EP0156840A4 - Traitement de membranes poreuses. - Google Patents

Traitement de membranes poreuses.

Info

Publication number
EP0156840A4
EP0156840A4 EP19840903426 EP84903426A EP0156840A4 EP 0156840 A4 EP0156840 A4 EP 0156840A4 EP 19840903426 EP19840903426 EP 19840903426 EP 84903426 A EP84903426 A EP 84903426A EP 0156840 A4 EP0156840 A4 EP 0156840A4
Authority
EP
European Patent Office
Prior art keywords
membrane
component
pores
walls
hydrophilic
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.)
Withdrawn
Application number
EP19840903426
Other languages
German (de)
English (en)
Other versions
EP0156840A1 (fr
Inventor
Douglas Lyons Ford
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Memtec Ltd
Original Assignee
Memtec Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Memtec Ltd filed Critical Memtec Ltd
Publication of EP0156840A1 publication Critical patent/EP0156840A1/fr
Publication of EP0156840A4 publication Critical patent/EP0156840A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix

Definitions

  • This invention relates to porous membranes, particularly those having pores in the range of about 0.01 to 1 micron which are hereinafter called "fine pored filtration membranes”.
  • voids or pores may be wetted by the addition of "surfactants” followed by continuous wet storage in water or humectant solutions, these procedures are not stable to washing, heating and drying as is required for heat sterilisation at 122°C. Such temporary wetting procedures fail with polypropylene.
  • hydrophilic special polymers such as cellulose, hydrophilic nylons and cellulose esters do not resist hot, strong acids nor do they resist small concentrations of chlorine or hydrogen peroxide sterilants. Furthermore, some of these cheaper polymers do not even tolerate repeated wetting and drying. Many of them swell greatly in water and shrink on drying. Thus, the prior art is characterised by expensive experimental procedures to create a particular hydrophilicity for each new polymer and no stable post-formation control has been possible.
  • a process of treating a hydrophobic porous membrane so as to render it hydrophilic in which a hydrophilic material is deposited on the walls of the pores of the membrane.
  • the invention also provides a method of treating a hydrophobic porous membrane so as to render it hydrophilic by coating the walls of the pores of the membrane with a hydrophilic material in which the hydrophilic material is deposited on the walls of the pores by the reaction of first and second components of the material within the membrane.
  • the method of the invention includes the steps of:
  • the invention also provides a method of treating a ' hydrophobic porous membrane so as to render it hydrophilic which comprises the steps of:
  • the deposition material is selected from:
  • Phenol/aldehyde resins which react very rapidly in aqueous media to precipitate fine, porous solids.
  • Gaseous acidic catalysts may be used to ensure reaction in a mixture of polyhydroxyaromatics and low volatile aldehydes or pre-polymers of these two components.
  • the water solvent can be easily evaporated from the hydrophobic porous base. Dry hydrochloric acid, sulphur trioxide, boron trifluoride or sulphury1 chloride may be admitted to speed up the reaction.
  • Epoxy resins include all epoxides and their reaction products with reactive hydrogen groups such as alcohols, amines, acids, ureas, urethanes, phenols and thiols.
  • the stabilisation step includes dissolving any unco bined material and hydrolysing excess terminal groups or reacting them further as desired to secure specific surface effects as given below.
  • the two components may be passed through the membrane together provided that there is sufficient delay in the commencement of the reaction between the components to enable them to be properly disposed.
  • the invention also provides a method of treating a membrane of non-uniform pore size so as to provide a membrane having a predetermined porosity in which a blocking material is deposited within selected pores and on the walls of the other pores of the membrane by the reaction of first and second components of the material within the membrane.
  • the first component is an emulsion in which the size of the dispersed phase and its interfacial tension with the continuous phase are such as to cause exclusion of the dispersed phase from pores which are smaller than the predetermined pore size.
  • the emulsion may be formed from a primary or secondary amine, which is converted into a polyamide by an acid halide as previously described.
  • the blocking material may also be formed from:
  • an alcohol such as polyvinylalcohol and an isocyanate
  • a method of treating a membrane of non-uniform pore size so as to provide a membrane having a predetermined porosity comprising the steps of:
  • the methods of the invention permit the preparation of fine pored filtration membranes of desired physical and/or chemical characteristics without the need of expensive experimental procedures.
