513B/zh active
- 1992-02-25 EP EP92103192A patent/EP0501425A1/en not_active Withdrawn
- 1992-02-26 MX MX9200822A patent/MX9200822A/en unknown
- 1992-02-26 KR KR1019920002962A patent/KR920016135A/en not_active Application Discontinuation
- 1992-02-27 CA CA002061990A patent/CA2061990A1/en not_active Abandoned
- 1992-02-28 JP JP4043668A patent/JPH04317733A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
JPH04317733A (en) | 1992-11-09 |
MX9200822A (en) | 1992-08-01 |
KR920016135A (en) | 1992-09-24 |
TW205513B (en) | 1993-05-11 |
EP0501425A1 (en) | 1992-09-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2008328C (en) | Semipermeable membrane made from a homogeneously miscible polymer blend | |
US4240914A (en) | Selective permeable membrane and process for preparing the same | |
US6887380B2 (en) | Silicone-coated organic solvent resistant polyamide composite nanofiltration membrane, and method for preparing the same | |
US5505851A (en) | Semipermeable membranes of homogeneously miscible polymer alloys | |
CA1104748A (en) | Semipermeable membranes of polyamides | |
CA1052707A (en) | Asymmetric, semipermeable membranes of cyclic polyureas | |
CA2061990A1 (en) | Porous semipermeable membrane resistant to chemicals and heat | |
JPH0380049B2 (en) | ||
US3841492A (en) | Production of semipermeable polybenzimidazole membranes | |
KR102573508B1 (en) | Gas separation membrane, gas separation membrane element, and gas separation method | |
JP4057217B2 (en) | Method for producing solvent-resistant microporous polybenzimidazole thin film | |
WO2008070216A1 (en) | Polyarylethernitrile hollow fiber membranes | |
AU600639B2 (en) | Macroporous, asymmetric, hydrophilic polyaramide membrane | |
US5536408A (en) | Hydrophilic, asymmetric, chemically-resistant polyaramide membrane | |
US5562826A (en) | Semipermeable, porous, asymmetric polyether amide membranes | |
CN112619443A (en) | Composite reverse osmosis membrane and preparation method thereof | |
US5859175A (en) | Process for the preparation of polyether amide solutions, steam-sterilizable dialysis membranes obtainable using the polyether-amide solutions, and a process for the production of these membranes | |
CA2081260A1 (en) | Semipermeable, porous, asymmetric polyether amide membranes | |
EP1356856A1 (en) | Silicone-coated organic solvent resistant polyamide composite nanofiltration membrane, and method for preparing the same | |
JP2003251152A (en) | Precision porous poly(ether sulfone) filter membrane | |
JP2508732B2 (en) | Selectively permeable hollow fiber composite membrane and method for producing the same | |
JPH01242106A (en) | Composite semipermeable membrane | |
JPH0628711B2 (en) | Permselective membrane | |
JPS62213807A (en) | Selective permeable membrane | |
KR20220069097A (en) | composite semipermeable membrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |