TW201024346A - Hydrophilic porous polymer blend membrane - Google Patents

Abstract

The invention relates to a hydrophilic porous polymer membrane comprising a polyolefin polymer and a hydrophilic component, optionally with a surfactant. The membrane being obtainable by blending the components with a solvent and extruding the blend. The invention further relates to a process of manufacturing the membrane and various uses of the membrane.

Description

201024346 VI. Description of the Invention: I [Technical Field of the Invention] j The present invention relates to a hydrophilic porous polymer film. More specifically, the present invention relates to a polyolefin film obtained by blending a polyolefin polymer and a hydrophilic component with a solvent and then a blend. Furthermore, the invention relates to a method of making and using the film. L 4 Chair 3 Polymer film can be widely used for separation, filtration and concentration of solutions, suspensions and gases. It has a wide range of applications and can be used in several applications such as gas filtration and liquid filtration such as microfiltration, ultrafiltration, nanofiltration, and for reverse osmosis, electrodialysis, electrodeionization, membrane extraction, and pervaporation. . Examples of applications include wastewater purification, fuel cells, controlled release of pharmaceutical components, batteries, filters, and humidifiers. Most of the polymer film is made of a hydrophobic material such as polyethylene (poly), polypropylene (fluorene), poly(difluoroethylene) (PVDF), and polytetrafluoroethylene (PTFE). These membranes are not suitable for use in water filtration because the polymer is hydrophobic and therefore requires a relatively high pressure gradient to force water through the membrane due to the high capillary forces in the hydrophobic membrane pores. In addition, hydrophobic surfaces are more prone to fouling than hydrophilic surfaces. Some membranes are inherently hydrophilic, such as membranes of cellulose-acetate and urethane-resistant materials. However, this cellulose-acetate film is more easily degraded by an enzyme, and nylon itself has a drawback in that it is difficult to prepare a high-porosity film. Conversely, many hydrophobic polymers are inherently stable. Therefore, methods for producing a more hydrophilic hydrophobic film have been developed for a long time, thereby maintaining stability and improving flux. 201024346 Several methods have been used to achieve hydrophilicity of hydrophobic membranes by surface modification. Examples are surface grafting by redox initiators, chemical treatments, chemical grafting, arc treatment, photochemical treatment, toothing, plasma treatment, and copolymerization. 5 One of them is to use plasma treatment (ie, gas plasma treatment) to modify the surface of the membrane. Plasma treatment can destroy or alter the original structure. In another method, a coating based on a hydrophilic acrylate monomer is applied or grafted onto a surface. Further, a polymer blend in which a hydrophilic and hydrophobic polymer is mixed and processed into a film is used. _ 10 It is also recommended to blend hydrophilic and hydrophobic polymers. However, as a result, the porosity and structure of the hydrophobic film itself are completely changed as compared with the film based only on the hydrophobic polymer. In addition, the natural incompatibility of hydrophobic (e.g., highly crystalline UHMWPE) and hydrophilic polymers may result in a phase separation, and it is difficult to obtain the desired water transport properties. 15 In WO2005/069927, it is proposed to electrically conduct micro-multi-hole and giant multi-hole films. The film comprises an ultra high molecular weight polyolefin, a carbon electrochemically activated powder, a conductive agent, and optionally a hydrophilic additive. It is recommended that a wide range of ® hydrophilic additives include inorganic powders and secondary polymers. The film is prepared by preparing a mixture of ultrahigh molecular weight polyethylene, a carbon-containing electrochemically activated powder, a passivating agent and a plasticizer, and reducing the film thickness by calendering, blown film or cast film. Squeeze the mixture before. The disclosure of W02005/069927 is not supported by experimental operations. JP 2002-194133 (Publication No.) discloses a porous film for a separator of a lithium battery or a capacitor. The film consists of a polyolefin resin and a second polymer selected from the group consisting of a hydrophilic polymer and a macromolecule. Presenting the example The embodiment describes the ultrahigh molecular weight polyethylene as polyethylene glycol dimethyl acrylate. The film was prepared by subjecting a mixture of hot pressed polyethylene, polyethylene glycol dimethyl acrylate vinegar and sarcophagus to stretching and annealing before removing the sarcophagus. The scope of other second polymers is not disclosed. It is known in the art that small molecules such as alcohols and/or interfaces (4) can hydrophilize different hydrophobic PE membranes to obtain a water flux. However, this basic hydrophilicity is only maintained for several hours and is clearly indicated to be suitable for long-term use (1-4 years). Another way to pass water through the hydrophobic membrane is to use a high pressure, i.e., the pressure at which the water passes through the pressure. A substantially commercial polyethylene film (Solupor® grade 7P03A exhibits a basic water passing pressure of about 22 bar and no water flux at a pressure below 2 bar). It can be wetted with a monol or an surfactant to obtain an initial water flux of about 3300 l/m2h, but this is only a short-acting effect. Therefore, both the film and its process are expected to be further improved. SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved hydrophilic membrane. Another object of the present invention is to provide a method of making a modified hydrophilic film. Still another object of the present invention is to provide an advantage of using the film. The improvement of the present invention may be, for example, one or more of the following: the need to pretreat the membrane is less important or to prevent the need for lengthy pretreatment, increase the long-term hydrophilicity of the membrane, reduce the cost of the membrane or membrane, and safely produce The process increases the strength or reproducibility of the film and increases the water flux available to the hydrophilic film. 5 201024346 One or more of the foregoing advantages can be understood from a porous polymer film that it comprises (a) a polyolefin polymer' and (b) a hydrophilic component, wherein the hydrophilic component comprises (bl) - Hydrophilic polymer and optional (b2) surfactant. The content of the polyolefin polymer (a) is less than or equal to 98 wt% of the total dry weight of the film (see the following definition) and the content of the hydrophilic component (b) is greater than or equal to 2 wt of the total dry weight of the film. %, and the porous polymer film is hydrophilic. Unexpectedly, the film can be obtained by a blending technique in which the polyolefin polymer (a), the hydrophilic wound (b) and the optional additive are mixed with a solvent to form a gel, a solution. Or a blend in the form of a homogeneous mixture, and then press 10 to extrude the blend. Herein, the membrane is hydrophilic and refers to a membrane having a water flux of at least 15 1/(m2h bar) measured by demineralized water passing through the membrane at 2 ° C in 〇.5 bar (see experimental section).

I: Embodiment; J 15 The term porous in this context means that the membrane has a plurality of open micropores. The average pore size is preferably at least 〇.〇5 μιη. If the average pore size is much lower than 〇.〇5 μιη ', the water flux through the membrane becomes too low for micro-transition. & Holes in this document 〖Inch and average hole size means that the average flow hole size is measured directly or indirectly by air flow technique (unless otherwise specified), as described below in the section on Example 20. It is advantageous to have an average pore size of at least the pottery and it is more advantageous when the average pore size is at least μ4 μηι, 0 which tends to result in a higher water permeability I of the porous hydrophilic membrane. The average pore size / preferably should be less than about 5 μηι to prevent impurities in the water from flowing through the membrane. In particular, an average pore size of less than about 2 μηη or even a flat hole of 201024346 is preferred because the smaller pores tend to be less prone to fouling or irreversible obstruction. For larger holes, reversible penetration is more likely to be successful when using back flushing. It should be observed that the bonding or accumulation of particles within the film during use is desirable in certain applications where the conformation and the initial (four) degree are important and the pore size should not be too low. The optimum hole size is determined by the specific application of the wide range. Therefore, since the pore size of the membrane can be adjusted within a certain range by adjusting the processing parameters and/or the membrane composition without damaging the membrane water permeability, this surprising fact can be tolerated within the respective ranges of the pore size. Used for a variety of advantageous uses. For example, a hydrophilic porous polymer blended ruthenium can have an average pore size of about nm5 nm or higher for reverse osmosis or nanofiltration applications. In a preferred embodiment, the pore size is about 10 nm or higher for ultrafiltration. In another preferred embodiment, the hole size is about 1 〇〇 nm or higher, so that 15 can be used for proper micro-passing action. Preferred pore sizes are about 1 〇μηι or less for particle filtration with high water flux and good separation. In a particularly preferred embodiment - good filtration is allowed in the micro and ultrafiltration ranges - the pore size will be about 1 μηη or lower. The membrane pores should preferably be configured to provide a gas permeability of less than 50 s/50 ml when expressed as Gurley 2 turns. This Gurley number is the time required for a volume of air to pass through a film of a zone and is measured as described in the Examples section. The most anticipated range of Gurley numbers (the best combination of the highest and lowest Gurley numbers) is based on practical applications. In general, it has been found that it is advantageous if the Gurley number is less than 20 s/50 ml and preferably less than 1 〇 ml, which tends to be very useful for some of the effects of 7 201024346. On the other hand, structures that are found to be too open < result in untransferred transport of fluid through the membrane, preferably a Gurley number of at least 〇ml and more preferably greater than s/5〇(6), and a Guriey number of preferably greater than about 1 s/50 mi. The Gurley number is preferably greater than 2 s/5. The total dry weight referred to herein refers to the weight of the membrane other than water and solvent. Thus the total weight includes the polymer, the hydrophilic component, the surfactant, and other optional additives described herein. The weight percentage (wt%) used herein is unless otherwise specified as the total dry weight of the film. The polyolefin polymer can be any of the 1 〇 polymers known in the art of polymer films and newly developed films. The polyolefin polymer is preferably selected from the group consisting of polyethylene, polypropylene, higher polyene or a combination comprising at least one of such polymers, and such physically or chemically treated polymers, such as plasma treatment or copolymerization. The polymer. In one embodiment of the invention, the primary polyolefin polymer comprises at least 15 90 wt% of polyethylene and/or polypropylene, as such polymers are available at suitable grades and provide suitable properties, particularly high molecular weight. grade. This polyalkylene polymer contains ultra-high molecular weight polyethylene (hereinafter referred to as UJJMWPE) which is very good because UHMWPE allows very high strength in film stretching. UHMWPE is a 20 polyethylene having a weight average molecular weight greater than about 5 Å, 〇〇〇 g/mole, such as 500,000 - 20,000,000 g/mole. The lower limit is the (lower) tensile strength required for the film, and the upper limit corresponds to the approximate limit of a material that is too rigid and not easy to handle. This UHMWPE can be a double or a multimodal mixture due to its increased processability. A UHMWPE-based film has the advantage of being highly dimensionally stable under stress and producing a thin micro-porous film with a high porosity of 201024346. In particular, high levels of UHMWPE have been found to be advantageous because UHMWPE can be processed by extrusion and then stretched to form a very strong and loadable film and even when combined with another polyolefin or hydrophilic component A component is a chemically and mechanically stable film (eg, 5 related to thermal cycling and expansion properties). A very useful film exemplified includes those in which at least 40% by weight of the polyolefin polymer (4) is UHMWPE. If a high temperature resistant film is desired, it is advantageous to use a film having at least 70 wt% of the polyolefin polymer (4) as UHMWPE, or even at least 80 wt% of the polyolefin is UHMWPE. In one embodiment, the polyolefin polymer is substantially UHMWPE. The remaining portion of this material is preferably another polyolefin such as high molecular weight polyethylene bake (HMWPE), LLDPE, LDPE, PP and the like. Preferably, a mixture of HMWPE and UHMWPE is used. A preferred polymeric polymer comprises 40-80 wt% UHMWPE and 60-20 wt% HMWPE. HMWPE herein refers to a polyethylene having a molecular weight of from 100,000 to 500,000 g/mole. In another embodiment in accordance with the invention, at least 5 wt% of the polyolefin polymer is HMWPE. At least 20 wt% of the polyolefin polymer (8) is preferably HMWPE, e.g., at least 30 wt% of the polythene is HMWPE because the substantial amount of HMWPE (particularly in combination with UHMWPE) tends to improve the processability of the membrane. Unexpectedly, the introduction of HMWPE allows the pore size of the membrane to be adjusted, so adjusting the amount of UHMWPE and HMWPE thus provides a means of controlling the average pore size of the membrane. It has further been found that for most applications, the polymeric polymer preferably comprises at least 60 wt% HMWPE, and the polyolefin polymer more preferably comprises less than 25 wt% HMWPE to prevent breakage of film properties, such as film Mechanical strength and microstructure. 201024346 In a preferred embodiment of the invention, the primary polyolefin polymer is a hydrophobic polymer of UHMWPE which acts as an autosupporting film. The hydrophilic polymer blend film comprising UHMWPE has the additional advantage that the film exhibits high strength and high porosity. 5 This solvent is at least a part of an organic solvent because it promotes the formation of the blend. Several solvents are available, but it has been found that the use of decalin promotes a suitable combination of film properties, such as processability, pore size, blend homogeneity, and solvent extraction, after extrusion. Other examples of solvents that may be employed are polar or low polarity solvents or solvent mixtures comprising decalin and/or other lipids of Group 10 or aromatic solvents, paraffin (oil) and/or other oils or long chain alcohols or ethers. . The water permeability of the membrane (also known as the water flux through the membrane) is a very important property of the membrane of the present invention, as many separation applications (e.g., humidifiers and water filters) require a significant water flux. It has been found that for most applications, the water flux should be substantially less than at least l〇〇l/(m2h bar). When measured at 0.5 bar, the water flux is preferably at least 400 l/(m2 h bar) and the water flux of at least 800 l/(m2 h bar) is more preferred. In most cases, a water flux of at least 1000 l/(m2h bar) is highly advantageous because it is sufficient for a basic commercial cost hydrophilic membrane. By appropriately selecting the structure, composition and/or composition, the water flux can be relatively high, such as at least 1200 l/(m2h bar) and in some cases, the flux can be as high as 20 10000 l/(m2 h bar) ) or even 50,000 l / (m2 h bar). The respective membranes can have very high throughput, but the basic flux needs to be kept below 2 〇〇, 〇〇〇l / (m2h bar), such as less than 20,000 l / (m2h bar) to achieve reasonable filtration of the membrane effect. In addition, a very high water flux tends to cause a severe blockage or fouling of the membrane, resulting in undesirable flow reduction and filtration capacity. However, this can be avoided by using 201024346 with a reverse flow system such as recoil or pullback. In one embodiment of the invention, the invention relates to a hydrophilic porous polymer membrane having a pore size of about 500 nm or less, while exhibiting a 500 l/(m2h bar) when measured at a pressure of 0.5 bar. The flux. Preferably, this 5 flux is about 1000 1 / (m 2 h bar) or more. Preferably, this flux is achieved with a membrane having a pore size of about 100 nm or less, as the lower pore size further eliminates biofouling. In another preferred embodiment of the present invention, the primary blended polymer package 10 comprises UHMWPE and a hydrophilic porous polymer blend film having a hydrophilic porous polymer film having a thickness of about 200 nm or less. The pore size and a flux of 250 l/(m2 h bar) if measured at a pressure of 〇5 bar, preferably about 500 l/(m2 h bar) or more, and more preferably, hydrophilic porous The polymer blend film has a pore size of about 200 nm or less and a flux of 15 800 l/(m2 h bar) if measured at a pressure of 0.5 bar. The porosity of the film was found to be relatively high. Porosity is defined as (l-BW/(rho xd))*100%, where BW is the basis weight of the film [g/m2], rho is the density of the film [g/m3] and d is the thickness of the film [m] . Apertures of at least 40 vol.% are advantageous in certain applications that limit the demand for water flow. In some instances, 20 having a porosity of at least 80 vol% or even at least 90 vol% is very useful because it provides a very open structure and a high total porosity. A distribution in which the porosity is not uniform is preferred. The most advantageous structure of the membrane is a fibrous layered structure having a substantially parallel outer surface of the membrane. The slate-like structure referred to herein is visually similar to the configuration of the fibrous web 11 201024346. A dough in which certain areas of the web are in contact with adjacent webs and separated by another substance (such as air, solvent or aqueous phase) in other areas. The inspection of the membrane structure is by scanning the electron micrograph of the cross section prepared by cooling the membrane in liquid nitrogen and then impacting it with a knife. A crack (not contacted with a knife) extending from the tip end of the 5 blade forms a sample suitable for inspection. The fiber web is formed from a polyolefin polymer and a non-woven polymeric filament of a hydrophilic component. The web itself is porous but has a porosity that is much lower than the overall porosity of the membrane. The polyolefin polymer and the hydrophilic component are substantially doped in the respective fiber mesh. A method for preparing such a lasagna structure-derived film is proposed, which is prepared by subjecting the film system to subsequent extrusion and stretching. This slate-like structure is highly advantageous for a wide range of separation applications, and it is very surprising that this slate-like structure can be obtained from a film made from a polymer blend having up to at least 35 % by weight of a hydrophilic polymer. For example, it has been found that a film having a lasagna structure as described herein provides excellent filtration properties. 15 This can be inferred but not limited to this inference' because of the highly rounded pore structure, which forces a fluid (gas, water or another fluid) to pass through the membrane along a relatively long path. because! Tb 'very surprisingly despite the highly stratified structure and the entangled pore structure, the very high water flux can be achieved as described elsewhere, which results in a unique high water flow rate and high filtration. The quality of the group is 20. The density of the lamellae-like fiber web can vary and depends on the thickness of the individual webs and the total porosity of the film. In one embodiment, the film has a cross-section of 3 to 15 fiber mesh/30 μηι film which may be disposed substantially parallel to the outer surface of the film. However, the cross-section of the film preferably has a 4 to 12 fiber mesh / 3 〇 12 201024346 μηη, and it is found that when the cross-section of the film has a cross-section of 6 to ι〇/3〇μηι film, it will result in the most Expect a combination of properties. The thickness of the individual fiber webs of this squall-like structure can also vary depending on the density of the web and the total porosity of the film. In an embodiment of the film of the invention, 5 at least 70% of the fiber web has a thickness of from 0.02 to 2.5 μηη parallel to the outer surface of the film. It has been found that when at least 90% of the web has a thickness of from 0. 02 to 25 μηη, it will result in the most desirable combination of properties. Even though the presence of the surfactant (b2) is optional, it is substantially preferred to have the surfactant present in addition to being in contact with food, medical problems or similar acceptable amounts of remaining extractables. This is because the surfactant will bleed out over time in some instances. In the case where an acceptable interface active agent is present, the amount of the surfactant in the blend is substantially at least 1 wt% of the total dry weight of the film prior to extrusion. Preferably, it has at least 3 wt% of the surfactant, and more preferably at least 4 of the total dry weight of the membrane is a 15-interface surfactant. In another aspect, an excessively high amount of surfactant tends to disrupt the mechanical properties of the film and can result in the elution of the surfactant during use, which is substantially unacceptable from a performance and/or contamination standpoint. Therefore, it has been found that in most of the examples, the amount of the surfactant _ should be less than 15 Wt%' and preferably less than 1% of the total dry weight of the film. The practice of the examples has shown that the optimum level of surfactant in the compound is less than 5%. It will be observed that some of the surfactant will be lost by the membrane during processing of the blend to the final film, e.g., between quenching bases (essentially in a solvent bath) or even during film use. The amount of surfactant loss depends on the nature of the surfactant, such as the molecular weight of the surfactant, the melting point/foam point and the domain glass, and the polarity and selectivity of the solvent. However, the loss of the surfactant is substantially limited, and thus measuring the amount of surfactant in the final film can provide an initial level of approximate surfactant in the blend prior to extrusion. In addition, the final film having the composition within the scope of the claim (including the content of the (optional) 5 surfactant) is based on the same technical idea of the present invention, and other films as in the present invention are claimed in the present invention. Apply for a patent.

A wide range of interfacial surfactants can be used in the films of the present invention, but it has been found to be highly advantageous to use a nonionic surfactant having a hydrophilic Q 10 end group and a hydrophilic-lipophilic balance ( The HLB number is about 2 to 1 Å, so the surfactant tends to stabilize the hydrophilic polymer in the polyolefin film without causing a sink in an optimum solvent such as decalin. As used herein, a nonionic surfactant is defined essentially as a molecule containing two structurally different groups having different solubilities in aqueous solution. See Kirk-Othmer Enclycopedia 15 〇f Chemical Technology, online version 5, Volume 10,

Emulsions ‘p. 126, j〇hn Wiley & Sons, Inc., New York, NY, 2001. Edward Kostanek, Published online 18 July 2003 _ (incorporated herein by reference). Conventional HLB grades range from 2 to 2, and lipophilic surfactants have an HLB of less than about 9 and hydrophilic surfactants have a HLB of greater than about 11. The surfactant having an HLB of about 4-6 is substantially w/〇 emulsifier' and the surfactant in the range of 8-18 is substantially a 〇/w surfactant. Preferably, the surfactant is a nonionic hydrophilic surfactant having an HLB number of 36. More preferably, the surfactant is selected from the group consisting of sorbitan monooleate, sorbitan monolaurate, sorbitan tristearyl 14 201024346 vinegar, sorbitol ginseng vinegar, sorbus Sugar alcohol needle oleic acid vinegar, sorbic acid needle pre-stearic acid self-purpose, polyoxyethylene _ stearic acid ether, polyoxyethylene (2) oleyl ether, polyoxyethylene / polyoxygen dilute block copolymer, A mixture of such a mixture and a package of the same. The best surfactant is sorbitol 5 needles monooleic acid s 曰 or this 'face active agent contains sorbitol liver oleic acid vinegar because this surfactant provides excellent combination when combined with decalin to (8) solvent The nature.

