Source: http://www.google.de/patents/US8057574?hl=de
Timestamp: 2013-05-26 09:01:40
Document Index: 213344398

Matched Legal Cases: ['Application No. 2003903507', 'Application No. 2006261581', 'Application No. 2', 'Application No. 200680022006', 'Application No. 2006', 'Application No. 04737543', 'Application No. 0229019', 'Application No. 0575700', 'Application No. 2008', 'Application No. 2008', 'Application No. 563980', 'Application No. 563980']

Patent US8057574 - Membrane post treatment - Google PatenteSuche Bilder Maps Play YouTube News Gmail Drive Mehr » Erweiterte Patentsuche | Webprotokoll | Anmelden Erweiterte Patentsuche PatenteThe invention relates to polymeric ultrafiltration or microfiltration membranes of, for instance, Halar, PVDF or PP, incorporating PVME or vinyl methyl ether monomers. The PVME may be present as a coating on the membrane or dispersed throughout the membrane or both. The membranes are preferably hydrophilic...http://www.google.de/patents/US8057574?utm_source=gb-gplus-sharePatent US8057574 - Membrane post treatment Ver�ffentlichungsnummerUS8057574 B2PublikationstypErteilung Anmeldenummer12/647,734 Ver�ffentlichungsdatum15. Nov. 2011Eingetragen28. Dez. 2009 Priorit�tsdatum8. Juli 2003Auch ver�ffentlicht unterCA2530805A1CN1819867ACN1819867BEP1654053A1EP1654053A4US7662212US8262778US20060157404US20100213117US20110290717WO2005002712A1 Ver�ffentlichungsnummerUS 8057574 B2US 8057574B2US8057574 B2US8057574B2 ErfinderDaniel MulletteJoachim MullerNeeta PatelUrspr�nglich Bevollm�chtigterSiemens Industry, Inc.Siemens Water Technologies Holding Corp. US-Klassifikation95/4555/DIG.500427/244210/640210/500.2896/14427/430.196/5496/11427/33196/1396/4210/651210/500.2755/524210/490210/650427/245210/500.42Internationale KlassifikationB01D71/34B01D39/20B01D71/32B01D71/82B01D71/26B01D69/14B01D71/38B01D67/00B01D53/22 UnternehmensklassifikationB01D2323/34B01D2323/02B01D67/0088B01D67/009B01D2323/30B01D71/32B01D71/34B01D2323/283B01D69/02B01D71/26B01D2323/10B01D67/0011B01D2323/12 Europ�ische KlassifikationB01D71/32B01D71/26B01D67/00R16B01D67/00R14B01D69/14BB01D67/00K14BB01D71/34B01D69/02ReferenzenPatentzitate (104)Nichtpatentzitate (47)Externe LinksUSPTO USPTO-Zuordnung EspacenetMembrane post treatmentUS 8057574 B2 Zusammenfassung The invention relates to polymeric ultrafiltration or microfiltration membranes of, for instance, Halar, PVDF or PP, incorporating PVME or vinyl methyl ether monomers. The PVME may be present as a coating on the membrane or dispersed throughout the membrane or both. The membranes are preferably hydrophilic with a highly asymmetric structure with a reduced pore size and/or absence of macrovoids as a result of the addition of PVME. The PVME maybe cross-linked. The invention also relates to methods of hydrophilising membranes and/or preparing hydrophilic membranes via thermal or diffusion induced phase separation processed.
1. A method of making a hydrophilic membrane prepared from a polymeric material, comprising preparing a dope comprising the polymeric material and a compatible at least partially water soluble polymeric hydrophilising agent comprising vinyl methyl ether monomers to produce a hydrophilic membrane comprising the polymeric material and poly(vinyl methyl ether).
2. A method according to claim 1 wherein the at least partially water soluble polymeric hydrophilising agent is soluble in an amount of at least 5-10 g/l at standard temperature and pressure.
3. The method according to claim 1, further comprising crosslinking the poly(vinyl methyl ether).
4. The method according to claim 3, wherein crosslinking the poly(vinyl methyl ether) comprises exposing the hydrophilic membrane to irradiation.
5. The method according to claim 1, wherein the dope comprises between 0.1 weight % and 2.5 weight %.
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of and claims priority to U.S. nonprovisional patent application Ser. No. 10/564,024 filed on Jan. 9, 2006, issued as U.S. Pat. No. 7,662,212 B2 on Feb. 16, 2010 titled MEMBRANE POST TREATMENT which is a U.S. national stage application and claims the benefit under 35 U.S.C. �371 of International Application No. PCT/AU2004/000922 filed on Jul. 8, 2004, entitled titled MEMBRANE POST TREATMENT, which is based on Australian Patent Application No. 2003903507 filed on Jul. 8, 2003, entitled MEMBRANE POST TREATMENT, each of which is entirely incorporated herein by reference for all purposes, and to which this application claims the benefit of priority.