  • the coatings or materials deposited by the methods of the invention will sometimes be in themselves novel and the particular method of application of the material may itself be novel. For example, it may be necessary to introduce new techniques such as supplying gaseous catalysts to affect spatially selected areas. When selecting the particular material with which to treat the otherwise unsuitable fine pored filtration membrane certain considerations must be borne in mind.
  • the choice of the material will be in the decreasing order of polyamide or polyimide, polyesters, polyurethanes, phenol/aldehyde resins, polyamine/aldehyde resins, epoxy resins, interpolymers of the foregoing and mixtures of the foregoing.
  • the reasons for this preferred order include the availability of a wide range of cheap. co
  • polyamides When the treatment is for hydrophilicity, acid and chlorine resistance, polyamides would be the best choice.
  • Cross-linked polyamides (or polyimides if suitable acid chlorides are used) are particularly useful as they are resistant to hot hydrochloric acid and chlorine and pH 13 for at least a year.
  • Many functional groups may be incorporated in their structure, for example, a -SO ⁇ H group may be incorporated by using sulfanilic acid. However, when incorporating such functional groups allowance must be made for the mono-functional nature of the single - H2 group.
  • the cheapest available aromatic acid chloride of functionality two is terephthaloylchloride and thus it would be the preferred material.
  • Such a material will give resistant products with any diamine or polyamine but high hydrophilicity demands that there will be a limit to the ratio of hydrophobic carbon groups to the hydrophilic nitrogen group.
  • Ethylene diamine or triethylene tetramine may be used.
  • any polyamine containing up to 20 carbon atoms per nitrogen atom may be used to give a continuous spectrum of reliable hydrophilicity.
  • the polyester treatment materials have advantages where phenolic functional groups or sulphonic functional groups are required.
  • the phenolic hydroxyl groups are useful when reactions with epoxides are required.
  • epoxides may be gaseous such as ethylene epichlorhydrin dilute vapour which produces highly hydroxylated surfaces.
  • Ethyleneimine can also be used in such circumstances.
  • the reaction is usually anhydrous and is most useful where very rapid homogeneous reactions precipitate fine polymeric substances.
  • the products are stable and swell well in water so that the membranes are often useful f.or electrodialysis.
  • the phenol/aldehyde resins are useful for chelating metals and they also form good electrodialysis membranes.
  • the polyamine/aldehyde resins tend to be most useful where excess aldehyde groups allow easy conversion to a wide range of other chemical groups or compounds. .
  • aldehydes are excellent for binding antibodies which are used in affinity chromatography to isolate useful or harmful biological products.
  • One of the main uses of the epoxy resins is to overcoat the phenol/aldehyde resins since the latter tend to be rather coarse. In some cases interpolymers and mixtures of the materials may be used.
  • the deposition formulation may bia prepared using a hydrophobic solvent such as hexane which is allowed to evaporate. In some cases, more uniform films are obtained if a small amount of surfactant is included in the formulation.
  • Chemical considerations may suggest addition of a hydrochloric acid absorbing substance such as a tertiary amine to ensure complete reaction of the substitutable amines.
  • the treatment material may be dissolved in water, ethanol or a hydrophilic solvent.
  • the hydrophilic solvent may contain a small amount of surfactant and a small amount of non-volatile hydrophilic humectant substance such as glycerol.
  • Such hydrophilic solvent mixtures usually need considerable pressure to ensure displacement of all air from the membrane. Complete displacement of the air is vital if all the surface of the membrane is to be made hydrophilic. Lesser pressures leave the smaller pores hydrophobic which may, in some instances, be desired.
  • control of the water content of the residual material film is essential for uniform results.
  • the water controls the rate of diffusion of terephthaloylchloride from a hydrophobic solvent in which it is applied.
  • Water content control may be obtained by the relative humidity and temperature of the drying atmosphere and the hydrophilicity of the deposited film depends greatly on the composition and amount of any surfactant or humectant used.
  • a bundle of hydrophobic polypropylene hollow fibre porous membranes are to be treated so as to be easily wettable with aqueous biological media after being heat sterilised and dried at 100°C.