In a very preferred embodiment, the hydrophilic component (8) is present in an amount of 10% by weight of the total dry weight of the film, since this allows the film to have more hydrophilic properties. 10 Hydrophilic wounds containing I can be - compounds (in this case it should be a hydrophilic polymer such as oxidized poly (10)) or hydrophilic silk can be composed of two or more hydrophilic! A combination of at least a portion of the other hydrophilic components is selected to achieve at least a portion of other hydrophilic components such as an surfactant. It has also been observed that the total content of the hydrophilic component (8) should preferably be less than 4 〇 15 Wt% of the total dry weight of the film, such as less than 3 G wt%, because the high content of the hydrophilic component will result in the mechanical properties of the film as well as the film. The handling is severely reduced. The hydrophilic polymer is basically selected from the group consisting of oxidized polyethylene (〇χ_ρΕ) (including its specialized street organisms such as ox_UHMWPE, οχ-HMWPE), polyethylene oxide (ΡΕΟ) or polyethylene glycol derivatives, PEjt, Polyacrylic acid, "methyl propylene 20 acid, polycyclopropene, polyethylene glycol, ethyl acetate, vinegar, cellulose and its derivatives 1 sub-amine, polymyramine, polyethylene A combination of benzopyrone, polyethylenimine, polyamine, copolymers thereof, and the like, and combinations comprising at least one of these. More preferably, the hydrophilic polymer (bl) is OX-PE and/or PEO. For films containing 〇χ_ΡΕ, it was unexpectedly found that the average number of acids 15 201024346 (expressed in mg KOH/g ox-PE) tends to be more pronounced in the full ox-PE content. In experimental procedures, it has been found that οχ-ΡΕ has an average acid number of at least 10 mg/g 〇x-PE which is advantageous, but higher values such as at least 30 mg KOH/g ox-PE and more particularly at least 40 mg KOH/gox- PE is very advantageous because of the lower content of ox-PE 5, the higher acid number tends to result in a film having a relatively lower hydrophilicity and a higher water flow than a lower acid number. Surprisingly, the film of ox-PE combined with PEO exhibited very good results. In particular, such membranes tend to have a very high initial water flow rate and a tendency to be very durable water flow rates, i.e., remain high during extended periods of time. It can be deduced (but not limited to this inference) that this high initial water flow rate can be derived from the contribution of PEO content, so the long-term utility of a larger expansion comes from the contribution of PEO content. In addition, PEO also introduces a known and highly anticipated anti-fouling effect. Similarly, the use of surfactants also tends to primarily increase the initial water flow rate. In a preferred embodiment the film comprises at least 2 wt% 〇χ_ΡΕ 15 (bla) and at least 2 wt% PEO (blb). A preferred embodiment of the film of the present invention is a film wherein the content of ox-PE and/or PEO is at least 1% by weight and the content of ox_pE and/or PEO is preferably at least i 5 %. . This allows for a film having a very south initial water flow rate with excellent compatibility and very resistance to fouling. 2〇 The molecular weight of the polymer f is very large (four) depending on the type of hydrophilic polymer. For PEO, it has been found that the weight average molecular weight should be relatively high, such as at least 100,000 g/mole and preferably at least 2 g/mole. The addition of PEO should be observed to promote the anti-fouling properties of the final film. advantageous. For ox-PE, a wide range of molecular weights appears to be acceptable. When 重量_ρΕ 16 201024346 has a weight average molecular weight of about 1000-100,000 g/mole, the best results are obtained for films containing ox-PE. A particularly advantageous group of membranes is a membrane containing oxidized PE as a hydrophilic polymer. In this example, '0X-PE preferably has an average acid number of at least 1〇5 mg/gox-PE, but a higher value such as at least 3〇mg/g of oxidized pE and especially at least 40mg/gox-PE is Very advantageous because, due to the lower content of 〇χ_ΡΕ, a higher acid number tends to result in a film having a relatively lower hydrophilicity and a higher water flow than a lower acid number. The combination of 0Χ_ΡΕ and UHMWPE allows for the use of a film with very high strength and high hydrophilicity, which is very suitable for self-supporting 10 membranes. Since the surfactant is substantially unsuitable for the use of the remaining extractables, such as food contact or other applications that allow the surfactant to move to the body of the animal, it requires a hydrophilic but no interface activity. Membrane of the agent. Unexpectedly, the present invention achieves this film when the hydrophilic polymer is 〇χ_ρΕ requiring only a limited amount of surfactant. In particular, the amount of the surfactant is from less than 1% by weight of the surfactant, such as less than 5% by weight of the interface. More preferably, however, the film does not contain any interfacing agent, i.e., without any interfacing agent. Among the hydrophilic components, it is advantageous to add 20 agents to the polyolefin porous film. For example, for water purification, odor or impurities can be removed simultaneously when filtering water. The electrically conductive material in the hydrophilic membrane can enhance the separation of charge molecules or ions, for example, in an aqueous environment. In addition to the anti-fouling effect of hydrophilic ingredients, other anti-fouling additives extend the life of the film and minimize the need for chemical cleaning. Used to increase the leakage of hydrophilic membranes 17 201024346 Examples of Chen's additives include organic powders such as oxides, oxidized granules, clay, f feng 4" JQ > 夂 aluminum. And the addition of carbon fiber, carbon nanotube, glass fiber or other fiber can facilitate the reinforcement of the hydrophilic porous polymer film, allowing higher ten degrees of freedom and / or increasing the life time of the material, and thus the final disposal At 5 o'clock, the impact on the environment is minimized. The final film can be of any known film shape. In particular, the preferred shape is a low sheet member. This element can be used, for example, in a substantially flat shape or in the form of a tube having a film or layers or a member having a wrinkled (like tone) surface. In another embodiment, the film is a hollow member, i.e., a shape obtained by extrusion through a die having an insert, such as a hollow tube, a hollow box, or a hollow fiber. These preferred shapes allow for a very variable design of the final component containing the film. This element is preferably self-contained and may also be referred to as an autogenous support, i.e., itself provides sufficient support strength to support the weight of the film and the forces generated on the film 15 during use. For the film containing UIiMWPE, this embodiment is the preferred embodiment because of the high strength and rigidity, UHMWPE can be used for relative film design despite the more stringent mechanical requirements of the stand-alone film. In a preferred embodiment, at least a portion of the film is disposed on a support member such that the film forms a flat major surface, a tubular major surface, and/or an enemy major surface. A tubular major surface may be obtained by spirally winding one or more membranes of the present invention or by extruding a tube and optionally, for example, by drawing with pressurized air or liquid. In many applications, the film according to the present invention is disposed in a module, such as an over-twist module comprising the film itself (usually formed into a binary or ternary element by the need of the application of the art known in the art) . Known examples of filter modules 18 201024346 is a convoluted film module or a wrinkle film module. A preferred configuration of the membrane is discussed elsewhere in the present invention. The module further includes a support member and/or frame to protect the filter or to enhance the handling of the filter. This branch building element is basically described in the form for supporting the membrane. This support element can also be used in other separate membranes, such as for further prevention of mechanical damage during use. The frame basically has an outer shape that enhances handling and systems suitable for utilizing the module. In this module, the membrane is the basic component of a device that provides for the separation of the membrane. In most applications, the membrane forms part of a larger system, such as a system for water osmosis cleanliness, a clean room (or a clean room air/air filtration system), a fuel cell, a medical device such as an implant The tablets or tablets are for example suitable for controlling the release and the like. In some instances, the film is as described elsewhere herein but in all instances is disposed in a module that provides a system feature or functionality as a major feature of the overall system, which is essentially the entire The function of the system. For example, a clean room without proper air filtration can be completely useless due to contaminants, and a permeate production plant containing a reverse osmosis membrane. If the water is obtained from sea or surface water, no pre-filter will be useless. The preferred film has a thickness of about 0.5 mm or less, preferably about 0.2 mm or less, such as 1 〇 -1 Torr. A thinner film has the advantage of a potentially higher water flux. In the embodiment of the invention (with respect to the self-supporting film), the film thickness will be about 10 μηη or more, preferably about 2 μm μη or more, to achieve a higher strength. The thickness will generally be about 500 μηη or less, preferably about 200 μηη or less. A suitable film may, for example, have a thickness of about 5 μm, about 1 μm, or about 120 μm 19 201024346. While the film can be self-supporting, several types of the inventive film can be used on a support to ensure sufficient strength. In another embodiment of the invention, the final film may be placed on a support layer during film fabrication or after film preparation, and the film thickness may be about 5 μηη or thicker, 5 preferably about 10 or thicker. 20 μπι or more. Usually, the film has a thickness of about ημηι or less, preferably 5 〇μπι or less. Suitable examples include a laminate comprising at least one support layer selected from the group consisting of non-woven fabrics, woven fabrics, woven mesh, mesh and/or grids such as PET, pp, pTFE, UHMWPE, rayon, inorganic materials such as Metal (such as Shao or not recorded steel) or ceramics 10 or glass. Examples of suitable ceramic and glass layers are ai2o3 and silicates, preferably sintered, porous Α1ζ〇3 and citrate. The layers in the laminate may be, for example, bonded to one another' which may be by ultrasonic welding, gluing, thermal bonding or by 'laser welding. In a preferred embodiment, the hydrophilic porous polymer 15 film according to the present invention is made by mixing less than 90 wt% of the polyolefin polymer based on the total dry weight of the film and a solvent (and optional additives). a) and at least 1% by weight of the hydrophilic component to form a blend. The total dry weight of the film to be observed corresponds to the weight of the non-solvent component of the blend Φ. Next, the blend is extruded and the solvent is removed. Preferably, the solvent is removed by evaporation prior to stretching the base member. In this manner, 20 produces a base member of a unique porous structure that promotes the formation of a layer structure that is highly advantageous in the final drawing operation. The preferred embodiment with respect to the illustrated components and ranges is identical to this embodiment of the first aspect of the invention, and thus can be seen elsewhere in the description. Further aspects of the manufacture are known to the art and are described, for example, in still U.S. Patent No. 5,376,445, U.S. Patent No. 5,370,889, issued to A. It was noted that no early phase separation was performed in the blend, i.e., prior to extrusion. A blend as referred to herein means a mixture of a membrane component and a solvent. The mixture can be essentially a highly viscous liquid in the form of a gel or emulsion. The extrusion used herein 5 encompasses extrusion techniques known in the art, such as gel techniques, solvent extrusion, and the like. In one embodiment, the blend is formed in an extruder, such as an extruder having one or more screws, to treat the blend as a viscous mass, such as a gel or emulsion. The mass is pulled through a die, ® - resulting in a thick component, such as a thick flat strip or a thick tubular strip. The solvent is removed from the belt to form a base member. The base element prepared as described above can be directly used as the film of the present invention, and is therefore itself a film of the present invention. However, in order to increase the specific strength, pore size, pore size, and cost per unit area of the membrane, the base film is preferably stretched by a factor of at least 10 times the area to form a film. This stretching can be carried out batchwise or continuously. It has been found to be advantageous to have a biaxial stretching of 2-10 factors in the direction of the mechanism and a factor of 3-10 in the transverse direction, since this tendency results in a combination of membranous properties. Basically, biaxial stretching The film comprising UHMWPE of the present invention exhibits a tensile strength of about 7 MPa or more in the machine direction, preferably about 1 MPa or more. In the case where a very high strength is required, the film can be substantially made to have a tensile strength of about 40 MPa or more by calendering of the film or base material. This high strength allows for thinner films and/or films that do not require a rigid support when in use. Further, the elongation of the polyethylene film in the elongation is substantially 10-30% in the machine direction. This allows substantial deformation (elasticity) in use without damaging the properties of the film. 21 201024346 The solids content of the blend prior to extrusion is important for the processability of the film and the final film quality. When the dry content in the blend (ie, the sum of the polyolefin polymer, the hydrophilic component, and the optional additive) is about 5 to 3 wt% of the dry content and the dissolved U?, a good Combination of properties. However, an optimum combination of properties is obtained when the dry content of the blend is about 10 to 25 wt% of the dry content and the total weight of the solvent. The additive is functional. For example, rheology modifiers (e.g., oils), colorants, and fillers (i.e., added to the passive component, for example, to reduce the weight or cost of the film). Additives may be added, for example, to the handle to increase processability or affect final film properties. 0 10 The processing method (extrusion/stretching) is more conducive to the production of hydrophilic du film than the traditional solvent casting method. The high-cost and very well-defined coating for the uniform support of the k on the entire surface (10) Obtain the material - (4). Film thickness. The recipe described in the examples of the present invention requires a support for the production of hydrophilic chess, or a low cost support such as a non-woven support if desired. The hydrophilic porous polymer blend film of the present invention can be used in a variety of applications requiring filtration of water or aqueous media. In a preferred embodiment of the invention, the hydrophilic porous polymeric membrane is used in molecular applications such as particle filtration (in liquid or gas), microfiltration, ultrafiltration, nanofiltration, reverse osmosis. In one embodiment of the invention, the hydrophilic porous polymer membrane is used in a membrane bioreactor (MBR) and/or water purification process. The crucible of the present invention is particularly suitable for use in this process because of the relatively high water flow rate at low pressure and the propensity for fouling. In another embodiment of the invention, the 'hydrophilic porous polymer membrane uses 22 201024346 for electrochemical applications, including electrodialysis, electrodeionization, and fuel cells. 5 ❹ 10 15 20 In still another embodiment of the invention, the hydrophilic porous polymer blend film is for controlled release applications, including medicinal and nutraceutical ingredients. This application can be used for internal use, such as removal; or external use, such as in a bandage or another component placed on the body surface, such as on the skin or in a body cavity such as in the ear, eyes or nose. This contact with the body can be direct or via a carrier material (solid, liquid or gas). A hydrophilic porous polymer blend film can also be used as a support for the functional group. In yet another embodiment of the invention, the hydrophilic porous polymer blend film is used in thin film extraction, pervaporation, and current contactor applications. As will be presented in the examples, it is possible to adjust the pore size of the hydrophilic porous polymer membrane by changing the blend formulation. Very unexpected, for hydrophilic porous polymer membranes prepared by blending techniques, it is possible to have an average pore size that is adjustable from micron to nanometer while maintaining a relatively high water flux at low pressure gradients. . Test Method: Water Permeability: Water permeability was measured at room temperature (20X:) at a pressure gradient of 500 m bar with a 4 cm film diameter disc. Under pressure, 250 ml of water passed through the crucible. Record the time per 50 ml flow on the penetration side. Next, the water flux is calculated according to the equation: J = Q / AtP (Equation 1) where J is the flux h bar)], Q is the amount of water (liters) flowing through the membrane during time (1) (8), the effective area of 4 membranes (m2), and p is the pressure difference of 臈. The average of five measurements is averaged and an average is presented. 23 201024346 Hole Dimensions The average flow hole size is obtained by using the rule of thumb between average flow hole sizes, presented in microns, and measures PMI and Gurley numbers. The relationship between Gurley numbers and air permeability is described in section 1 of IS0 5636_5. The correction between the 5 Gurley number and the average flow hole size measured by the PMI device (see below) is derived from empirical positivism, which is the average flow hole size [μπι] to the Gurley number measured according to ISO 5635-5 ( Seconds / 5 〇 ml) Obtained in addition to i 77 "All values listed in the tables of the following examples are based on Gurley number measurements. φ 1〇 The average flow hole size is measured by the PMI device and is also based on air permeability, but using a wet fluid, Galwick type. The average flow hole size method of the pmi device is generally based on ASTM F316_〇3. The 25 mm diameter sample was wetted with a low surface tension fluid, Galwick type, and placed in a fixture. An air pressure differential removes the wetting fluid from the sample. After the wet test group, 15 a dry test group (dry flow) was performed. The PMI software calculation uses the differential pressure to calculate the average flow 'where wet flow equals half of the dry flow. Air permeability: Guangdong

