Surface-modified porous battery separator

Abstract

Products using or incorporating surface-modified or functionalized polymers and textile materials are provided. A surface-modified substrate comprising a surface modifier chemically bonded to a substrate, the substrate being selected from a polymeric substrate, a fibrous substrate, a fiber, a polyolefin material, a polypropylene material, a polyethylene material, a porous polymeric substrate, a non-porous polymeric substrate, a porous hollow fiber, a non-porous hollow fiber, a porous battery separator, a thin film, a polymeric surface layer, a composite material, and combinations thereof, the surface modifier comprising a substrate-binding component that is a nitrene precursor and / or a carbene precursor.

Description

[Technical field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of U.S. Provisional Patent Application No. 61 / 754,100, filed Jan. 18, 2013, which is incorporated herein by reference in its entirety.

[0002] According to at least selected embodiments, the present invention is directed to new, improved or optimized surface modifiers, materials made or modified with such agents, methods of making and / or using such agents and / or modified materials, and / or new, improved or optimized polymeric and / or textile materials, separators, garments, fabrics, etc. incorporating such agents and / or modified materials. According to at least certain embodiments, the present invention is directed to surface modifiers for polymeric and / or textile materials, modified materials, methods of making and / or using surface modifiers to modify and / or functionalize polymeric and / or textile materials, and / or methods of using surface modified or functionalized polymeric and / or textile materials.

[0003] According to at least certain embodiments, the present invention is directed to surface modifiers comprising suitable nitrene and / or carbene precursors that can undergo chemical reaction, optionally in the presence of heat or light, to form one or more nitrene and / or carbene functional groups. In some cases, preferred nitrene precursors include, but are not limited to, materials such as sulfonyl azide-containing styrene monomers, polymers or copolymers that can undergo chemical reaction in the presence of heat or light to form one or more nitrene functional groups. At least selected certain embodiments are directed to surface modifiers that include styrene sulfonated monomers, polymers or copolymers that contain one or more sulfonyl functional groups, such as sulfonyl azide functional groups, that can be chemically reacted with the surface of a polymer or textile material upon activation to impart a particular or desired chemical surface functionality to the surface of the polymer or textile material.

[0004] The imparted modification or functionality can change the physical properties of the polymer and / or textile material or enable the material to be used in new functional roles. For example, the functionality can impart properties such as hydrophilicity, hydrophobicity, oleophilicity, oleophobicity, etc. to the polymer and / or textile material and / or the functionality can change the surface energy of the polymer or textile material to modify the polymer and / or textile material to make it suitable for a particular end use application. Furthermore, a particular surface modification can provide a particular functionality for a new functional role. For example, the imparted functionality can be aimed at enabling the material to be used in applications where the material becomes interactive, e.g., can interact with other materials, such as other molecules. Other examples include, but are not limited to, particular applications where the modified or functionalized material interacts with other materials, coatings, layers, etc., and can be particularly suitable for applications such as separators, barrier fabrics, membranes, substrates, layers, fabrics, textiles, etc. in electrochemical cells or batteries, textiles, clothing, filtration, adsorption, testing, drug delivery, analyte sensing, medical devices, medical diagnostic devices, etc. [Background technology]

[0005] There are various methods to modify the physical or chemical properties of the surface of a polymer or textile material. Certain known modifications to the surface of a polymer or textile material are often temporary and do not permanently modify the polymer and / or textile substrate for various end use applications.

[0006] One such known method is, for example, UV light (without the use of special surface modifiers) ), plasma treatment, corona treatment, or fluorine oxidation. Such treatments can be harsh, especially for thin films and certain polymer classes. The use of these methods can pose a risk of mechanical or chemical damage to the surface of the polymer substrate. Damage can potentially impair the performance of the modified polymer substrate for the intended end-use application.

[0007] More generally, other such known methods of treating or pre-treating the surface of a polymeric or textile substrate include, for example, coating, dip-coating, spraying, etc., the surface of the polymeric or textile substrate with some functional material according to known procedures, such existing treatments may not be durable and may wear away over time from the surface of the polymeric or textile substrate, after a period of time the polymeric or textile material may no longer be suitable for its intended end use application.

[0008] Thus, there is a need for improved methods for modifying the physical and / or chemical properties of the surface of polymeric or textile materials, at least for certain applications or uses. In particular, there is a need for improved or new methods for permanently modifying polymeric or textile substrates for various end use applications, surface modified polymeric or textile materials, modified functionalized polymers, functional polymers, uses of such materials, and the like. Summary of the Invention [Problem to be solved by the invention]

[0009] According to at least selected embodiments, the present invention can provide, or at least address the need for, new, improved or optimized methods of modifying the physical and / or chemical properties of one or more surfaces of polymeric materials, improved or novel methods of permanently modifying polymeric substrates for various end use applications, surface modified polymeric materials, modified functionalized polymers, functional polymers, uses of such materials, and the like. [Means for solving the problem]

[0010] At least certain embodiments of the present invention can address the above needs and are directed to modified functionalized polymers, functional polymers, and chemically modified substrates comprising the modified functionalized polymers, methods of modifying the functionalized polymers and / or methods of using the modified functionalized polymers to chemically react with the surface of a substrate, and / or methods of using such chemically modified substrates.

[0011] The present invention may also provide improved methods of using surface modifiers to modify the physical and / or chemical properties of one or more surfaces (or sides) of polymeric or textile materials, and / or improved or novel methods of permanently modifying polymeric or textile substrates for various end use applications.

[0012] Additionally, the present invention may provide improved methods of modifying polymers and / or textile materials using surface modifiers, methods of making and / or using surface modifiers to modify and / or functionalize polymers and / or textile materials, and / or methods of using surface modified or functionalized polymers and / or textile materials. The present invention may also provide improved methods of using surface modifiers to modify the physical and / or chemical properties of the surface of a polymer or textile material, and / or improved or novel methods for permanently modifying polymer or textile substrates for various end use applications.

[0013] In some cases, it is desirable for the surface modifier to be an agent capable of reacting to form nitrene and / or carbene functional groups. The groups can be used to react with the surface to give it the desired functionality. In some cases, it is preferred that the surface modifier is an agent that can react to form a nitrene functional group. The nitrene functional group can then be used to react with the surface to give it the desired modification and / or functionality. For porous surfaces, the modification and / or functionality can be across the entire surface, not just on one surface, on both sides, etc., over the pores, in the pores, on the surface, and even under the pores.

[0014] At least selected embodiments are directed to a method of preparing a surface modifier, which includes a styrenesulfonyl azide-containing monomer. The sulfonyl azide-containing monomer can chemically react in the presence of heat or ultraviolet (UV) light to form a chemical species known as a nitrene. A nitrene is a reaction intermediate that is an electronically neutral chemical species with only six valence electrons. The nitrene can react with certain substrates, such as saturated hydrocarbons, as well as other CH or heteroatom bonds, by an insertion reaction, in which the nitrene inserts into one or more of the CH or heteroatom bonds of the substrate. The nitrene group of the polymer provides a reactive site where a multifunctional nitrene precursor can activate and covalently insert into one or more CH or heteroatom bonds of the substrate for the purpose of modifying the chemical properties of the substrate.

[0015] At least selected embodiments are directed to a method of preparing a surface modifier comprising a sulfonyl azide-containing polymer or copolymer. The sulfonyl azide-containing polymer or copolymer can chemically react in the presence of heat or ultraviolet light to form a chemical species known as a nitrene. A nitrene is a reaction intermediate that is an electronically neutral chemical species having only six valence electrons. The nitrene can react with a substrate by an insertion reaction in which the nitrene inserts into one or more of the substrate's CH or heteroatom bonds. The sulfonyl azide group of the styrene polymer or copolymer provides a reactive nitrene site that can covalently insert itself into one or more of the substrate's CH or heteroatom bonds for the purpose of modifying the substrate's chemical properties.

[0016] In this way, the functional groups of the nitrene precursors act as reactive sites or cross-linking connectors to bond the sulfonyl azide-containing polymer or copolymer to a substrate for the purpose of modifying the chemical properties of the substrate. For example, if the substrate is a polymer or textile material, once the styrene sulfonyl azide-containing polymer or copolymer has been attached, the surface chemical reactivity of the polymer or textile material can be modified, either by itself or by blending with one or more polymers selected to provide the appropriate interface for the desired application. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a diagram of one embodiment of modifying or functionalizing the surface of a substrate to form a modified functionalized substrate, material, layer, base, membrane, separator, porous membrane, non-porous precursor membrane, etc., in accordance with the present invention. [Diagram 2] FIG. 2 is a diagram of another embodiment of modifying or functionalizing the surface of a substrate to form a modified functionalized substrate, material, layer, base, membrane, separator, porous membrane, non-porous precursor membrane, and the like, in accordance with the present invention. [Diagram 3] 1 shows a schematic side or end view of a modified and / or functionalized substrate, material, layer, base, membrane, separator, porous membrane, non-porous precursor membrane, etc., according to the present invention. [Figure 4] 1 shows two schematic side or end views of a modified and / or functionalized substrate, material, layer, base, membrane, separator, porous membrane, non-porous precursor membrane, etc., according to the present invention. [Diagram 5] FIG. 1 shows a schematic side or end view of a modified and / or functionalized substrate, material, layer, base, membrane, separator, porous membrane, non-porous precursor membrane, etc., including an additional component D, such as a coating, layer, etc., according to the present invention. [Figure 6] FIG. 1 shows two schematic side or end views of a modified and / or functionalized substrate, material, layer, base, membrane, separator, porous membrane, non-porous precursor membrane, etc., including an additional component D, such as a coating, layer, etc., according to the present invention. [Figure 7] 4 is a FTIR spectrum of materials made according to various embodiments of the present invention. [Figure 8] 1 is a DSC curve representative of materials made according to various embodiments of the present invention. [Figure 9] FIG. 1 is a thermogravimetric analysis of materials made according to various embodiments of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] At least selected embodiments of the present invention are directed to surface modifiers for polymers and / or textile materials, methods of making and / or using the surface modifiers to modify or functionalize polymers and / or textile materials, and / or methods of using the surface modified or functionalized polymers and / or textile materials, and / or products using or incorporating the surface modified or functionalized polymers and / or textile materials. The present invention can also provide improved methods of using the surface modifiers to modify the physical and / or chemical properties of one or more surfaces (or sides or portions) of polymers or textile materials, as well as improved or novel methods of permanently modifying polymeric or textile substrates or materials for various end use applications.

[0019] At least selected embodiments are directed to a method of preparing a surface modifier that can be used to modify or functionalize the surface of a polymeric or textile substrate. The surface modifier of certain embodiments comprises a precursor capable of forming nitrene or carbene functional groups, reactive sites and / or crosslinking sites. In one particular embodiment, the surface modifier comprises a styrenesulfonyl azide-containing monomer, polymer or copolymer. The sulfonyl azide-functional monomer can undergo chemical reaction under appropriate conditions, for example, in the presence of heat or ultraviolet light, to form a chemical species known as a nitrene. Nitrenes (R-:N:) are reaction intermediates that have only six valence electrons and are electronically neutral chemical species. Nitrenes can react with polymeric or textile substrates by an insertion reaction in which the nitrene inserts into a C-H or heteroatom bond of the substrate. Step 1 of the schematic diagram below is RN=N + =N - (also commonly referred to as R-N3) represents a generalized example of an azide that forms nitrenes R-:N: upon exposure to UV light or heat, with nitrogen gas as a by-product.

[0020] Step 1: [ka]

[0021] Step 2: [ka]

[0022] In step 2 of the schematic above, the nitrene can then insert into an exemplary C-H bond and react with an alkyl or aryl moiety (shown in this diagram as R'-CH) to form R-N-CH-R'. The nitrene intermediate is a reactive moiety that covalently inserts into one or more C-H bonds of an exemplary R'-CH hydrocarbon substrate for the purpose of modifying the chemical properties of the exemplary hydrocarbon substrate.

[0023] Certain embodiments of the present invention are directed to a method for preparing a sulfonyl azide-containing monomer, represented as RS=O2-N3, which upon exposure to heat or UV light can form a nitrene intermediate. The nitrene intermediate can be reacted with a substrate to modify the chemical properties of the substrate. The sulfonyl azide-containing monomer can be activated to a nitrene intermediate and inserted into one or more of the CH or heteroatom bonds of a polymer or textile material, thereby modifying the chemical reactivity of the surface of the polymer or textile material based on the chemical properties of the sulfonated functionalized monomer. One such example is the sulfonated styrene azide monomer 4-styrenesulfonyl azide.

[0024] [ka]

[0025] Furthermore, when 4-styrenesulfonyl azide is exposed to UV light or heat, it can insert into one or more CH or heteroatom bonds of a polymer or textile material, modifying the chemical reactivity of the surface of the polymer or textile material. When activated, a polymer containing a monomer containing a sulfonyl azide group can generate multiple nitrene intermediates that can insert into various CH or heteroatom bonds along the surface of the polymer or textile material or substrate, and change the chemical reactivity of the surface of the polymer or textile material to some extent based on the composition of the sulfonyl azide-containing polymer that reacts with the surface of the polymer or textile material substrate.

[0026] Another embodiment is directed to a method for preparing a surface modifier, the agent comprising a small molecule such as a sulfonyl azide-containing small molecule. When the sulfonyl azide-containing small molecule is exposed to heat or UV light and converted to a nitrene functional group, it can be inserted into the CH or heteroatom bond of a polymer or textile material, and can modify the chemical reactivity or other interfacial properties of the surface of the polymer or textile material based on the chemical reactivity of the selected sulfonyl azide-containing small molecule. Essentially, the nitrene precursor provides the chemical functionality of the attached functional group, changing the chemical reactivity or interfacial properties of the surface of the polymer or textile material based on the chemical properties of the selected functional group. An example of a sulfonyl azide-containing molecule that can be surface modified with a simple aliphatic hydrocarbon can be represented as follows:

[0027] [ka]

[0028] Furthermore, when one or more sulfonyl azide-containing molecules or polymers are exposed to heat or ultraviolet light to chemically react to form one or more nitrenes, the one or more nitrenes can react at various CH or heteroatom bonding sites of the substrate by insertion reactions, and depending on the number of nitrene groups inserted, the chemical functionality or interfacial properties of the polymer or textile substrate can be further modified. In this way, the multiple nitrene precursors can act as reactive sites or cross-linking connectors to bond the sulfonyl azide-containing molecules or polymers to the substrate for the purpose of modifying the chemical properties of the substrate. Furthermore, when the substrate is a polymer or textile material, the attachment of one or more sulfonyl azide-containing polymers can modify the surface chemical reactivity of the polymer or textile material to make it suitable for the intended end use application.

[0029] Besides combining two monomers, one way to generate such sulfonyl azide-containing polymers is by post-polymerization modification of materials such as polyvinyl sulfonate or polysodium styrene sulfonate. These types of polymers can be readily converted to sulfonyl azides by standard chemical modification techniques as depicted below.

[0030] [ka]

[0031] Another embodiment of the present disclosure is directed to a method for preparing a surface modifier, the agent comprising a sulfonyl azide-containing polymer. Generally, in various embodiments described herein, the surface modifier can be referred to as component B (where component B contains a crosslinking or reactive material, such as a nitrene group derived from a nitrene precursor material used to functionalize the polymer or textile substrate), or component A+B (where component B is defined above and component A is any functional polymer or functional group that is paired with the polymer or textile substrate to provide a specific formulation, property, chemical property, etc., to the polymer or textile substrate). Furthermore, component B, in various embodiments herein, can simply contain monomer X, where monomer X comprises a monomer that is a precursor of a reactive nitrene or carbene functional group. However, component B, in other embodiments herein, can contain monomer X+monomer Y, where monomer Y is any other monomer that can reduce the overall cost of materials (relative to component B containing only monomer X) or can provide some property or functionality to the polymer or textile substrate. By way of example, the sulfonyl azide-containing polymer may be prepared by reacting the following monomer X in a homopolymer system:

[0032] [ka]

[0033] That is, it can be prepared by polymerizing sulfonated styrene azide monomers. In such homopolymer systems, using the above nomenclature, component B, i.e., the surface The modifier comprises only monomer X (rather than monomer X+Y). In other embodiments, sulfonyl azide-containing polymers can be prepared by polymerizing monomer X, i.e., a sulfonated styrene azide monomer, and including another monomer Y, where monomer Y does not contain a nitrene (or carbene) precursor material. Some examples of monomer Y include, for example, styrene, pentafluorostyrene, or the sodium salt of sulfonated styrene, all of which are shown in the formula below, respectively:

[0034] [ka]

[0035] The above method has the advantage that the resulting sulfonyl azide-containing polymers are more easily tailored to desired properties by incorporating orthogonal functional groups or alternative surface properties that may be advantageous for further formulation. Further, other examples of monomer Y can be as follows:

[0036] [ka]

[0037] Here, the first and second examples of monomer Y are methacrylate and acrylate monomers, respectively, which can alter the physical properties (such as glass transition temperature) of the surface modifier based on the selection of the R group, and the third example is an anhydride, a reactive species that provides opportunities for further orthogonal chemical reactions. Additional examples of monomer Y can include, but are not limited to, 2-vinylpyridine, 4-vinylpyridine, and / or N-vinylpyrrolidone.

[0038] Other examples shown below are copolymers produced by polymerizing a sulfonylstyrene azide-containing monomer (monomer X, hereinafter designated by the amount "n") copolymerized with a second monomer (monomer Y, hereinafter designated by the amount "m") having an R group with a particular chemical functionality, which may include, but is not limited to, any one of the following examples:

[0039] [ka]

[0040] The prepared sulfonyl azide-containing copolymers can be chemically reacted to form nitrene intermediates when exposed to heat or ultraviolet light. The nitrene reacts with the polymer or textile substrate by an insertion reaction, where the nitrene functional group is inserted into one or more of the CH or heteroatom bonds of the substrate. Furthermore, the ratio of n and m, which are repeating units of the sulfonated styrene copolymer, can be 0.1≦n / (n+m)≦0.75. Another way of expressing this is that in certain embodiments, the azide content by the molar ratio of monomers (n / (n+m)) can be expressed as a percentage, here 10-75%. In certain preferred embodiments, the azide content (n / (n+m)) based on the molar ratio of monomers can be 10 to 40%, in other preferred embodiments, the azide content (n / (n+m)) based on the molar ratio of monomers can be 15 to 30%, and in yet other preferred embodiments, the azide content (n / (n+m)) based on the molar ratio of monomers can be 20 to 25%.

[0041] In this manner, one or more of the nitrene functional groups serve as reactive sites or cross-linking connectors to bond the sulfonyl azide-containing copolymer, i.e., component B (here containing monomers X+Y), or in some embodiments, component AB, to a substrate (here the polymer or textile substrate is also referred to herein as component C) for the purpose of modifying the chemical properties of the substrate. For example, if a sulfonated styrene copolymer contains pentafluorostyrene as an R group (e.g., the R group in the "Y" monomer), then insertion of one or more of the nitrenes into a hydrocarbon substrate or polymer or textile material can reduce the surface energy of the polymer or textile surface. Another example of a sulfonyl azide-containing functionalized material with alternative functionality is dansyl azide, which is formed by reaction of dansyl chloride with sodium azide as shown below.

