Gas separation: processes – Selective diffusion of gases – Selective diffusion of gases through substantially solid...
Reexamination Certificate
2001-02-07
2003-06-17
Spitzer, Robert H. (Department: 1724)
Gas separation: processes
Selective diffusion of gases
Selective diffusion of gases through substantially solid...
C096S006000, C096S013000, C096S014000, C096S224000, C096S225000, C055S524000, C055SDIG005
Reexamination Certificate
active
06579342
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to filtration media having both hydrophobic (water repellent) and oleophobic (oil repellent) properties. The properties are produced by forming a fluorosulfone oligomer coating on a substrate such as a hydrophobic or hydrophilic membrane or other filtration medium. The invention also relates to methods of preparing such filtration media.
BACKGROUND OF THE INVENTION
Hydrophobic filters are used in filtration of gases, in venting filters, and as gas vents. These hydrophobic filters allow gases and vapors to pass through the filter while liquid water is repelled by the filter.
Polytetrafluoroethylene (PTFE) has been the most commonly used material in filters for gas venting. PTFE is chemically and biologically inert, has high stability, and is hydrophobic. PTFE filters therefore allow gases to be selectively vented while being impervious to liquid water.
Hydrophobic membranes are used as filters in healthcare and related industries, for example, as vent filters for intravenous (IV) fluids and other medical devices. In the healthcare industry, the membrane is sterilized before use. PTFE membranes can be sterilized for these health-related applications with steam or by chemical sterilization without losing integrity.
Treating PTFE membranes with steam can cause pore blockage due to condensation of oil from the machinery used to generate the steam. The resulting loss of air permeability reduces the membrane's ability to serve as an air vent. Although chemical sterilization minimizes exposure of the membrane to oil, chemical sterilization uses toxic chemicals and can generate byproducts which cause waste disposal problems. Ionizing radiation has also been used for sterilization of materials used in medical and biological devices. PTFE may become unstable when exposed to ionizing radiation. Irradiated PTFE membranes have greatly reduced mechanical strength and cannot be used in applications where they are subjected to even moderate pressures.
Perhaps the two biggest drawbacks to PTFE as a filter for venting gases are the high cost and the low air permeability of PTFE membranes. PTFE membranes are formed by extruding and stretching PTFE. Both the PTFE raw material and the processing to form the PTFE membrane are expensive. Furthermore, the extruding and stretching processes used to form PTFE membranes create a membrane which has relatively low air permeability.
The oleophobicity of PTFE can be improved by impregnating or coextruding the PTFE with siloxanes (for example, U.S. Pat. No. 4,764,560), fluorinated urethane (U.S. Pat. No. 5,286,279), or perfluoro-2,2-dimethyl-1,3-dioxole (U.S. Pat. No. 5,116,650). Although the oil resistance of the PTFE is improved, the treated PTFE membranes are expensive, and air permeability remains fairly low.
As a result, efforts have been made to identify alternative substrates which are less expensive and have higher air permeability than PTFE and which can be modified to be hydrophobic and oleophobic.
Coating filtration substrates allows one to retain the desirable bulk properties of the substrate while only altering the surface and interfacial properties of the substrate. Coating substrates to increase their hydrophobic and oleophobic properties has not been very practical, because the coatings can reduce permeability. Furthermore, many of the coating materials are expensive.
Scarmoutzos (U.S. Pat. No. 5,217,802) modified the surface of substrates made of nylon, polyvinylidene difluoride (PVDF), and cellulose by treating the substrate with a fluorinated acrylate monomer. The substrate was sandwiched between two sheets of polyethylene, and the monomer was polymerized by exposing to ultraviolet light. The resulting composite filters had hydrophobic and oleophobic surfaces. The air permeability of the filters decreases with time.
Moya (U.S. Pat. No. 5,554,414) formed composite filters from polyethersulfone and PVDF membranes with a method similar to that of Scarmoutzos. The resulting filters did not wet with water or hexane. The disadvantage of the Moya filters is that air permeability of the treated filters was lower than the untreated substrates, and the fluorinated monomer is expensive.
Sugiyama et al. (U.S. Pat. No. 5,462,586) treated nylon fabric and PTFE membranes with solutions containing two different preformed fluoropolymers. The treated filters were resistant to water and oils. The durability of filters coated with preformed polymers is often less than that for filters where the coating is formed by polymerizing a monomer on the surface of the substrate, however.
Kenigsberg et al. (U.S. Pat. No. 5,156,780) treated a variety of membranes and fabrics with solutions of fluoroacrylate monomers and formed coatings on the substrate by polymerizing the monomer. The coating conferred oil and water repellency onto the substrate. However, the airflow through the treated membrane was reduced, compared to the untreated membrane.
Hydrophobic media suitable for garments have been made by extruding mixtures of polypropylene or PTFE and the fluorochemical oxazolidinone as disclosed in U.S. Pat. No. 5,260,360. The media made by extrusion tend to have relatively low air permeability.
In copending U.S. application Ser. No. 09/323,709 filed Jun. 1, 1999, now U.S. Pat. No. 6,355,081 issued Mar. 12, 2002 (incorporated herein by reference in its entirety), oleophobic and hydrophobic filters are prepared by forming a polydimethylsiloxane coating on a polymeric substrate by polymerizing vinyl terminated siloxane with a crosslinker such as hydrosilicon in the presence of a catalyst.
SUMMARY OF THE INVENTION
There is a need for an oleophobic and hydrophobic filter which is inexpensive and has high air permeability. Specifically, there is a need for a coating for filter medium substrates that makes the substrate oleophobic and hydrophobic, and also a need for a more cost-effective process of making oleophobic filters.
In a first embodiment of the present invention, an oleophobic filter is provided including a substrate and a coating, the substrate including a polymer and the coating including a fluorosulfone oligomer capable of being covalently bonded to the polymer, wherein the substrate is rendered oleophobic by grafting the fluorosulfone oligomer to the substrate.
In various aspects of the first embodiment, the polymer includes a polysulfone, for example, a polyalkylsulfone, a polyethersulfone, and a polyarylsulfone. The polymer may also include a polyvinylidene fluoride, a polyethylene, poly(tetrafluoroethylene), a poly(tetrafluoroethylene-co-ethylene), a polyamide, a polyacrylate, a polymethacrylate, a polyester, a polypropylene, a nylon, or a polyurethane.
In another aspect of the first embodiment, the substrate includes a porous membrane. The porous membrane may include an isotropic membrane or anisotropic membrane, such as an asymmetric membrane. If the substrate is an asymmetric membrane, the asymmetric membrane may have a supporting structure, a first porous face and a second porous face, each porous face having pore diameters, wherein an asymmetry between the pore diameters of the first porous face and the second porous face is at least about 2:1, at least about 5:1, or at least about 10:1. The supporting structure may also include an isotropic region adjacent the second porous face, the isotropic region having substantially constant pore size, the supporting structure further including an asymmetric region adjacent the isotropic region. The asymmetric region may extend through at least about 50% of the supporting structure but not more than about 85% of the supporting structure. The average diameter of the pores of the second porous face may be between about 0.01 &mgr;m and about 50 &mgr;m, between about 0.01 &mgr;m and about 10 &mgr;m, or may be less than about 0.01 &mgr;m.
In a further aspect of the first embodiment, the polymeric substrate includes a material including a nonwoven material, a woven material, or a melt blown material.
In another aspect of the first embodiment, the fluorosulfone oligom
Palpallatoc Jeff
Wang I-fan
Knobbe Martens Olson & Bear LLP
Pall Corporation
Spitzer Robert H.
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