The Gurley test method (according to ISO 5636-5) covers the determination of the resistance of the membrane to air passage. This method is used for membranes that can allow 2 helium gas to pass through in 1 second or more. In this test, 'using a Gurley Densometer of the type b of Toyoseiki Company, the recording time was 〇. 1 sec; with a 5 〇mi cylinder capacity, the cylinder weight was 567 gram and the measuring surface was 6.45 cm ^ 2 (1 ft 2 ) . After the correction, a long film is cut across the width of the reel. A smooth, undamaged test specimen is placed on the clamping plate hole and clamped. In the air penetration 24 201024346 permeability test method, air passes through the test sample thickness without using a wetting liquid. The measurement was started and was calculated in 0.1 second units at the required time of 50 ml. 5 ahr Millitrom; gi] volume, using a 0.5 mm tension with a 12 mm straight interface (footh). EXAMPLES The invention is illustrated by the following non-limiting examples. Example 1: A sample was prepared in accordance with the following general procedure. 10 a 16 to 24 wt% UHMWPE and a hydrophilic wound/valley solution in decalin (corresponding to the components in the patent application & and extrusion at a temperature of about 18 ° C. Extrusion The machine head is equipped with a die of 1 mm opening. The extruded film is cooled in a quench bath. The solvent is removed from the gel film by evaporation in an oven. The film which has been removed by the solvent is at a temperature of about 120°. C. The continuous or batch biaxial stretching is shown in Table 15. The materials used to prepare the film in the examples: • UH 210, UHMWPE [MW 4,600,000] obtained by DSM Stamylan