[0042] [ka]

[0043] An interesting chemical property of dansyl azide is that it fluoresces when the sulfur atom is attached to a nitrogen. Therefore, dansyl azide may be useful as a biomarker for proteins. Dansyl azide reacts in the presence of UV light or heat to form nitrenes, which are then converted to nitriles. When the dansyl fluorescer is covalently bonded to a polymer or textile substrate, the substrate will fluoresce permanently, indicating the covalent attachment of one or more nitrene groups of the dansyl nitrene to one or more C-H bonds of the polymer or textile substrate. Subsequent washing can verify the durability of the dansyl fluorescer on the substrate. The schematic below shows the formation of the nitrene upon exposure to UV light or heat, which is then reacted with the polymer or textile substrate, represented here as R'-CH3.

[0044] [ka]

[0045] In certain embodiments, dansyl azide is applied as a coating from a hexane solution to a polypropylene thin film substrate, and the thin film substrate is then exposed to UV light, resulting in the thin film emitting an intense fluorescence that does not decrease after rinsing with a solvent (such as acetone) and / or water, indicating that one or more molecules are covalently attached to the surface of the polypropylene thin film substrate via a nitrene intermediate.

[0046] As another example, when the sulfonyl azide-containing copolymer contains sulfonate functionality (previously shown as possible monomer Y), deposition of the nitrene intermediate onto the polymer or textile exhibited a significant increase in the surface energy of the treated material. Increasing or decreasing the surface energy of the polymer or textile material surface changes the chemical properties of the polymer or textile material surface, which makes the surface more or less chemically reactive with other chemicals such as colorants, finishes, waterproofing agents, antimicrobial agents, oils, fragrances, etc.

[0047] Other examples of chemically modifying the properties of polymeric or textile substrate materials include, but are not limited to, copolymerizing a sulfonyl azide-containing monomer with a monomer or polymer selected based on chemical functionality to make the polymeric or textile substrate hydrophilic, hydrophobic, oleophilic, or oleophobic. For example, when a sulfonyl azide-containing monomer is polymerized with a copolymer containing hydrophilic, hydrophobic, oleophilic, or oleophobic functional groups, the chemical properties of hydrophilic, hydrophobic, oleophilic, or oleophobic functional groups can be chemically attached to the surface of the polymeric or textile substrate.

[0048] Further, in accordance with selected embodiments of the present invention, a sulfonyl azide-containing monomer or polymer, defined as component B, can be combined with a copolymer, monomer, polymer, or other functional group, defined as component A, to form component AB, which can be applied as a coating to the surface of a polymer or textile material (which can also be referred to as component C). Exposing the coated surface of the polymer or textile material to heat or UV light can generate one or more nitrene reactive groups on component AB (or component B) that can covalently bond component AB (or component B) to the surface of the polymer or textile material (component C) to form a modified substrate ABC (or BC).

[0049] In some embodiments, component B, which contains a material that generates nitrene and / or carbene groups upon activation by heat or light, comprises monomer X or monomer X+Y. In Figure 1, component B comprises monomers X and Y. In Figure 1, component B is attached to the surface of a polymer or textile material (component C) via a nitrene reaction to alter the chemical reactivity of the polymer or textile material (component C) for a wide variety of end uses.

[0050] A similar approach, shown in Figure 2, involves attaching component B to the surface of a polymer or textile material (component C) via a nitrene reaction to alter the chemical reactivity of the polymer or textile material (component C) for a wide variety of applications. In the embodiment shown in Figure 2, component B comprises monomer X rather than monomer X+Y.

[0051] When the sulfonyl azide is exposed to UV light, it forms a nitrene group, which can initiate an insertion reaction into a C-H or other heteroatom bond by additional reaction with N2 as a by-product. When component B or component AB is exposed to optimized UV light with a selected range of wavelengths, the modified azide can also function as a labeling reagent with its newly generated reactive nitrene end group. When the nitrene group reacts at a site on the surface of the substrate material, it inserts the functionalized component AB (or component B) and introduces a new desired tagging functionality into component C, the polymer or textile substrate.

[0052] Furthermore, the insertion reaction has the advantage that chemical radical species cannot initiate propagation from the insertion reaction site. In the case of polyolefin substrates such as polyethylene (PE) or polypropylene (PP), this aspect is important because when exposed to UV light, PE and PP tend to crosslink or decompose when radicals are introduced into the backbone of the polyolefin polymer.

[0053] In this way, the surface of a substrate material, such as a polymer or textile material, can be modified or labeled in a desired chemical manner and, thanks to the chemical reactivity of the nitrene groups, the desired surface properties can be tailored for a wide variety of end uses. One such example is modifying the surface energy and / or hydrophobicity and / or oleophobicity of a polyolefin surface, such as polypropylene, by transforming a normally unreactive surface into a reactive surface.

[0054] Most polyolefins are essentially "non-functional" since they do not readily accept chemical modification without significant consequences to the mechanical or chemical stability of the material. Nitrene-based intermediates offer the opportunity to modify non-functional polyolefins without the severe damage or degradation that typically occurs with many conventional surface modification approaches, damage or degradation that can in some cases reduce the performance of the modified polyolefin substrate for its intended end-use application.

[0055] At least certain selected embodiments of the present invention are directed to modified functionalized polymers, functionalized polymers and chemically modified substrates comprising modified functionalized polymers, methods of modifying functionalized polymers and / or methods of using modified functionalized polymers to chemically react with the surface of a substrate, and / or methods of using such chemically modified substrates. At least certain embodiments are directed to modified functionalized polymers, functionalized polymers and methods of modifying functionalized polymers to chemically modify porous, microporous and non-porous polymeric substrates, and methods of using such modified substrates. In at least selected embodiments, the carbene group RC: or nitrene group R-:N: is a reactive intermediate capable of carrying out a heteroatom insertion chemistry. The carbene or nitrene intermediates can be formed from a variety of thermal and photochemical reactions. Examples of nitrene precursors include aryl azides, acyl azides, azidoformates, phosphoryl azides, phosphonyl or sulfonyl azides. Examples of carbene precursors include haloalkanes, diazoalkanes, diazoketones, diazonacetates, beta-keto-alpha-diazoacetates, aliphatic azo or diaziridine. In some embodiments, the carbene material can be generated from an alpha-elimination reaction using one or more of the carbene precursors described above.

[0056] At least certain selected embodiments of the present invention address the need to modify the surface of a porous polymeric substrate. At least selected embodiments of the present invention address the above need and / or provide modified porous polymeric membrane substrates, methods of making modified polymeric porous membrane substrates, and / or methods of using modified polymeric porous membrane substrates, chemically modified polyolefin microporous membranes, methods of making chemically modified polyolefin microporous membranes, and / or methods of using chemically modified polyolefin microporous membranes, chemically modified polyolefin microporous battery separators or battery separator membranes, methods of making chemically modified polyolefin microporous battery separators or battery separator membranes, and / or The present invention is directed to methods of using chemically modified polyolefin microporous battery separators or battery separator membranes, chemically modifying polyolefin microporous battery separators or separator membranes by reacting modified functionalized polymers containing carbene or nitrene intermediates with carbon-hydrogen bonds of the polyolefin to form carbon or nitrogen-carbon covalent bonds in the polyolefin, methods of improving the hydrophilicity or wettability of polyolefin microporous battery separators or separator membranes in lithium ion rechargeable batteries, and / or methods of introducing crosslinks into polyolefin microporous battery separators or separator membranes.

[0057] According to at least selected and possibly preferred embodiments of the present invention, at least a portion of the chemical modification of the polyolefin microporous separator or membrane can be carried out with a functionalized polymer or copolymer containing a carbene and / or nitrene intermediate, for example, by carbon-hydrogen bonding of the polyolefin. The above chemical reaction or treatment based on the functionalized polymer or copolymer containing a carbene and / or nitrene intermediate provides a method to further improve the wettability of the polyolefin microporous separator of a lithium-ion rechargeable battery in a permanent manner. Also, the reaction of the functionalized polymer or copolymer containing a carbene and / or nitrene intermediate with a C-H bond can be used to introduce crosslinking functionality into the polyolefin, at least in the surface layer of the polyolefin microporous separator membrane, which can be used to improve the high temperature stability of the polyolefin microporous separator or membrane.

[0058] According to at least certain selected embodiments, the present invention addresses the need to modify the surface of a porous polymeric substrate. At least selected embodiments of the present invention address the above-mentioned need and are directed to modified porous polymeric membrane substrates, methods of fabricating modified polymeric porous membrane substrates, and methods of using modified polymeric porous membrane substrates. More particularly, the present invention is directed to chemically modified polyolefin microporous membranes, methods of fabricating chemically modified polyolefin microporous membranes, and methods of using chemically modified polyolefin microporous membranes. More particularly, the present invention is directed to chemically modified polyolefin microporous water-resistant and breathable textile membranes, methods of fabricating chemically modified polyolefin microporous water-resistant / breathable textile membranes, and methods of using chemically modified polyolefin microporous water-resistant / breathable textile membranes. In accordance with at least selected preferred embodiments, the present invention is directed to chemically modifying polyolefin microporous water-resistant / breathable textile membranes by reacting functionalized polymers containing carbene and / or nitrene intermediates with the carbon-hydrogen bonds of the polyolefin, methods for reducing the surface energy of the water-resistant / breathable textile membranes or imparting oleophobic properties thereto to improve the soil resistance of the water-resistant / breathable textile membranes and / or improve the durability of the membrane's water resistance, and the like.