FIELD OF THE INVENTION The invention relates to compositions and methods for the hydrophilisation of membranes, particularly hollow fibre membranes for use in microfiltration and ultrafiltration. The invention also relates to membranes prepared in accordance with these methods.
BACKGROUND ART The following discussion is not to be construed as an admission with regard to the common general knowledge.
Hydrophobic surfaces are defined as �water hating� and hydrophilic surfaces as �water loving�. Many of the polymers used in the manufacture of porous membranes are hydrophobic polymers. Water can be forced through a hydrophobic membrane, but usually only under very high pressure (150-300 psi). Membranes may be damaged at such pressures and under these circumstances generally do not become wetted evenly.
Hydrophobic microporous membranes are characterised by their excellent chemical resistance, biocompatibility, low swelling and good separation performance. Thus, when used in water filtration applications, hydrophobic membranes need to be hydrophilised or �wet out� to allow water permeation. Some hydrophilic materials are not suitable for microfiltration and ultrafiltration membranes that require mechanical strength and thermal stability since water molecules present in the polymer can play the role of plasticizers.
BRIEF DESCRIPTION OF THE FIGURES FIG. 1 depicts the results of leaching tests for PVME in accordance with the present invention.
DESCRIPTION OF THE INVENTION The present applicants have found that, in certain cases. Poly(VinylMethylEther) (PVME) can be used to modify, and in particular, reduce, the hydrophobicity of certain hydrophobic membranes. The PVME can be incorporated either by means of post-treatment, such as by soaking hollow-fibre membranes in a solution of PVME, or by incorporating PVME into the dope solution for forming the membrane. Either approach could be demonstrated for a variety of reaction types, including different types of membranes such as Poly(vinylidene fluoride) (PVDF). Poly(ethylene-chlorotrifluoroethylene) sold under the trademark HALAR and Poly(propylene) (PP).
PVME as a post-treatment was found to make PVDF and Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) membranes hydrophilic, although the treatment was also useful on PP membranes.
As used herein. PVME also encompasses not only the polymeric form of the product, but also the monomeric form of the compound, namely vinylmethyl ether, as well as di-, tri-, and oligomeric forms.
SUMMARY According to a first aspect, the invention provides a polymeric ultra or microfiltration membrane incorporating PVME. The polymeric ultra or microfiltration membrane may incorporate a coating of PVME or, alternatively include a homogeneous dispersion of PVME throughout the polymer or both.
The polymeric ultra or microfiltration membranes preferably contain 0.4 to 30 with % PVME.
Preferably, the at least partially water soluble polymeric hydrophilising agent is soluble in an amount of at least 5-10 g/l at standard temperature and pressure.
Preferably, the at least partially water soluble polymeric hydrophilising agent contains vinylmethyl ether monomers. More preferably, the polymeric hydrophilising agent is polyvinylmethyl ether (PVME).
The polymeric material may be a formed membrane treated with a solution of PVME. Preferably, the polymeric material is treated with a solution of PVME at a concentration and for a time sufficient to allow PVME saturation of said membrane to take place. In one preferred embodiment, the polymeric material is post treated by soaking in a solution of PVME in ethanol. In another preferred embodiment, the polymeric material is post treated by soaking in a solution of PVME in water
It is preferred that the concentration of PVME is less than 10%, more preferably less than 5% and even more preferably less than 3%, however it is preferred that the concentration of PVME is greater then 0.1%.
PVME was surprisingly found to be effective at hydrophilising otherwise hydrophobic PP, PVDF and Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) membranes either by soaking the membrane as a post treatment or by including the PVME as a hydrophilising agent incorporated in the membrane dope. Hydrophilisation can be achieved either by soaking the membranes in a solution of PVME in a suitable solvent, for example, ethanol or water, preferably at a level greater than 0.5 wt %. PVDF and Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) membranes in particular demonstrate long term stability with PVME adsorbed onto the surface, although PVME also appears to have good affinity with PP. Leaching tests show minimal leaching of PVME from the membranes after 10 days with the PVDF and Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) samples are all still hydrophilic after this period of time.
Including PVME into the dope via a TIPS process was also successful in imparting hydrophilicity to the membranes. The proportion of PVME in the dope was most preferably between 0.1 and 0.5%, although this is dependent upon the amount of non-solvent in the dope. If the proportion of non-solvent used was lower than 60 wt % a larger amount of PVME could be incorporated into the dope. Surprisingly, it was found that the introduction of PVME into membrane dope induced structural changes in the membranes, such as increased asymmetry and smaller pores in addition to imparting hydrophilicity to the membrane.