· PE0 200K, poly(ethylene oxide) [MW 200,000] powder, 20 Scientific Polymer Products Company Catalog #136B • PEO 300K, poly(ethylene oxide) [MW 300,000] powder, which is owned by The Dow Chemical Company. Polyox WSR N-750

• PEO 400K, poly(ethylene oxide) [MW 400,000] powder, Scientific Polymer Products catalogue #136E 25 201024346 • PE0 4000K, poly (ethylene oxide) [MW4, 〇〇〇, 〇〇〇] Powder, Scientific Polymer Products Catalog #344 • SMO: Liquid interface surfactant sorbitan monooleate, Rhodia's Alkamuls S/80 from 5 · Ox-PE (7 KOH), AC 307A, Oxidized polyethylene with 5-9 mg KOH/g acid number, obtained by Honeywell • Ox-PE (16 KOH), AC 316A, oxidized polyethylene with 15-18 mg KOH/g acid number, Honeywell obtained • Ox-PE (28 KOH), an oxidation _ 10 polyethylene with 28 mg KOH/g acid number, Scientific Polymer Products Catalog #406 • Ox-PE (43 KOH), AC 395A, with 40-45 mg KOH/g acid number of oxidized polyethylene, obtained by Honeywell Company • PE-AA (40 KOH), AC 540A, an ethylene succinic acid copolymer having an acid number of 37-44 mg KOH/g 'Acquired by Honeywell. 15 26 201024346

Table: Formulation of samples, all containing UHMWPE

Sample Ox-PE PEO SMO Blend + Dry Weight Stretch Batch or Continuous AN1 Amount [wt%] Type Amount [Wt%] [wt%] [wt%] [MxT] B/C 1 0 0 0 20 5x6 B 2 0 0 5 21 5x6 B 3 0 200K 5 0 21 5x6 B 4 0 200K 9 0 22 5x6 B 5 0 300K 15 0 16 5x6 B 6 0 300K 14 6 17 5x6 B 7 0 400K 28 6 17 5x6 B 8 0 4000K 14 6 17 5x6 B 9 0 300K 24 6 17 5x6 B 10 28 5 0 0 21 5x6 B 11 28 9 0 0 22 5x6 B 12 7 50 0 0 20 5x6 B 13 7 48 0 5 21 5x6 B 14 16 29 0 5 21 5x6 B 15 16 48 0 5 21 5x6 B 16 43 5 0 6 17 6x9 C 17 43 15 0 0 16 5x6 B 18 43 14 0 6 17 5x6 B 19 40 14 PE-AA2 0 4 23 5x6 B 20 43 15 300K 15 0 16 5x6 B 21 43 5 300K 5 6 17 6x9 C 22 43 9 300K 9 6 17 6x9 C 23 43 14 300K 14 6 17 6x9 C

AN=acid number mgKOH/gOx-PE ethylene-acrylic acid copolymer (ie non-PEO) 27 201024346 The thickness of the sample for continuous stretching is 3〇± 1〇μιη, and the tensile specimen for the batch is 90 ± 20 Ηηι. The experimental results based on these membranes are shown in the following table. Table 1: Addition of bismuth and / or SMO sample composition 3 Mfp4 [μιη] water drop [l / (m2h bar)] Gurley [s / 50ml] 1 100% UH210 0.2 0 12.2 2 5% SMO 0.5 0 3.4 3 5% PEO 200K 0.2 0 8.9 4 9% PEO 200K 0.2 0 11.2 5 15% PEO 300K 0.3 113 5.8 6 14% PEO 300K + 6% SMO 0.2 835 11.2 7 28% PEO 400K + 6% SMO 0.1 920 17.0 8 14 % PEO 4000K + 6% SMO 0.1 540 12.7 9 24% PEO 300K + 6% SMO 0.1 809 22.3 Based on wt% dry weight. The composition was added from UHMWPE (UH210) to 100 wt%. 4 The average pore size calculated from the Gurley number. In Table 1, it can be observed that the pure PE film and the PE film having only the surfactant are not hydrophilic. Hydrophilic membranes can be achieved by the addition of about PEO, but to achieve a water flux of, for example, > 500 l/(m2 h bar), an interfacial surfactant is required. However, when PEO and SMO are combined, a surprisingly high and stable water flux can be achieved for a wide range of SMO and PEO concentrations and a wide range of PEO levels. 28 201024346 Table 2: Adding sample composition of οχ-ΡΕ and/or SMO 5 Mfp6 [μιη] Water filling [l/(m2h bar)] Gurley [s/50ml] 1 100% UH210 0.1 0 12.2 10 5% Οχ-PE (28 ΚΟΗ) 0.4 0 4.1 11 9% Οχ-ΡΕ (28 ΚΟΗ) 0.3 0 5.2 12 50% Οχ-ΡΕ (7 ΚΟΗ) 0.4 <100 4.1 13 48% Οχ-ΡΕ (7 ΚΟΗ) + 5 % SMO 0.4 <100 4.0 14 29% Οχ-ΡΕ (16 ΚΟΗ) + 5% SMO 0.3 <100 6.3 15 48% Οχ-ΡΕ (16 ΚΟΗ) + 5% SMO 0.6 <100 3.1 16 5% οχ- ΡΕ (43ΚΟΗ) + 6% SMO 1.0 1146 1.8 2 5% SMO 0.5 0 3.4 17 15% οχ-ΡΕ (43 ΚΟΗ) 4.4 16064 0.4 18 14% οχ-ΡΕ (43 ΚΟΗ) + 6% SMO 3.3 18635 0.5