[0059] In accordance with certain selected embodiments, the present invention addresses the need to modify the surface of woven polymeric fibers. At least selected embodiments of the present invention address the above need and are directed to modified woven polymeric fibers, methods of making modified woven polymeric fibers, and methods of using modified woven polymeric fibers. More particularly, the present invention relates to chemically modified woven polymeric fibers. The present invention is directed to modified textile polyolefin fibers, methods of making chemically modified textile polyolefin fibers, and methods of using chemically modified textile polyolefin fibers. According to at least selected and possibly preferred embodiments, the present invention is directed to a method of chemically modifying textile polymer fibers, such as reducing the surface energy of textile polymer fibers or imparting oleophobic properties thereto, thereby improving the soil resistance of textile polymer fibers and / or improving the durability of the textile polymer fibers' water resistance, by reacting modified functionalized polymers containing carbene and / or nitrene intermediates with the carbon-hydrogen bonds of the textile polymer fibers.

[0060] At least certain objects, embodiments, aspects and / or examples of the present invention are directed to surface modified polymeric materials, modified functionalized polymers, functional polymers, chemically modified substrates comprising modified functionalized polymers, and / or methods of making and / or using surface modified polymeric materials, modified functionalized polymers, functional polymers, and / or chemically modified substrates comprising modified functionalized polymers, methods of modifying functional polymers and / or methods of using modified functionalized polymers to chemically react with the surface of a substrate, and / or methods of using such chemically modified substrates. At least certain embodiments are directed to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers to chemically modify porous and / or non-porous polymeric substrates and / or methods of using such modified substrates. At least selected embodiments are directed to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers to chemically modify porous and / or microporous polymeric substrates and methods of using such modified substrates. At least certain embodiments are directed to modifying certain functionalized polymers to make possible the alteration of the surface properties of a substrate. According to at least selected and possibly preferred embodiments, the present invention is directed to chemically modifying a functionalized polymer (component B) using a carbene and / or nitrene bridge modifier (component B, which can include monomer X or monomer X+Y) to form a modified functionalized polymer AB having a carbene or nitrene functionality that can chemically react with the surface of the substrate to alter the surface properties of the substrate for the intended application. According to at least selected and possibly preferred embodiments, the present invention is directed to covalently modifying a polymer surface (component C) with a functionalized polymer (component A) using a carbene and / or nitrene bridge modifier (component B, which can include monomer X or monomer X+Y) to form a modified substrate ABC. Such modification can alter the chemical reactivity of the polymer surface, thereby allowing the modified substrate to have functionality specifically designed for the intended end use or application.

[0061] Modified substrates according to the present invention are illustrated, for example, in Figures 3 to 6. In Figure 3, modified substrate ABC includes component C (polymer or textile substrate) that has been modified by combining component A (functional polymer, fluoropolymer, marker, etc.) with component B (carbene and / or nitrene crosslinking modifier). Component A provides the modified substrate with one or more desired properties (e.g., fluorescent marker, hydrophobicity, hydrophilicity, etc.), and component B provides reactivity to the surface of component C to modify it with some functionality like component A. In Figure 4, two modified substrates include component C (polymer or textile substrate) that has been modified by component B that includes monomers X and Y. In Figure 4, monomer X provides nitrene and / or carbene reactivity to modify the surface of component C, and monomer Y provides some desired property or functionality to the system.

[0062] FIG. 5 illustrates a modified substrate A-BCD where an additional component, here component D, has been added to the system. In FIG. 5, component D can be a coating, such as a ceramic coating. Component C can be any polymeric material or textile substrate that is not normally compatible with component D. By combining a functional polymer A (also referred to as component A) with a modifying component B to modify the surface of component C, component D can be surface modified without the surface modifier of the present invention. The surface modifier of the present invention can adhere to the surface of component C more easily and more durable than in the absence of the surface modifier of the present invention. Similarly, two modified substrates are illustrated in Figure 6 where an additional component, component D, is added to the system. In Figure 6, component D can be a coating, such as a ceramic coating. By modifying the surface of component C with a material comprising monomer Y and monomer X, component D adheres to the surface of component C more easily and more durable than in the absence of the surface modifier of the present invention.

[0063] At least certain objects, embodiments, aspects, and / or examples of the present invention are directed to improved or novel methods of permanently modifying polymeric substrates, surface modified polymeric materials, modified functionalized polymers, functional polymers, uses of such materials, and the like for various end uses or applications.

[0064] At least certain embodiments of the present invention can address current demands and / or are directed to new, improved or modified surface-modified polymeric materials, modified functionalized polymers, functional polymers, and / or chemically modified substrates comprising modified functionalized polymers, and / or methods of modifying functional polymers, and / or methods of using modified functionalized polymers to chemically react with the surface of a substrate, and / or methods of using such chemically modified substrates.

[0065] More particularly, certain embodiments are directed to modifying certain functionalized polymers, thereby enabling changes in the surface properties of a substrate to be effected. According to at least selected preferred embodiments, the present invention is preferably directed to chemically modifying a functionalized polymer (component A or functional or functionalized component A) using a nitrene (or carbene) crosslinking modifier (component B, which may include monomer X or monomer X+Y) to form a modified functionalized polymer AB, which can then chemically modify the surface of a polymeric substrate to alter the surface properties of the polymeric substrate for an intended application.

[0066] At least selected embodiments are directed to methods of preparing surface modifiers, which in some embodiments include styrene sulfonated monomers, polymers, or copolymers containing nitrene or carbene precursor functional groups that can undergo a chemical reaction initiated by heat or UV light to form nitrene and / or carbene entities. At least selected embodiments are directed to surface modifiers that include styrene sulfonated monomers, polymers, or copolymers containing nitrene entities that can chemically react with the surface of a polymer or textile material to impart a particular or desired chemical surface functionality to the polymer or textile material.

[0067] At least certain embodiments are directed to a method of copolymerizing monomer X with monomer Y, where monomer Y can contain any type of functional group that can change the surface energy and / or chemistry of a polymer or textile material (component C) to form component B comprising monomer X+Y. Also, some embodiments are directed to combining component A, which contains functional groups specifically selected to have a desired functionality such as hydrophilic, hydrophobic, oleophilic, or oleophobic and / or selected to change the surface energy of the polymer or textile material, with a modified styrenesulfonyl azide monomer, polymer, or copolymer to form a modified functionalized AB species that can react with heat or light (such as UV light) to form a modified styrenesulfonyl nitrene monomer, polymer, or copolymer with nitrene functionality that can chemically react with saturated hydrocarbon substrates, labeled component C, to form an ABC polymer or textile material suitable for the intended end use application.

[0068] When aliphatic or aryl azides are exposed to UV light, they form nitrene groups that can initiate insertion reactions into C-H bonds by additional reaction with N2 as a by-product. With optimized exposure to UV light in a selected wavelength range, the modified azides show their reactivity. With the nitrene end groups, it can function as a cross-linking and labeling reagent. If the modified aliphatic or aryl azide also contains specific chemical groups with functionality, such as hydrophilic, hydrophobic, oleophilic, or oleophobic, reaction of the R-:N:nitrene groups with saturated CH sites on the surface of the substrate material inserts the functionalized AB moiety, introducing new and desirable chemical functionality into component C, the polymer or textile substrate.

[0069] Nitrenes (R-:N:) are the nitrogen analogues of carbenes and have only six valence electrons. Nitrenes and carbenes are reactive intermediates that can have unique reactivity towards both functional and nominally non-functional substrates. While there may be methods available for modifying certain functional polymer substrates, the present invention provides a method that is highly suitable for modifying those polymer substrates that are non-functional, i.e., do not contain functional groups. Most polyolefins are essentially "non-functional" because they do not readily accept modification without significant consequences to the mechanical or chemical stability of the material. Nitrene-based intermediates provide the opportunity to modify non-functional polyolefins without the severe degradation that typically occurs with many conventional surface modification approaches. Furthermore, the use of the nitrene-based intermediates of the present invention can provide the opportunity to be applied to most, if not all, polymer substrates, regardless of functional group-specific chemical modification. The reactive nitrene-based intermediates of the present invention have the advantage of being able to penetrate into the carbon-hydrogen chemical bonds of polyolefin polymer substrates. The unique chemical reactivity of the nitrene-based intermediate component B provides a means to attach selected functional groups to polymeric or textile substrates.

[0070] Examples of azides capable of forming reactive nitrene groups include, but are not limited to, aryl azides, acyl azides, azidoformates, phosphoryl azides, and sulfonyl azides. A preferred embodiment shown below is a polystyrene sulfonyl azide polymer copolymerized with a modified polystyrene polymer of R groups, with a preferred 'n / n+m' ratio of 0.1≦n / n+m≦0.75. Three examples of R functional groups for modified polystyrene polymers shown below are styrene, 2,3,4,5,6-pentafluorostyrene, and 4-styrenesulfonate.

[0071] [ka]

[0072] According to one embodiment of the present invention, a modifier component B having multiple nitrene intermediates or precursors can be mixed with one or more desired functional components A to form a specific chemical species referred to herein as a "multiple reactive site modified functionalized polymer AB." In the proper ratio and formulation, said polymer AB can further react with a given polymer substrate, which can be polyolefinic in nature, or with any other synthetic or naturally occurring polymeric material, resulting in the attachment of specific desired chemical functional groups to the polymer substrate, which specifically tailors the chemical structure of the polymer substrate for the intended end use.