PVDF and fluoropolymers with a similar structure (e.g. PVC, PVF, and PVDC) are known to undergo some cross-linking upon irradiation with electrons or γ-radiation and similar crosslinking with PVME is also possible. Those skilled in the art will appreciate that when y-radiation is used on fluoropolymers, caution must be taken because there is possibility of chain scission (degradation).
EXAMPLES Post Treatment Studies The post-treatment of a variety of membranes with a cross-linkable hydrophilising agent was investigated, PVDF, Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) and PP membranes were all tested. For the Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) membranes, both MF (microfiltration) and UF (ultrafiltration) membranes were tested.
The membrane was then tested for the �wicking� of an aqueous solution of dye and the permeability of the fibre was also tested.
PVDF�Wicking and Permeability results
PVME in
after PVME
after 65� C.
The results in Table 1 demonstrate that PVDF is made hydrophilic by PVME post-treatment. Different concentrations of PVME (0-3 wt %) in water or in ethanol were investigated. The concentration of PVME in solution appears unimportant provided it is above a certain critical value, which is believed to be about 0.1%. There would appear to be little benefit in using more than 0.5% PVME. It is pox postulated that this may be dependent upon the fibre density in the solution, or in other words the ratio of available membrane surface area to free solution, since if PVME is adsorbing to the membrane surface there is a minimum PVME quantity in solution required to obtain a totally hydrophilic membrane surface. There will simply be no room on the membrane surface for any excess PVME to adsorb and as a consequence will be washed out of the membrane upon filtration.
PP�Wicking and Permeability results
Poly(ethylene-chlorotrifluoroethylene) (sold under the
trademark HALAR)�Wicking and Permeability results
The results from the Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) membranes are difficult to quantify with precision because it is believed that glycerol in the pores results in lower initial clean water permeabilities that slowly increase towards a fixed value as the glycerol is completely removed from the pores. This may explain why the ethanol washed fibres have a slightly higher apparent permeability, since glycerol is more readily soluble in ethanol than in water.
Leaching tests were conducted by soaking the fibres in reverse osmosis (RO) water for 240 hrs. The leach water was refreshed every 24 hours (the wash water being replaced a total of 9 times) and an aliquot was analysed by UV-Vis absorption and compared against a PVME calibration curve. The results above show that there is an immediate decline in the detection of PVME which this occurs for both wet and dry standards as well as for all samples. The biggest decline comes from the samples soaked in PVME, while of these samples the fibres soaked in 1 wt % ethanolic PVME have the lowest starting concentration. The general trend appears to be that some MIME leaches out immediately but after approximately 48 hrs there is no significant change in the PVME level in the wash water compared to the standard. As described above however, the change in the concentration cannot be considered significant compared to the standards on the basis of this examination.
MEMBRANE PERMEABILITY BEFORE AND AFTER
Ethanol washed Blank�
1 wt % PVME in Ethanol�
1 wt % PVME in Water�
Dry Blank�
PVME was added to standard TIPS PVDF or TIPS Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR) dope in proportions varying from 0 to 1 wt %. The TIPS extrusion was operated in a continuous process (although there is nothing to prohibit its use in batch processes if desired). For PVDF, PVME was dissolved into the solvent/non-solvent mixture of GTA and diethylene glycol, triethylene glycol or 1,4-butanediol. For Poly(ethylene-chlorotrifluoroethylene) (sold under the trademark HALAR), PVME was simply dissolved in GTA. PVME is highly soluble in GTA but insoluble in more polar compounds like diethylene glycol, triethylene glycol and 1,4-butanediol.
HALAR 901
Solef 1015�
GTA�
Break Force/
unit area (N/mm2)
4838 1440 301
1367 707
Three dopes were prepared with the compositions listed in Table 6 below. Two different proportions of PVME a 1 wt % and 2.5 wt %) were compared with a DIPS PVDF dope that contained poly(vinylpyrrolidone-vinylacetate) (S630) as an alternative additive. These fibres were all extruded in an identical manner and the results are compared below.
The SEMs in FIG. 5 demonstrate the trend apparent from the fibre properties�adding PVME to the structure decreases the formation of macrovoids. Less than a 0.4 wt % replacement of S630 with PVME is required to induce a dramatic change in properties however, as demonstrated by the DIPS examples.
All samples wicked water quite thoroughly, and there was no difference observed from the hydrophilicity of the standard formulation. The permeability measurements were conducted without a �wetting� step�a manual wetting out of the membrane with ethanol. The permeability of 2.3 wt % PVME samples appears to increase over 0.4 wt % PVME samples. Since the bubble point is the same for these two samples while permeability varies, it can be seen that increasing the PVDF concentration and adding different PVME concentrations allow a UF membrane with a high permeability to be produced.
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