5 based on wt% dry weight. The composition was added to 100 wt% by UHMWPE (UH210). 6 The average hole size calculated from the Gurley number.

5 In Table 2, the height is unexpectedly observed for the blend containing UHMWPE and οχ-ΡΕ, the acid number of οχ-ΡΕ is much more significant for the hydrophilicity generated than that of #οχ-ΡΕ. If all are observed, the water flow rate of the sample having a low acid number of οχ-ΡΕ (even if combined with an surfactant) is very limited. On the other hand, even a 5 wt% οχ-ΡΕ results in a very high and durable water flux for a sample of 10 〇x-PE having an acid number greater than 30 mg 每 per gram. When the film comprises οχ-ΡΕ having a high acid number, an interfacing agent is not required to achieve a hydrophilic film with a south water flux, but the surfactant appears to reduce the pore size, which is desirable in many applications, For example, fouling due to membranes having lower pore sizes is reduced. 29 15 201024346

Table 3: Blending UH with ox-PE and SMO and PE-AA & SMO sample composition 7 Mfp8 [μιη] water zen amount [l/(m2h bar)] Gurley [s/50ml] 2 5% SMO 0.5 0 3.4 18 14% ox-PE (43 KOH) + 6% SMO 3.3 18635 0.5 19 14% PE-AA (40 KOH) + 4% SMO 0.05 < 100 37.2 Based on wt% dry weight. The composition was added to 100 wt% by UHMWPE (UH210). 8 The average hole size calculated from the Gurley number. Based on the observations in Table 2, the high acid number of 〇χ-ΡΕ tends to cause high water flux, 5 and it is investigated whether only a hydrophilic component having a high acid number is sufficient to obtain a high water flux. In Table 3, a sample without a hydrophilic polymer is compared to a sample having ox-PE or an ethylene-acrylic acid copolymer (PE-AA); wherein both ox-PE or ethylene-acrylic copolymer have High acid number. It was observed that the presence of only one high acid number component was not sufficient to achieve high water flux. In other words, the presence of ox-PE 10 with a high acid number appears to result in a film with a very unique nature, especially when considering films obtained by very simple and low cost blending techniques.

Table 4: Blend UH and PEO and / or ox-PE sample composition 9 Mfp10 [μιη] water volume [l / (m2h bar)] Gurley [s / 50ml] 1 100% UH210 0.1 0 12.2 5 15 % PEO 300K 0.3 113 5.8 20 15% PEO 300K + 15% ox-PE (43 KOH) 1.2 7327 1.5 21 5% PEO 300K + 5% ox-PE (43 KOH) + 6% SMO 0.4 2292 4.5 22 9% PEO 300K + 9% ox-PE (43 KOH) + 6% SMO 0.3 1771 7.0 23 14% PEO 300K + 14% ox-PE (43 KOH) + 6% SMO 0.2 1334 8.3 9 based on wt% dry weight. The composition was added to 1% by weight from UHMWPE (UH210). 1Q The average hole size calculated from the Gurley number. 201024346 In Table 4, it was observed that the combination of SMO and PEO increased the water permeability factor by 5 or more. In addition, the combination of PEO and ox-PE results in a particularly high and stable water flux film with relatively low pore size. I: Simple description of the diagram 3 5 (none) [Explanation of main component symbols] (none) • 31

Claims (1)