[0073] The modified functionalized polysulfonated nitrene monomers, polymers or copolymers can undergo chemical reactions, particularly intercalation reactions, to insert themselves into one or more C-H bonds on the surface of the polymer substrate, thereby permanently covalently modifying the surface of the polymer substrate. A polystyrene sulfonated nitrene monomer, polymer or copolymer with a nitrene-generating species can be attached to multiple sites on the surface of a polyolefin by an insertion reaction into one or more C-H bonds of the polyolefin polymer substrate to form the resulting functionalized material (polyolefin substrate ABC). The resulting composite material (polyolefin substrate ABC) has similar bulk properties to the polyolefin substrate, but the surface properties of the polystyrene sulfonated monomer, polymer or copolymer. For example, a modified polyolefin surface may appear to have a much higher surface energy than normal polyolefins, depending on the quality and extent of the modification. Also, a modified polyolefin surface may appear to have a higher or lower degree of hydrophilicity, hydrophobicity, oleophilicity or oleophobicity.

[0074] According to at least selected embodiments of the present invention, the polyolefin polymer substrate can be a microporous polyolefin membrane substrate with a surface that has been chemically modified with component AB functionality, for example to have a higher or lower degree of hydrophilicity, hydrophobicity, oleophobicity or oleophilicity, or to have a different surface energy. Microporous polyolefin membranes tend to absorb large amounts of oil into their pores. The functionalized component AB treatment or modification of the present invention can be used to modify the oleophilic surface of microporous polyolefin membranes, reducing their oil absorption or eliminating their oil absorption, thereby producing modified microporous polyolefin membrane substrates for use in new types of separation or filtration performance of various materials.

[0075] One example of an end use application made possible by using functionalized component AB to change the oleophilicity of the microporous polyolefin membrane is a "water-resistant / breathable" outerwear, where the comfort of the water-resistant outerwear garment containing the microporous polyolefin membrane can be greatly improved by improving the breathability of the garment, thereby allowing the moisture of the wearer's body to evaporate through the fabric of the water-resistant outerwear. Such functionality is usually referred to as a "water-resistant / breathable" outerwear. Many water-resistant / breathable garments incorporate non-porous materials that achieve breathability using molecular transport of water molecules. Improved breathability must be provided by incorporating a truly porous membrane that allows the water vapor molecules to evaporate by diffusion in the air, thus greatly improving breathability and enhancing wearer comfort. One drawback of certain microporous membranes is that they can be fouled by natural body oils or other oils, resulting in a decrease in the water-resistant performance of the membrane. The drawback can be overcome using the present invention by modifying the surface of the microporous membrane with, for example, a fluorinated compound, to make the membrane surface oleophobic and resistant to fouling by natural body oils or other oils.

[0076] According to at least selected embodiments of the present invention, there are also applications where the functionalized component AB is used to reduce the surface energy of polymeric textile fibers and / or fabrics. Water and / or stain resistance of polymeric textile fibers and fabrics is often achieved by applying durable water repellent ("DWR") coatings and finishes. These DWR coatings and finishes are less durable and wear off with repeated washing and / or use. Some textile fibers and fabrics, such as those made of acrylic resins, are not as easily treated with DWR coatings and are often not used in applications where water and / or stain resistance is important. At least certain methods or embodiments of the present invention can be used to modify polymeric textile fibers and / or fabrics, for example using fluorinated compounds, to make the polymeric textile fibers and / or fabrics durably water and / or stain resistant.

[0077] Additionally, in accordance with at least selected embodiments of the present invention, the functionalizing compound AB can be used to reduce the surface energy of polyolefin films used in the walls of certain fragrance container devices. Certain fragrance container devices function by the controlled release of fragrance materials through one or more walls of the fragrance container device. The fragrance container devices can typically include polyolefins, and are often made of polyethylene. However, fragrance container devices can also be used to reduce the surface energy of polyolefin films used in the walls of certain fragrance container devices. The release rate of fragrance through the polyolefin membrane wall of the device can be limited by the non-porous nature of the polyolefin membrane, and as a result, the fragrance container device must be increased in size and / or the concentration of fragrance in the fragrance container device must be increased (thereby increasing cost) to achieve a desired release rate of fragrance.

[0078] There is an economic demand to reduce the amount of fragrance used in such fragrance container devices while achieving desired fragrance release rate.For the above reasons, the use of microporous polymer membrane as the wall material of fragrance container devices or containers promotes the movement of fragrance through the membrane wall of fragrance container devices at a much faster rate.However, the use of microporous polyolefin membranes in fragrance container device applications has been limited by the tendency of fragrance oil to leak through the membrane wall of the container.The above drawbacks can be overcome by using the present invention, which modifies the surface energy of microporous membranes, for example by using fluorinated functionalized polymer AB, to make the membrane or wall of fragrance container devices oleophobic, preventing fragrance oil from leaking.

[0079] According to at least selected embodiments of the present invention, the modified functionalized polymer AB can modify a polymer substrate, which in the absence of the modified functionalized polymer AB has a lowered or increased surface energy that would prevent direct attachment of a desired chemical entity. Alternatively, the modified functionalized polymer AB can covalently modify a polymer substrate, which in the absence of the modified functionalized polymer AB has a polarity that would normally limit and / or prevent direct attachment of a desired chemical entity. The modified functionalized polymer AB can also modify a polymer substrate, which has a surface that is hydrophilic or hydrophobic, i.e., a surface property that would normally limit and / or prevent direct attachment of a desired chemical entity, in the absence of the modified functionalized polymer AB. Alternatively, the modified functionalized polymer AB can modify a polymer substrate, which has a surface that is oleophilic or oleophobic, i.e., a surface property that would normally limit and / or prevent direct attachment of a desired chemical entity, in the absence of the modified functionalized polymer AB.

[0080] At least certain embodiments are directed to modifying certain functionalized polymers with the purpose of including biologically derived polymers and small molecules for end use applications that may require biological detection or assays. Proteins, DNA, RNA, natural polysaccharides, or other biologically relevant materials can be used in these types of applications. In such embodiments, modification can occur by modifying certain functionalized polymers with a single carbene and / or nitrene component B, or with multifunctional carbene and / or nitrene components B. At least certain embodiments are also directed to modifying the surface of a polymer substrate with a mixture of multifunctional carbene and / or nitrene precursor components B reacted with a desired component A, such as a functional synthetic polymer, a small molecule, a biologically active surface modifier, and the like.

[0081] The surface of a polymeric substrate can be modified to change its functionality. For example, a normally chemically inert polymeric substrate can be modified by decorating the surface of the substrate with functional groups, either with a functional component A or with a modified functional component AB, which is designed to participate in a secondary post-treatment reaction that modifies the polymeric substrate. Such a change modifies the functionality of the polymeric substrate for the intended end-use application. An example of such a post-treatment reaction is a textile end-use application in which the surface of the textile substrate is reacted with a modified component AB so that it can accept standard textile dyeing chemicals and precursors to produce a substantially different end result.

[0082] The polymeric substrate (e.g., component C) can include any synthetic or natural polymer or copolymer, such as olefin, styrene, silicone, urethane, acrylate, ester, vinyl, cellulose, amide, aramid, ether, or copolymer, and mixtures thereof. The polymeric substrate can also include crosslinked polymers such as phenol-formaldehyde resins. The polymer substrate may be a network material, or a rubber-type material such as butadiene, isoprene, and neoprene, and the polymer substrate may be a halogen-containing polymer such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinylidene dichloride (PVDC), and / or polyvinyl chloride (PVC).

[0083] The chemical structure of the modified functional styrene sulfonated monomer, polymer or copolymer, which may also be referred to as component AB, contains the desired surface functional groups (e.g., component A) required by the polymer substrate (component C) of the end-use application. The functional polymer A or component A can include polymers similar to the polymer substrate. The functional polymer A or component A can also include polyamines, polyols, polyamides, and mixtures or copolymers thereof.

[0084] At least selected embodiments of the present invention are directed to modified porous membranes, methods of making modified porous membranes, and methods of using modified porous membranes. More particularly, the present invention is directed to chemically modified polyolefin microporous membranes, methods of making chemically modified polyolefin microporous membranes, and methods of using chemically modified polyolefin microporous membranes. Even more particularly, the present invention is directed to chemically modified polyolefin microporous battery separators or battery separator membranes, methods of making chemically modified polyolefin microporous battery separators or battery separator membranes, and methods of using chemically modified polyolefin microporous battery separators or battery separator membranes.

[0085] In accordance with at least selected preferred embodiments, the present invention is directed to chemically modifying polyolefin microporous battery separators or separator membranes by chemical reaction of carbene and / or nitrene intermediates with carbon-hydrogen bonds of polyolefins, methods of improving the hydrophilicity or wettability of polyolefin microporous battery separators or separator membranes in lithium ion rechargeable batteries, methods of introducing crosslinks into polyolefin microporous battery separators or separator membranes, and the like.

[0086] According to at least selected preferred embodiments of the present invention, chemical modification of at least a portion of the surface of the polyolefin microporous separator or separator membrane can be achieved by chemical reaction of carbene and / or nitrene intermediates with carbon-hydrogen bonds of polyolefins. The above chemical reactions or treatments based on carbene and / or nitrene intermediates provide a method to further permanently improve the wettability of polyolefin microporous separators in lithium-ion rechargeable batteries. In addition, the preferred reaction of carbene and / or nitrene intermediates with C-H bonds in at least the surface layer of the polyolefin microporous separator membrane can be used to introduce crosslinks into the polyolefin, which can improve the high temperature stability of the polyolefin microporous separator or membrane.

[0087] Exemplary battery separators or membranes can be single layer, multi-layer, or multi-ply battery separators made of one or more layers or plies of polyolefin porous or thin films. The microporous membranes can be symmetric or asymmetric membranes. The membranes can be made from one or more polyolefin polymers or blends, including but not limited to polyethylene (PE, e.g., LDPE, LLDPE, and HDPE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polymethylpentene (PMP), copolymers of any of the above, and mixtures thereof. The membranes are made by any suitable method, including but not limited to the dry stretching method (also known as the CELGARD process) or the solvent process (also known as gel extraction or phase separation or phase inversion or extraction or wet process) or the netting (or aperture) method (a thin film is cast onto a chill roll, which has a pattern embossed into the film, and then the embossed film is stretched (MD / TD), thereby forming large holes along the embossed pattern). Such membranes can have a thickness of about 75 microns or less. The membrane preferably has the necessary characteristics to act as a battery separator in batteries such as lithium batteries, and more preferably rechargeable lithium ion batteries. The chemically modified membrane of the present invention can be a tri-layer membrane (e.g., PP / PE / PP or PE / PP / PE) or other multi-layer membrane or separator, such as the outer layer of a tri-layer separator.

[0088] Polyolefins are a class or group of thermoplastic polymers derived from simple olefins. Polyolefins typically include polyethylene, polypropylene, polybutylene, polymethylpentene, and copolymers thereof. Polyolefin commercial products generally include fibers and films, but also microporous films and microporous hollow fibers. "Microporous" refers to commercial products that have multiple pores with effective diameters of 1 micron or less. Hydrophobic polyolefins refer to polyolefins that have a surface energy equal to or less than that of polyethylene.

[0089] According to at least certain embodiments, polyolefin articles are made more hydrophilic or wettable by chemically modifying at least a portion of the surface of the polyolefin article, such as a microporous separator or membrane, by chemically reacting a carbene and / or nitrene intermediate with the carbon-hydrogen bonds of the polyolefin. Also, the preferred reaction of the carbene and / or nitrene intermediate with the C-H bonds in at least the surface layer of the polyolefin article can be used to introduce crosslinks into the polyolefin, which can improve high temperature stability, strength, etc. The hydrophilic polyolefin articles can be used in any application where hydrophilic polyolefins are needed or desired, such as air filtration, air purification, water filtration, water purification, water purification, medical devices, separation devices, semiconductor manufacturing, battery cell separators, ultrafiltration devices, etc.

[0090] For battery or cell separators, the chemical treatment is applied to one or both sides of the microporous polyolefin membrane. The treated separator is particularly suitable for lithium secondary batteries. For separation, filtration, cleaning, and purification equipment, especially when using microporous polyolefin hollow fiber or flat membranes, higher flux rates can be obtained by using the modified materials.

[0091] Chemically modifying the carbon-hydrogen and other bonds of polyolefins as a means of permanently modifying their hydrophobic properties can be problematic due to the limited number of chemical reactions available. Carbon-hydrogen bonds are very stable, making polyolefins such as polypropylene and polyethylene difficult to permanently modify. Polyolefins such as polypropylene and polyethylene are commonly used in microporous separator membranes for lithium-ion rechargeable batteries. An important performance characteristic of polyolefin microporous separator membranes is that they are easily wettable by non-aqueous electrolyte solvents commonly used in lithium-ion rechargeable batteries. Currently, various surfactants are applied as coatings that modify the hydrophobic properties of polyolefin microporous separator membranes and improve their wettability by non-aqueous electrolyte solvents. Certain surfactant coatings may only provide temporary wettability because they are only physically adsorbed onto the surface of the polyolefin microporous separator membrane.

[0092] Carbene and / or nitrene surface treatment can also be accomplished with a wide variety of small molecule functional groups. Carboxylic acids, alcohols, thiols, amines (primary, secondary, tertiary, and quaternary), guanidinium, ethers, esters, and carbonates are functional groups that can impart some hydrophilic properties to the polyolefin microporous separator membrane.

[0093] A significant increase in the wettability of polypropylene microporous separator membranes with superpolar electrolytes can be achieved by the inventive chemical modification of polypropylene microporous separator membranes, thereby expanding the scope of current and future electrolytes that can be used in lithium ion rechargeable batteries. can be further expanded.

[0094] For example, the wetting properties of substrates can be drastically modified based on substitution with molecular additives. Perfluoro groups can impart superhydrophobic behavior, while the addition of poly(ethylene glycol) can improve wettability. The feel of the material can be improved by using poly(dimethylsiloxane) to make the substrate more pleasant to the touch. Furthermore, cross-web toughness can be improved by surface or internal cross-linking and processing of the material with multifunctional carbene and / or nitrene precursors.

[0095] Carbene and / or nitrene intermediates involving multiple chemical reactions can also be used to insert specific structures designed to induce cross-linking in the polyolefin microporous separator membrane. Cross-linking of polyolefin materials locks the polymer molecules together, thus achieving the additional benefit of enhancing the cross-web strength of the microporous polyolefin separator membrane, thereby improving battery safety.

[0096] As an example, after pores are formed, molecules incorporating multiple carbene and / or nitrene precursors can be applied to the polyolefin microporous separator membrane to create a crosslinked surface. Crosslinking of the polyolefin microporous separator membrane surface can be important in high temperature end use applications. By creating a lightly crosslinked surface, the temperature at which the polyolefin microporous separator membrane loses structural integrity can be increased and tailored to a specific temperature range based on the density of crosslinks. This can be achieved because the crosslinked material can hold the molten bulk material without crosslinks. As the density of surface crosslinks increases, so does its ability to act as an exoskeleton to maintain the structural integrity of the polyolefin microporous separator membrane.

[0097] Additionally, cross-linking molecules incorporating multiple carbene and / or nitrene precursors can be added to polyolefin polymer resins during the extrusion process to form a non-porous precursor separator membrane, which is then stretched to form pores in a microporous polyolefin membrane, resulting in a microporous polyolefin membrane with improved tensile strength and melt completeness at elevated temperatures.

[0098] In at least selected embodiments, the separator can be a nonwoven material, such as a nonwoven fabric composed of fibers, which can be chemically modified to improve the high temperature melt integrity of the nonwoven fabric and / or to improve the wettability of the nonwoven fabric.

[0099] In accordance with at least certain objects of the present invention, new, improved or modified surface-modified polymeric materials, modified functionalized polymers, functional polymers, chemically modified substrates comprising modified functionalized polymers, methods of making and / or using surface-modified polymeric materials, modified functionalized polymers, functional polymers and / or chemically modified substrates comprising modified functionalized polymers, methods of modifying functionalized polymers, and / or methods of using modified functionalized polymers to chemically react with the surface of a substrate, and / or methods of using such chemically modified substrates. At least certain embodiments or objects are directed to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers to chemically modify porous and / or non-porous polymeric substrates, and / or methods of using such modified substrates. At least selected embodiments or objects are directed to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers to chemically modify porous and / or microporous polymeric substrates, and methods of using such modified substrates. At least certain embodiments or objectives are directed to modifying certain functionalized polymers, thereby enabling the modification of the surface properties of a substrate. According to at least selected and possibly preferred embodiments, the present invention relates to carbenes and The present invention is directed to the use of carbene and / or nitrene crosslinking modifiers to chemically modify a functionalized polymer, thereby chemically modifying the surface of a substrate to form a modified functionalized polymer that can alter the surface properties of the substrate for an intended application. According to at least selected and possibly preferred embodiments, the present invention is directed to the use of carbene and / or nitrene crosslinking modifiers (component B, which can include monomer X or monomer X+Y) to covalently modify a polymer surface (component C) with a functionalized polymer (component A) to form a final product that is a modified functionalized polymeric material or substrate ABC. Such modification can change the chemical reactivity of the polymer surface, thereby enabling the modified substrate to have functionality specifically designed for an intended end use or application.

[0100] The present invention relates to new, improved or modified polymeric materials, membranes, substrates, etc., and to new, improved or modified methods of permanently modifying the physical and / or chemical properties of one or more surfaces, sides or portions of a polymeric substrate for various end uses or applications. For example, one improved method uses carbene and / or nitrene modifiers to chemically modify a functionalized polymer to form a chemical species that can chemically react with the surface of the polymeric substrate to change its chemical reactivity. Such methods can include intercalation reactions or mechanisms that modify the polymeric substrate to increase or decrease its surface energy, polarity, hydrophilic or hydrophobic, oleophilic or oleophobic, etc., to improve the compatibility of the polymeric substrate with coatings, materials, adjacent layers, etc. Additionally, the present invention can be used to produce chemically modified membranes, fibers, hollow fibers, fabrics, etc. For example, the present invention can be used to produce polyolefin microporous battery separators or membranes that have improved hydrophilicity or wettability, have crosslinks in the polyolefin that can improve high temperature stability, etc.

[0101] Various embodiments of the present invention relate to a polymer comprising a polymerized arylsulfonyl azide or copolymer thereof. In such embodiments, the arylsulfonyl azide may be styrenesulfonyl azide. The arylsulfonyl azide may also be copolymerized with a vinyl monomer. In such cases, the vinyl polymer may be hydrophilic or hydrophobic. The vinyl monomer may also be styrenesulfonic acid or a salt thereof. The vinyl monomer may also be selected from the group consisting of substituted styrene, acrylic acid, methacrylic acid, vinylpyridine, vinylpyrrolidone, acrylamide, methacrylamide, salts thereof, and the like. The vinyl monomer may also be substituted with a reactive group.

[0102] In various other embodiments of the present invention, the modified substrate comprises a surface modifier, the agent comprising a first polymer comprising a polymerized arylsulfonyl azide or copolymer thereof, at least one azide of the first polymer reacts with a carbon atom of the substrate to form a sulfonamide linking group. In such embodiments, the azide can react with the carbon atom by exposing the first polymer and the substrate to UV light. In such embodiments, the substrate can be selected from the group consisting of polymers, woven substrates, fibers, polyolefin materials, polypropylene materials, polyethylene materials, porous polymer substrates, non-porous polymer substrates, microporous polymer substrates, porous hollow fibers, non-porous hollow fibers, porous battery separators or membranes, microporous polymer membranes, thin films, chemically modified polymer substrates, polymer surface layers, composites, compounds thereof, and the like.

[0103] Other embodiments of the invention include methods of modifying a substrate, the methods comprising contacting the substrate with a polymer that can include a polymerized arylsulfonyl azide or a copolymer thereof. In such methods, the substrate can be contacted with the polymer in the presence of UV light and / or heat. Also, in such embodiments, the polymer can be a copolymer with a vinyl monomer substituted with a reactive group, and the methods can further include a step of reacting the reactive group. The substrate includes a surface treatment step, thereby modifying the surface of the substrate.

[0104] In at least some embodiments related to selected oleophobicity: 1. Polymer surfaces (thin films, fibers, or bulk materials) can be modified with a mixture of multifunctional carbene and / or nitrene precursors (component B, which can include monomer X or monomer X+Y) and the desired functional synthetic monomer or polymer (component A). The polymer surface may be any synthetic or natural polymer or copolymer, including but not limited to the following polymer classes: olefin, styrene, silicone, urethane, acrylate, ester, vinyl, cellulose, amide, aramid, ether, etc. The polymer surface may be a cross-linked network material such as phenol-formaldehyde resin or rubber type materials, e.g., butadiene, isoprene, and neoprene. Modification of other halogen-containing polymers / polymer surfaces may also be performed, such as PTFE, PVDF, PVDC, and PVC.

[0105] b. Component A can be a material commonly found in hydrophobic or oleophobic treatment applications. Materials such as fluorinated acrylic copolymers, which are used extensively as textile treatments, or chitin-based materials can provide adequate oil resistance. Component A can also be a composite with additional nanoparticles to create nanoscale roughness for enhanced resistance. c. Component B can be a monofunctional material (f=1), or in other embodiments, a multifunctional material (f>2.0) with side functional groups tailored to generate carbene and / or nitrene species in situ.

[0106] 2. A coating weight of a mixture of components A and B can be derived from an organic or aqueous solution, and surface modification of the polymer surface is further advanced by heat treatment or exposure to UV light. a. The modification can be added to the surface in sufficient quantity to provide the necessary surface properties for the intended application. A typical application rate is 0.05 g / m 2 ~1.0g / m 2and may depend on the surface area of ​​the substrate, solution viscosity, and / or cure speed, among other factors. b. The ratio of components A and B can be varied to produce optimum properties. Typical A / B application weight ratios can range from 1.0 to 200.0 depending on the desired surface properties and the reactivity of A and B.

[0107] According to at least selected objects or embodiments, the present invention provides or is directed to the following: A modified polymeric substrate, a surface-modified polymeric material, a modified functionalized polymer, a functional polymer, or a chemically modified substrate comprising a modified functionalized polymer as illustrated or described herein.

[0108] The above invention, wherein the modified polymer substrate is a chemically modified polymer substrate.

[0109] The above invention, wherein the modified polymer substrate is at least one of a porous polymer substrate, a non-porous polymer substrate, a porous hollow fiber, a non-porous hollow fiber, a porous battery separator or membrane, a thin film, a chemically modified polymer substrate, a fiber, a fabric, a polyolefin material, a polyolefin blend, a polypropylene material, a polyethylene material, a polymer surface layer, a composite, a combination thereof, and the like.

[0110] The above invention, wherein the modified polymer substrate is chemically modified by chemical reaction of at least one of a carbene and nitrene intermediate with carbon-hydrogen bonds of the polymer substrate to covalently attach at least one modified functionalized polymer thereto.

[0111] Modified polymeric substrates, surface modified polymeric materials, modified functionalized polymers, functional polymers, or chemically modified substrates comprising modified functionalized polymers, thin films, hollow fibers, fibers, fabrics, composites, layers, surfaces, chemically modified polyolefin microporous membranes, chemically modified polyolefin microporous battery separators or battery separator membranes, microporous battery separators or battery separator membranes, ribbed materials, methods of making or using the compounds thereof, methods of improving the wettability of polyolefin microporous battery separators in lithium ion rechargeable batteries, methods of introducing crosslinks into polyolefin microporous separators, and the like, as shown or described herein.

[0112] The above method includes at least one of the steps of chemically modifying a polyolefin microporous battery separator membrane by chemically reacting at least one of a carbene and a nitrene intermediate with carbon-hydrogen bonds of the polyolefin, improving the wettability of the polyolefin microporous battery separator adapted for use in a lithium ion rechargeable battery, and introducing crosslinking bonds into the polyolefin microporous battery separator.

[0113] The improvement in a battery separator includes a polyolefin microporous membrane having at least a portion of at least one surface that is chemically modified.

[0114] The separator, wherein the chemically modified polyolefin has a surface energy equal to or greater than a surface energy of polyethylene.

[0115] The separator, wherein the chemical modification increases the surface energy of the polyolefin to at least about 48 dynes / cm.

[0116] The separator, wherein the polyolefin microporous membrane is chemically modified to increase the surface energy of the membrane.

[0117] The separator, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, blends, mixtures, and copolymers thereof.

[0118] An improvement in a battery comprising a negative electrode, a positive electrode, an electrolyte, and a separator, including said separator.

[0119] An improvement in a fabric comprising a polyolefin microporous membrane, said polyolefin microporous membrane having at least a portion of at least one surface chemically modified.

[0120] The textile, wherein the chemically modified polyolefin membrane has a surface modification comprising a cellulosic material for the purposes of secondary standard textile processing such as dyeing or other finishing steps.

[0121] The fabric, wherein the chemically modified polyolefin membrane has a surface energy equal to or less than a surface energy of polytetrafluoroethylene.

[0122] The fabric, wherein the chemical modification reduces the surface energy of the polyolefin film to a maximum of about 20 dynes / cm.

[0123] A textile laminate comprising at least one synthetic or natural textile associated with the polyolefin membrane.

[0124] Polyolefin microporous membranes chemically modified to reduce their surface energy wherein said polyolefin is selected from the group consisting of polyethylene, polypropylene, and blends, mixtures, and copolymers thereof, and said chemically modified polyolefin has a surface modification comprising an oleophobic polymer or combination of polymers, or the like.

[0125] A microporous polymer membrane having at least one surface or portion that has been chemically modified by chemical reaction of at least one of a carbene and a nitrene intermediate to have at least one modified functionalized polymer covalently attached thereto to provide a durable chemical modification that provides at least one of improved wettability, reduced wettability, hydrophilicity, hydrophobicity, oleophobicity, oleophilicity, resistance to fouling by biological materials, resistance to wetting by organic solvents, resistance to wetting by methanol, ethanol, 1-propanol, acetone and / or other polar type solvents, and resistance to wetting by aliphatic and / or aromatic type solvents.

[0126] Non-limiting Examples Example 1 - Synthesis of 4-styrenesulfonyl azide monomer In Example 1, 4-styrenesulfonyl azide monomer was synthesized. In detail, 34.4 grams of thionyl chloride (290 mmol) was added to a flask and cooled in an ice bath. 10 grams of sodium-4-styrene sulfonate (48.4 mmol) was added in portions to the cooled thionyl chloride with stirring. As the solids were added, the solution was observed to thicken and become a slurry. 60 mL of DMF was added in 20 mL aliquots and stirring was continued to produce a homogenous solution. The solution was stirred in an ice bath for 45 minutes, allowed to warm to room temperature, and then stirred for an additional 1-2 hours. Once complete, the reaction product was poured onto ice (approximately 200 grams) and the mixture was extracted with ethyl acetate (3 x 50 mL). The sulfonyl chloride layer was collected, dried over magnesium sulfate, and concentrated to 7.24 grams of a light yellow-orange oil.

[0127] The sulfonyl chloride obtained in the previous step (35.1 mmol) was dissolved in acetone and placed in an ice bath. 20 mL of ionized H2O was added, followed by 2.39 grams of sodium azide (36.9 mmol) in portions over a period of 5 minutes. The reaction was allowed to stir for 5 days, at which point the solution was washed with ethyl acetate (3 x 20 mL). The resulting organic portion was collected, dried over magnesium sulfate and concentrated to a light yellow oil (7.21 g was obtained). The light yellow oil constituted the 4-styrene sulfonyl azide monomer.

[0128] Example 2-4-Synthesis of styrene-based polymer containing styrenesulfonyl azide The sulfonyl azide monomer produced in Example 1 above (1.5 grams, 7.1 mmol) was added to a flask along with various desired comonomers (described in more detail below) (7.1 mmol) and a chain transfer agent. Here, the specific chain transfer agent used was 2-cyano-2-propyldodecyl trithiocarbonate (28 mg, 0.08 mmol). The initiator (here 4,4'-azobis(4-cyanovaleric acid)) (42 mg, 0.15 mmol) was separately dissolved in a DMF (3 mL) solution that was added to the polymerization flask. The polymerization flask was then sealed with a rubber septum and the solution was sparged with nitrogen for 5 minutes. The polymerization flask was then placed in a constant temperature bath at 60°C for 5 hours. After the polymerization had proceeded, the reaction was quenched by exposure to oxygen and the sulfonyl azide polymer was recovered by precipitation in an appropriate solvent.

[0129] Comonomers polymerized with the sulfonyl azide monomers included 2,3,4,5,6-pentafluorostyrene, styrene, and 4-styrene sulfonate. In the case of 4-styrene sulfonate polymerization, additional DMF was required to aid in dissolving the solid 4-styrene sulfonate material.

[0130] Example 3 - General activation of sulfonyl azide polymers to form nitrenes and react with substrates upon exposure to UV Formulation and activation of the sulfonyl azide material was performed by dissolving it in acetone with an appropriate polymer for the desired surface modification, typically at a weight ratio of 1:1 to 1:10 sulfonyl azide:functional polymer. The solution was applied to the substrate and the solvent was allowed to dry. The resulting thin film and substrate were exposed to high intensity long wave UV local illumination for 15 to 45 seconds and rinsed again with acetone to remove any physisorbed material. In some cases, good results were obtained with 254 nm wavelength UV treatment.

[0131] The activated sulfonyl azide polymer was examined using various analytical techniques. By way of example, Figure 7 shows a graph of the FTIR spectrum of a polymer formed with about 50% monomer content of sulfonyl azide monomer and about 50% monomer content of 4-sulfonic acid styrene comonomer. By way of example only, Figure 7 shows the FTIR spectrum at 2000 cm -1 ~2500cm -1 peak which appears to correlate with the azide content of the polymer.

[0132] 8 also shows the DSC curve of a polymer formed with about 50% monomer content of sulfonyl azide monomer and about 50% monomer content of 4-sulfonic acid styrene comonomer. The calorimetric curve shows, for example, that water escapes at about 100° C., followed by nitrene activation, resulting in nitrogen loss just above 190° C., which may be considered the nitrene activation temperature in this particular example.

[0133] 9 shows a graph of a thermogravimetric analysis performed on a polymer formed with about 50% monomer content of sulfonyl azide monomer and about 50% monomer content of 4-sulfonic acid styrene comonomer. The analysis of the polymer shows that the polymer decomposes at various temperatures, and nitrene formation can also be traced from the graph. For example, nitrene formation is observed at various temperatures and correlates with the weight loss of the polymer.

[0134] Example 4 - Reactive dyeing of polypropylene nonwoven fabric Poly(sodium styrene sulfonate-co-styrene sulfonyl azide) was synthesized with 37% sulfonyl azide monomer content by dissolving 210 mg in 12.5 grams of hot water at 70° C. To the above solution was added 440 mg of a 50% by weight solution of branched polyethyleneimine (BPEI). Then, 2.98 grams of acetone was added for wetting purposes. The solution was applied to a polypropylene nonwoven material (100 grams per square meter (gsm)) and after exposure to the solution, the substrate was dried in a convection oven at 110° C. for approximately 5 minutes. The dried substrate was then heated to 0.2 J / cm 2 The materials were then exposed to a 5 mg / mL solution of Drimaren Navy reactive dye. Results from these prepared samples demonstrated a patchy but durable coloration of the nonwoven fabric. The addition of an additional 440 mg of BPEI solution improved results, producing a uniform and durable blue color on the nonwoven material. An untreated section of the nonwoven fabric was also exposed to the dye solution but did not color by the above process.

[0135] Example 5 - Durable Oil Repellency of Polypropylene Nonwoven Fabric Poly(sodium styrene sulfonate-co-styrene sulfonyl azide) was synthesized with 50% sulfonyl azide monomer content and 102 mg was dissolved in 3 mL water and 1 mL acetone along with 1.5 mL TG-8731 (20 wt%, Daikin) fluoropolymer. Polypropylene nonwoven fabric (45 gsm) was treated with the above solution and dried in a convection oven at 115°C for 5 minutes. Once dry, the substrate was exposed to long wave UV light for 5 minutes. After UV treatment, the sample was exposed to an agitated acetone bath to remove any material that was not covalently attached. The samples were again dried at 115°C for 5 minutes and rinsed with acetone before being tested for dodecane repellency. All four samples showed dodecane repellency after the acetone removal step. The control sample did not exhibit dodecane repellency throughout the process.

[0136] According to at least selected embodiments, aspects, objectives, etc., the present invention is directed to new, improved or optimized surface modifiers, materials made or modified with such agents, and / or methods of making and / or using such agents and / or modified materials, and / or new, improved or optimized polymeric and / or textile materials, separators, garments, fabrics, etc. incorporating such agents, modified materials, layers, substrates, precursors, etc. According to at least certain embodiments, the present invention is directed to surface modifiers for polymeric and / or textile materials, modified materials, and / or methods of making and / or using surface modifiers that modify and functionalize polymeric and / or textile materials, and / or methods of using surface modified or functionalized polymeric and / or textile materials.

[0137] According to at least certain embodiments, the present invention is directed to surface modifiers comprising suitable nitrene and / or carbene precursors that can chemically react, optionally in the presence of heat or light, to form one or more nitrene and / or carbene functional groups. In some cases preferred nitrene precursors include materials such as styrene sulfonyl azide monomers, polymers or copolymers that can chemically react in the presence of heat or light to form one or more nitrene functional groups. At least selected certain embodiments are directed to surface modifiers comprising styrene sulfonated monomers, polymers or copolymers that contain one or more sulfonyl azide functional groups that can chemically react with the surface of a polymer or textile material upon activation to impart or provide a particular or desired chemical surface functionality to the surface. At least certain possibly preferred embodiments are directed to surface modifiers comprising styrene sulfonated monomers, polymers or copolymers that contain one or more sulfonyl functional groups that can chemically react with the surface of a polymer or textile material to impart or provide a desired chemical functionality to the polymer or textile material.

[0138] The imparted modification or functionality can change the physical properties of the material or enable the material to be used in a new functional role. For example, the functionality can impart properties such as hydrophilicity, hydrophobicity, oleophilicity and / or oleophobicity and / or change the surface energy of the polymeric or textile material to covalently modify the polymeric or textile material, for example, to make it suitable for a specific end-use application. Furthermore, a specific surface modification can provide functionality specific to a new functional role. For example, the imparted functionality can be aimed at enabling the material to be used in applications where the material is interactive, for example, when it can interact with other materials, such as other molecules. Further examples include, but are not limited to, specific applications where the modified or functionalized material interacts with other materials, coatings, layers, etc., and may be particularly suitable for applications such as battery separators, barrier fabrics, membranes, substrates, layers, fabrics, textiles, etc., used in electrochemical cells or batteries, textiles, clothing, filtration, adsorption, testing, drug delivery, analyte sensing, medical devices, medical diagnostics, etc.

[0139] This application is generally related to U.S. Provisional Patent Application No. 61 / 508,725, filed July 18, 2011, U.S. Provisional Patent Application No. 13 / 551,883, filed July 18, 2012, and U.S. Provisional Patent Application No. 61 / 547,812, filed October 17, 2011, all of which and each of which are incorporated herein by reference in their entirety.

[0140] According to at least selected embodiments, aspects, objects, etc., the present invention provides new, improved, or optimized surface modifiers, materials made or modified with such agents, methods of making and / or using such agents and / or modified materials, and / or new, improved, or optimized polymeric and / or textile materials, separators, garments, fabrics, etc. incorporating such agents and / or modified materials, surface modifiers for polymeric and / or textile materials, modified materials, modified and / or functionalized polymeric and / or textile materials. The present invention also relates to a method of making and / or using surface modifiers and methods of using surface modified or functionalized polymers and / or textile materials to modify the physical properties of the polymers and / or textile materials, comprising: a surface modifier comprising a suitable nitrene and / or carbene precursor, optionally capable of chemically reacting in the presence of heat or light to form one or more nitrene and / or carbene functional groups; a surface modifier comprising, for example, a styrene sulfonated monomer, polymer or copolymer, containing one or more sulfonyl functional groups, such as sulfonyl azide functional groups, which upon activation, can chemically react with the surface of the polymer or textile material to impart a particular or desired chemical surface functionality to the surface of the polymer or textile material; or directed to enabling the material to be used in a new functional role, where the functionality can impart properties such as hydrophilicity, hydrophobicity, oleophilicity, oleophobicity, etc. to the polymer and / or textile material, and / or the functionality can modify the polymer and / or textile material by changing the surface energy of the polymer or textile material to make it suitable for a particular end use application, further directed to providing a specific functionality for a new functional role, where the imparted functionality can be aimed at enabling the material to be used in applications where the material is interactive, for example where it can interact with other materials such as other molecules, further directed to specific applications where the modified or functionalized material interacts with other materials, coatings, layers, etc., making it particularly suitable for applications such as battery separators, barrier fabrics, membranes, substrates, layers, fabrics, textiles, for use in electrochemical cells or batteries, textiles, garments, filtration, adsorption, testing, drug delivery, analyte sensing, medical devices, medical diagnostic devices, etc.

[0141] Other objects, embodiments, aspects, or examples of the invention may be shown or described in the drawings, detailed description, or claims. Many other variations or modifications of the invention will occur to those skilled in the art in light of the disclosure herein. Thus, within the scope of the claims, the invention may be practiced other than as specifically described herein.

[0142] The terms "comprises / comprising" and "having / including" when used herein in relation to the present invention are used to specify the presence of stated forms, integers, steps or components, but do not exclude the presence or addition of one or more other forms, integers, steps, components or groups thereof.

[0143] It will be appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for clarity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

Claims

1. a surface modified porous battery separator comprising a surface modifier chemically and covalently bonded to said surface modified porous battery separator, said surface modifier comprising a substrate binding component that is a nitrene precursor; the substrate binding component further comprises a carbene precursor; the surface modified porous battery separator comprises at least one membrane; A surface modified porous battery separator, wherein said membrane is selected from the group consisting of a polymeric material, a polyolefin material, a polypropylene material, a polyethylene material, a porous polymeric material, a porous membrane, a polymeric surface layer, and combinations thereof.

2. 10. The surface modified porous battery separator of claim 1, wherein said surface modifier is selected from the group consisting of a hydrophilic component, a hydrophobic component, an oleophilic component, an oleophobic component, a surface energy modifying component, a crosslinking component, a fragrance component, a water repellent component, a biological component, and combinations thereof.

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