  • the treated bundle of membranes must be clearable by back-blowing with water containing 10 ppm chlorine and soaking at 50°C in 20% hydrochloric acid to dissolve any protein clots therein.
  • the pore sizes of the polypropylene fibres to be treated are from 0.05 to 0.5 microns but the use to which the bundle will be put indicates that some selective plugging of a small proportion of 1 to 5 micron large holes which undesirably allow the permeate to appear optically hazy.
  • a fine dilute emulsion in which the dispersed phase was of a size about 1 micron and its interfacial tension with the continuous phase was such so as to cause exclusion of the dispersed phase from the smaller pores but to allow entry into the coarser pores.
  • the emulsion was formed as a mixture of:
  • Petroleum spirit (b.p. 60-80°C) 950 millilitres Absolute ethanol - 50 millilitres
  • the treated membrane was washed in a 20% weight per volume aqueous hydrochloric acid to dissolve any uncro'ss- linked material and to hydrolyse the excess terminal acid chloride to carboxylic acid groups. A thorough water wash and drying at 60°C completed the treatment.
  • the properties of the treated membrane were excellent. Although the initial polypropylene had shown nil permeation rate of water at 125 kPa, the permeation rate of the treated membrane was 1800 litres per square metre per hour. Microfiltration was excellent since at 125 kPa suspension of extra-fine (i.e. under 1 micron) titanium oxide filtered at 1800 litres per square metre per hour gave a permeate which was optically clear at 650 nanometres. A 0.1% suspension of the cutting oil B.P. FEDARO M which is partly solubilised by wetting agent (i.e.
  • the oil phase is not highly hydrophobic and has about zero interfacial surface tension between the suspended and continuous phases) at 125 kPa gave a permeate at 1080 litres per square metre per hour with 85% rejection of the turbidity at 650 nanometres. It should be noted that the oil is not a solid and that separation was determined by hydrophilicity. A coated polypropylene was so hydrophilic that it selectively passed the wetter solution rather than the hydrophilic micelles.
  • OMPI but which had 5 leaky tubes at 300 kPa.
  • the treatment required a high level of hydrophilicity so that 100% rejection of solubilised cutting oil B.P. FEDARO M would occur.
  • the membrane must have all the pores below 100 nanometres so as to reject over 50% of protein of molecular weight 43,000 (ovalbumin).
  • the treated membrane must be able to cope with a wide range of food industry wastes and must be able to produce optically clear permeates. It must also be able to withstand a hypochlorite sterilisation and a hot 20% hydrochloric acid clean.
  • Example 1 a polyamide system as described in Example 1 will meet the cleaning and chemical criteria.
  • An initial effort was made to deposit a formulated (H ⁇ NtCE ⁇ ) 2 NH film (the first component of the polyamide) using a solution of terephthaloylchloride (the second component of the polyamide).
  • the pores will have to contain considerable fine pored filtration polyamide filling of the highest hydrophilicity.
  • polyamide fine pored filters absorb proteins to form a dynamic interactive pseudo-membrane, the pores may be larger than the radius of gyration of the ovalbumin. This requirement ensures that polyamides, polyesters and phenol/aldehyde resins are the main choices for the treatment material since they best absorb protein.
  • Example 1 is necessary in order to give the finer porosity.
  • OMPI A deposition formulation was made from:
  • the treated membrane was stabilised by washing with water at 400 kPa at a high rate of flow and it was then immersed in 7N hydrochloric acid overnight. It was then washed until neutral and its permeability tested with tap water. At 125 kPa the permeation rate was 864 litres per square metre per hour which confirmed a finer pore than that of Example 1.
  • the 0.1% B.P. FEDARO M oil showed over 99.95% rejection which was the limit of instrumental detection. A faint haze in 40 cm thickness could just be detected and this was possibly due to wetter micelles. The ovalbumin showed 50% rejection. Biological wastes from a variety of food processes showed optical clarity. In a modification of this example another membrane was produced using a reaction time of one hour instead of 30 minutes. The resultant membrane was excellent in every way.
  • a defective polypropylene hollow fibre porous membrane cartridge leaked in many tubes when water was applied at only 40 kPa. As such a cartridge should not leak at 300 kPa it was apparent that there were many over-sized pores present in the membranes. Thus the object of the example was to seal the defective larger pores by position. As there were over 30% leaks, heat sealing and blocking off each end of a tube was uneconomical. Other requirements of the finished cartridge were that it must withstand concentrated hydrochloric acid, it must wet readily and it must possess no pore over 0.5 micron in diameter. The emulsion process of the previous examples was used except that the emulsion was made coarser by using:
  • the cartridge at 125 kPa gave an 80% rejection of 0.1% B.P. FEDARO M soluble cutting oil at 254 litres per square metre per hour.
  • the cartridge was saturated with a 2% weight per volume aqueous solution sodium phosphate (Na 3 P0 4 .12H 2 0) and 0.2% ethoxylated octylphenol and dried with air at 60°C.
  • a 2% weight per volume aqueous solution of zirconium chloride (Zr0 2 Cl 2 .6H 2 0) was then poured down the fibres under gravity and left for 30 minutes.
  • the fibres were then washed with water and testing at 125 kPa with 0.1% FEDARO M cutting oil gave a permeation rate of 87 litres per square metre per hour but 100% rejection of visible oil.
  • OMPI hydrophilic base The phosphate was washed out from untreated polypropylene.
  • the zirconium phosphates resist ION hydrochloric acid, chlorine and most chelating agents. They may be washed out with hydrofluoric solution and redeposited.
  • All the fibres used in the following examples 4 to 9 were from the same batch of polypropylene. Their internal diameter was 200 microns and their external diameter was 600 microns. The porous walls had an average pore size of 0.2 microns. Bubble points varied- between 220 and 320 kPa, when using air and water.
  • the polypropylene fibres were soaked in a solution of 5% l,2-bis(3-aminopropylamino)ethane and 1% p- tertiaryoctylphenoxypolyethyleneglycolether (I.C.I. TERIC X10) in ether for 15 minutes. After drying in air for 3 minutes the fibre was soaked in a solution of 5% I.C.I. SUPRASEC 5005 (the first component of the polyurethane) in acetone for 1 hour. It was then dried for 15 minutes at r ONTI
  • the polypropylene porous, hollow fibres were soaked in 5% CIBA-GEIGY ARALDITE LCI91 (the first component of the resin) in acetone, dried in air for 3 minutes and then soaked for 2 hours in a solution of 5% l,2-bis(3- aminopropylamino) ethane and 1% TERIC X10 in ether. After the standard wet/dry sterility test hydrophilicity was good but a greater bubble-point test showed selective blocking of the larger pores. Selective blocking is against thermodynamic prediction and is economically more important when obtained simultaneously with hydrophilicity than either selective blocking or hydrophilicity.
  • Polypropylene fibres were soaked in a solution of 5g of resorcinol (the first component of the resin) and 2.5 ml of diethyleneglycol in 20 ml. of ethanol. They were dried at 65°C for 30 minutes and soaked for 1 hour in a 1:1 mixture of ION hydrochloric acid and 40% formaldehyde, (the second component of the resin) , redried as before, rinsed with 10% aqueous sodium hydroxide then water and then soaked for 2 hours in a solution of 5% chloroacetic acid in ethanol. The treated fibres were given the standard test and showed good hydrophilicity as well as the highly desirable increase in bubble-point without loss of much permeation rate. Similar coatings were obtained from:-
  • Polypropylene hollow fibres were soaked for 10 minutes in a solution of 5% l,2-bis(3-aminopropylamino)ethane (the first component of the polyamide) in ether and dried in air for 3 minutes. They were then soaked for 10 minutes in 5% terephthaloylchloride (the second component of the polyamide) in ether, again dried and soaked in a solution of 2% JEFFAMINE M2005 in acetone for 15 hours. After the standard test hydrophilicity was excellent.
  • Polypropylene hollow fibres prewetted with ethanol then water were impregnated with a solution of 1.5% polyvinylalcohol (Molecular Weight 15,000) (the first component of the resin) in water by forcing the solution through the pores. They were dried at 65°C for 2 hours and soaked for 3 hours in a solution of 1% SUPRASEC 5005 (the second component of the resin) and 0.16% triethylenediamine in N-methyl-2-pyrrolidone.
  • SUPRASEC 5005 the second component of the resin
  • the chemical structure is a form of polyurethane. After the standard sterility cycle the hydrophilicity was good and the bubble-point was raised desirably, showing blocking of the larger pores.
  • the methods of the invention provide good control of pore size and distribution, good control of hydrophilic distribution and supply of functional groups can be obtained on cheap hydrophobic porous supports. Physical faults in such cheap porous supports can be corrected without recourse to monomolecular layers or surface chemical changes of the hydrophobic base.
  • the methods of the invention form adherent coatings, networks and interstitial porous precipitates and in so doing form novel membrane products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP19840903426 1983-09-12 1984-09-12 Traitement de membranes poreuses. Withdrawn EP0156840A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AU1368/83 1983-09-12
AUPG136883 1983-09-12
AUPG175983 1983-10-10
AU1759/83 1983-10-10

Publications (2)

Publication Number Publication Date
EP0156840A1 EP0156840A1 (fr) 1985-10-09
EP0156840A4 true EP0156840A4 (fr) 1987-07-08

Family

ID=25642704

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840903426 Withdrawn EP0156840A4 (fr) 1983-09-12 1984-09-12 Traitement de membranes poreuses.

Country Status (2)

Country Link
EP (1) EP0156840A4 (fr)
WO (1) WO1985001222A1 (fr)

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JPS61161103A (ja) * 1985-01-10 1986-07-21 Terumo Corp 親水性多孔質膜およびその製法
JPS61283305A (ja) * 1985-06-05 1986-12-13 Ube Ind Ltd 多孔質中空糸膜
US4774132A (en) * 1986-05-01 1988-09-27 Pall Corporation Polyvinylidene difluoride structure
DK169616B1 (da) * 1986-08-27 1994-12-27 Dow Danmark Permeabel, porøs, polymerbehandlet plastmembran med hydrofil karakter, fremgangsmåder til fremstilling heraf samt anvendelse heraf
JP2646685B2 (ja) * 1988-08-11 1997-08-27 三菱瓦斯化学株式会社 感湿素子
CN1045756A (zh) * 1989-03-18 1990-10-03 王英 全自动动力形成膜净水***
US5136274A (en) * 1990-02-01 1992-08-04 Mitsubishi Gas Chemical Company, Inc. Humidity sensor
JPH08502534A (ja) * 1992-10-21 1996-03-19 コーネル リサーチ ファウンデーション、インコーポレーテッド 多孔物質の細孔サイズ選択的修飾法
US5627217A (en) * 1993-06-29 1997-05-06 Minnesota Mining And Manufacturing Company Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups
IL109840A (en) * 1993-06-29 1998-02-22 Minnesota Mining & Mfg Interfacial polymerization in a porous medium and intermediates bearing photochemical functional groups
DE10228148B4 (de) * 2002-06-24 2006-08-24 Saehan Industries Inc. Selektive Membran mit hoher Fouling-Beständigkeit
CN117654288B (zh) * 2024-02-01 2024-04-19 蓝星（杭州）膜工业有限公司 复合膜及其制备方法和应用

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DE2537389A1 (de) * 1975-08-22 1977-02-24 4 P Verpackungen Gmbh Verfahren zum herstellen einer filtrationsmembran aus kunststoff, filtrationsmembran, filtrationsmatte, hergestellt unter verwendung einer filtrationsmembran und filtrationssystem zur filtration waessriger loesungen und dispersionen
FR2361439A1 (fr) * 1976-08-10 1978-03-10 Sumitomo Electric Industries Structures poreuses hydrophiles de resine fluorocarbonee et leur procede de preparation
US4239714A (en) * 1978-11-15 1980-12-16 Washington University Method for modifying the pore size distribution of a microporous separation medium
EP0117919A2 (fr) * 1982-12-24 1984-09-12 Toray Industries, Inc. Procédé de traitement de membranes semi-perméables

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US3744642A (en) * 1970-12-30 1973-07-10 Westinghouse Electric Corp Interface condensation desalination membranes
DE2537389A1 (de) * 1975-08-22 1977-02-24 4 P Verpackungen Gmbh Verfahren zum herstellen einer filtrationsmembran aus kunststoff, filtrationsmembran, filtrationsmatte, hergestellt unter verwendung einer filtrationsmembran und filtrationssystem zur filtration waessriger loesungen und dispersionen
FR2361439A1 (fr) * 1976-08-10 1978-03-10 Sumitomo Electric Industries Structures poreuses hydrophiles de resine fluorocarbonee et leur procede de preparation
US4239714A (en) * 1978-11-15 1980-12-16 Washington University Method for modifying the pore size distribution of a microporous separation medium
EP0117919A2 (fr) * 1982-12-24 1984-09-12 Toray Industries, Inc. Procédé de traitement de membranes semi-perméables

Also Published As

Publication number Publication date
WO1985001222A1 (fr) 1985-03-28
EP0156840A1 (fr) 1985-10-09

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