201024346 VII. Patent Application Range: L A porous polymer film comprising (a) a polyolefin polymer, and (b) a hydrophilic component, wherein the hydrophilic component comprises (bl) a hydrophilic polymer and optionally (b2) interfacial surfactant, 5 wherein (a) is the total dry weight of the film (refer to the following definition K98 wt% and the content of the hydrophilic component (b) is 22 wt% of the total dry weight of the film, blending the group Parts (a), (b) and optional additives are mixed together with a solvent to form a blend, and then the blend is extruded, wherein the porous polymer film is measured at 20 ° C at 〇.5 bar The water flux of the demineralized water passing through the membrane is - 1010 〇.5 l / (m2h bar). 2. The membrane of claim 1, wherein the polyolefin polymer comprises at least 90 wt% Polyethylene and/or polypropylene, preferably the polyolefin is polymerized. The film is a polyethylene according to claim 1 or 2, wherein at least 4% by weight of the polyolefin polymer (a) 15 It is preferably UHMWPE, preferably at least 70 wt% of the polyolefin polymer (a) is UHMWPE, more preferably the polyolefin polymer (a) 80 wt% is UHMWPE and preferably the polyolefin polymer (a) ® is substantially composed of UHMWPE. 4. The film according to any one of claims 1 to 3, wherein the polyolefin poly 20 (a) At least 5 wt% of the HMWPE, preferably at least 20 wt% of the polyolefin polymer (a) is HMWPE, such as at least 30 wt% of the polyolefin polymer (4), and the polyolefin polymer (a) Less than 60 wt% is HMWPE, such as less than 25 wt% of polyfluorene. 32 201024346 5. The film of any one of claims 1 to 5, which is based on ISO 5636-5 丨 0.1 The measured Gurley number is less than 50 s/50 m. Preferably, the Gurley number is less than 2 〇 s/5 〇 m. The Gurley number is better than ι〇s/50 ml, and 5 (5111'1 The number of # is at least 33 s/50 ml and preferably greater than 〇.5 s/50 m. The Gurley number is preferably greater than about 1 s/5 〇 ml and most preferably greater than 2 s/50 ml. The film of any one of claims 1 to 5, wherein the pore size is at least 〇.05 μιη, preferably the pore size is at least 0.1 μηι, more preferably 10, the pore is at least 0.4 μιη, And the hole size is less than 5 μm Preferably, the pore size is less than 2 μηη and more preferably the pore size is less than 7. The membrane of any one of the above-mentioned items, wherein the membrane has a pressure gradient of 20 C and a pressure gradient. The water flux measured for 5 〇〇m bar through a disc of 4 cm diameter is at least 1 〇〇 l / (m 2 h bar), and the water flux is preferably up to 400 1 / (m 2 h bar) Preferably, the water flux is at least 8〇〇1/(m2h bar), and the water flux is preferably at least 1〇〇〇1/(m2h bar), and the water flux is preferably at least 1200 l/ (m2 h bar), and preferably the water flux is less than 2 〇〇, 〇〇 0 1 / (m2 h bar), such as less than 20 20,000 1 / (m2h bar). 8. The film of any one of claims 1 to 7 wherein the film thickness is less than about 500 μηι, preferably the film thickness is less than about 2 〇 (¥ 〇 1, such as between 10 and 100 μm And preferably, the film has a thickness of at least 1 μm, and more preferably the thickness of the crucible is from 30 to 201024346, which is less than 20 μm. 9. The film according to any one of claims 1 to 8, wherein the film porosity Preferably, the porosity is at least 8 ν 〇 1%, and the porosity is at least 8 〇 〇 % % and more preferably at least 90 vol %. 5 10. The film of any one of claims 1 to 9, wherein The film has a layered structure of a fiber mesh, wherein the cross section of the film has 3 to 15 fiber mesh / 30 μπι '. Preferably, the cross section of the film has 4 to 12 fiber mesh / 3 〇 μηι, and more preferably The film has a cross-section of the film having a 6 to 1 〇 fiber mesh / 3 〇 μιη. U. The film of any one of claims 1 to 10, wherein the film has a layered structure of 0 fiber mesh, at least The 7% by weight fiber mesh has a thickness of 〇〇2 to 2·5 μηη, preferably at least 90% of the fiber mesh has a thickness of 〇.〇2 to 2.5 μηη. 34 201024346 And a mixture comprising at least one of these, and the preferred surfactant is sorbitan monooleate or the surfactant comprises sorbitan monooleate S. 5)· .10 15 20 14 The film of any one of claims 1 to 13, wherein the hydrophilic polymer (bl) is selected from the group consisting of oxidized polyethylene (οχ-PE) (including derivatives thereof such as ox-UHMWPE, ox -HMWPE), polyethylene oxide (PEO) or polyethylene glycol derivatives, PE wax, polyacrylic acid, polyacrylic acid, polycyclopropane, polyvinyl alcohol, ethyl acetate, cellulose, etc. a derivative, polymethyleneamine, polyetherimide, polyvinylpyrrolidone, polyethyleneimine, polyamine, a copolymer thereof, combinations thereof, and combinations comprising at least one of these; The polymer is preferably ox-PE (bla) and/or PEO (blb), and the ox-PE (bla) preferably has an average acid number of at least 1 mg/g ox-PE, preferably at least 30 mg. /g 〇χ-ΡΕ and more preferably at least 40 mg/g ox-PE. 15. The film of any one of claims 1 to 14, wherein the hydrophilic component (b) is present in an amount of 2 10 wt% of the total dry weight of the film. 16. The film of any one of claims 1 to 15, wherein the hydrophilic polymer (bl) comprises ox-PE (bla) and PEO (bib), and the content of strontium-strontium is 2 wt. % and the content of PEO (bib) is 22% by weight, preferably 0X_PE (bla) > 10 wt% and/or PEO (bib) 2 10 wt%, more preferably 0X-PE (bla) 2 15 wt% And / or PEO (bib) 2 15 wt%. 17. The film of any one of claims 1 to 16, wherein the hydrophilic polymer (bl) comprises PEO (bib) and the weight average molecular weight of the PEO (bib) is at least 100,000 g/mole, PEO ( The weight average molecular weight of the bib) 35 4 201024346 is preferably at least 200,000 g/mole. The film according to any one of claims 1 to 15, wherein the hydrophilic polymer (bl) comprises OX-PE and the weight average molecular weight of οχ-PE (bla) is 1000-1 〇〇, 〇〇 〇g/莫耳. The membrane of any one of claims 1 to 17, wherein the hydrophilic component (b) is lanthanum-strontium, and the cerium-lanthanum preferably has at least 1 〇mg KOH/g ox-PE The average number of acids is more preferably at least 3 mg KOH/g oxidized PE and more preferably at least 40 mg KOH/g οχ-ΡΕ. 20. The film of claim 19, wherein the film comprises less than 1% by weight of the 10 surfactant, preferably the film comprises less than 0.5% by weight of the surfactant, and preferably the film does not comprise any Interface active agent. 21. The film of any one of claims 120, wherein the film is a sheet-like element or a hollow element. 22. If you apply for a patent scope! The film of any one of the 21 items further comprises a 15 additive which is selected from the group consisting of anti-odor additives, P and a fuel, a filler, a conductive material and an anti-fouling additive such as activated carbon, carbon black, graphite, and high. Surface area metal powder, nana carbon tube, synthetic oxide, naturally occurring oxidized G #^ oxide and fibrous materials such as glass fiber, stone fiber, ceramic fiber, organic fiber and metal fiber. An element comprising a film according to any one of claims 1 to 21, wherein the film is independently at least partially on the support member to form a flat main surface, a tubular main surface and/or a crucible Main surface. 24. The component of claim 23, wherein the building element is a laminate comprising 3 non-woven fabrics, fabrics, woven mesh, mesh and/or peach components, 36 201024346. Free polymers such as PET, PP, PTFE, UHMWPE, nylon, and copolymers comprising any of these; inorganic materials such as metals (such as aluminum or stainless steel) or ceramics or glass (such as Al2〇3 and citrate) a combination of materials in the group; and at least a combination of at least two components of 5 of the group 'the support member and film are preferably joined to each other by ultrasonic welding, gluing, thermal bonding or by laser welding . 25. A module comprising a film according to any one of claims 2 to 21 or an element as claimed in claim 23 or 24, and further comprising a * support and/or frame. And a system comprising a film according to any one of claims 1-6 to 21, a component of claim 23 or 24, or a module of claim 25 of the patent application. 27. A method of making a hydrophilic porous polymer film comprising the step of - less than 90 wt% of a non-solvent component of a polyolefin polymer (... and 15 at least 丨〇 wt% of a non-solvent component of hydrophilicity And a solvent to form a blend, - extruding the blend to form a thick component, and - removing the solvent to form a base component. 28. The method of any one of claim 27, Further comprising the step of stretching the base film by a factor of at least 10 times the area to form a film, the stretching preferably being a biaxial pull in the direction of the mechanism of 2-10 factors and a cross direction of 3-10 factors. 29. The method of claim 27 or 28, wherein the dry content in the blend is from about 5 to 30 wt% of the dry content and the total weight of the solvent, 37 201024346 the blend The dry content is preferably from about 10 to 25 wt% of the dry content and the total weight of the solvent. The method of any one of claims 27 to 29, wherein the solvent is passed before stretching the base member Evaporation removal. 5 31. The use of a film according to any one of claims 1 to 21, As a separate film or a support film. 32. The use of a film according to any one of claims 1 to 21 for separation (especially in particle filtration, gas filtration or liquid filtration); For membrane bioreactor; a humidified membrane; for reverse osmosis; 10 for controlled release applications (including medicinal and nutraceutical components (implants or tablets) for internal use or for external use (eg In a bandage)); as a scaffold for functional groups; for thin film extraction applications; for pervaporation applications; for contactor applications; or for electrochemical applications (including electrodialysis, electrodeionization and fuel Battery) 201024346 IV. Designated representative map: (1) The representative representative of the case is: () (No) (2) The symbol of the symbol of this representative is simple: 5. If there is a chemical formula in this case, please reveal the most A chemical formula that shows the characteristics of the invention: