阅读说明：本技术 隔板设有表面改性剂的电池 (Battery with separator provided with surface modifier ) 是由 克里斯托弗·K·斯托克斯 于 2014-01-17 设计创作，主要内容包括：一种电池,其隔板具有表面改性剂,前体形式的表面改性剂可以是一个或多个苯乙烯磺酰叠氮单体、聚合物或共聚物,其能够选择性地在热和光存在的条件下通过化学反应形成一个或多个苯乙烯磺化氮宾单体、聚合物或共聚物,其能够与聚合物或纺织材料的表面发生化学反应将特定或所需的化学表面官能化引入聚合物或纺织材料的表面。此外,本发明可能优选地涉及一种表面改性剂,其包含含一个或多个氮宾官能团的苯乙烯磺酰叠氮单体、聚合物或共聚物,所述氮宾官能团能够凭借插入到聚合物或纺织材料表面的一个或多个碳-氢键的插入反应引发化学反应,从而将特定或所需的化学官能化结合到聚合物或纺织材料表面。(A battery having a separator with a surface modifying agent, the surface modifying agent in precursor form being one or more styrene sulfonyl azide monomers, polymers or copolymers capable of chemically reacting selectively in the presence of heat and light to form one or more styrene sulfonated nitrene monomers, polymers or copolymers capable of chemically reacting with the surface of a polymer or textile material to introduce specific or desired chemical surface functionalization into the surface of the polymer or textile material. Furthermore, the present invention may preferably relate to a surface modifying agent comprising a styrene sulfonyl azide monomer, polymer or copolymer containing one or more nitrene functional groups capable of initiating a chemical reaction by virtue of an insertion reaction of one or more carbon-hydrogen bonds inserted into the surface of a polymer or textile material, thereby binding a specific or desired chemical functionality to the surface of the polymer or textile material.)

1. A battery comprising an anode, a cathode, an electrolyte, and a modified substrate comprising a surface modifying agent applied to at least one surface of the substrate, wherein,

the substrate is one or more battery separators;

the surface modifying agent comprises a first moiety comprising an arylsulfonyl azide or a copolymer thereof and a second moiety; the second portion comprises a chemical composition capable of imparting a property to the substrate surface;

the surface modifier is used at a ratio of 0.05-1.0g/m²Is applied to the substrate; and

at least one azide group of the first moiety has reacted with a carbon atom of the substrate to form a sulfonamide-crosslinking group.

2. The cell of claim 1, wherein the azide group reacts with one carbon atom by exposing the first moiety and the substrate to Ultraviolet (UV) light.

3. The battery of claim 1, wherein the arylsulfonyl azide is a styrene sulfonyl azide.

4. The battery of claim 1, wherein the arylsulfonyl azide is copolymerized with a vinyl monomer.

5. The battery of claim 4, wherein the vinyl monomer is hydrophilic.

6. The battery of claim 4, wherein the vinyl monomer is selected from the group consisting of: substituted styrenes, acrylic acid, methacrylic acid, vinylpyridine, vinylpyrrolidone, acrylamide, methacrylamide, and salts thereof.

7. The battery of claim 4, wherein the vinyl monomer is substituted with a reactive group.

8. The battery of claim 4, wherein the vinyl monomer is hydrophobic.

9. The battery of claim 4, wherein the vinyl monomer is styrene sulfonate or a salt thereof.

10. The battery of claim 1, wherein the arylsulfonyl azide is 4-styrenesulfonyl azide.

11. A battery comprising an anode, a cathode, an electrolyte, and a surface modifying agent for modifying a surface of a battery separator, the surface modifying agent comprising:

a first moiety comprising a sulfonyl azide;

a second portion comprising a chemical composition capable of imparting a property to the substrate surface;

wherein the surface modifier is used at a ratio of 0.05-1.0g/m²Is applied to the surface of the battery separator; and

the property is selected from: a hydrophilic component, a hydrophobic component, an oleophilic component, an oleophobic component, fluorescence, increased or decreased surface energy, increased soil resistance, and increased adhesion between the battery separator and another material.

12. The battery of claim 11, wherein the sulfonyl azide is 4-styrene sulfonyl azide.

13. A surface modifier for modifying a surface of a battery separator, the surface modifier comprising:

a first moiety comprising a sulfonyl azide;

a second portion comprising a chemical composition capable of imparting a characteristic to a surface of the battery separator;

wherein the surface modifier is used at a ratio of 0.05-1.0g/m²Is applied to the surface of the battery separator; and

the property is selected from: a hydrophilic component, a hydrophobic component, an oleophilic component, an oleophobic component, fluorescence, increased or decreased surface energy, increased soil resistance, and increased adhesion between the battery separator and another material; alternatively, at least one azide group of the first moiety has reacted with a carbon atom of the substrate to form a sulfonamide-crosslinking group.

14. A surface-modified substrate comprising the surface modifying agent of claim 13.

15. A battery separator comprising the surface modified substrate of claim 14.

16. A surface modifying agent comprising a suitable nitrene and/or carbene precursor capable of undergoing a chemical reaction, optionally in the presence of heat or light, to form one or more nitrene and/or nitrene functional groups; nitrene precursors, including materials such as polystyrene sulfonyl azide monomers, polymers or copolymers that can selectively undergo a chemical reaction in the presence of heat or light to form one or more nitrene functional groups; or

The surface modifying agent comprises a sulfonated styrene monomer, polymer or copolymer containing one or more sulfonyl azide functional groups capable of chemically reacting with the surface of a polymeric or textile material to introduce specific or desired chemical surface functionalization to the surface; or

The surface modifying agent comprises a sulfonated styrene monomer, polymer or copolymer, comprising one or more sulfonyl azide functional groups, capable of chemically reacting with the surface of a polymeric or textile material to introduce desired chemical surface functionalization into the polymeric or textile material, which functionalization may introduce properties such as hydrophilicity, hydrophobicity, oleophilicity and/or oleophobicity, and/or alter the surface energy of the polymeric or textile material to covalently modify the polymeric or textile material, for example to render it suitable for a particular end-use application.

17. A material made or modified from the modifier of claim 16; a method of making and/or using the modifier of claim 16; a polymer and/or textile material, separator, garment, fabric incorporating the modifier of claim 16; the surface modifying agent of claim 16 for polymeric and/or textile materials; a method of making and/or using the surface modifier modified and functionalized polymer and/or textile material of claim 16; a method of using the surface modified or functionalized polymer and/or textile material of claim 16; products using or comprising the surface modified or functionalized polymeric and textile materials of claim 16; alternatively, the modified or functionalized material of claim 16, which is interactive with other materials, coatings, layers, etc., particularly suitable for applications such as battery separators, barrier fabrics, films, substrates, layers, fabrics, textiles, etc., for use in electrochemical cells or batteries, textiles, apparel, filtration, adsorption, testing, drug delivery, analyte sensing, or medical diagnostics.

Technical Field

In accordance with at least selected embodiments, the present invention is directed to novel improved or optimized surface modifying agents; a material made or modified by the modifying agent; methods of making or using the modifying agents and/or modifying materials; and/or novel modified or optimized polymers and/or textile materials, separators, garments, fabrics, etc., incorporating the modifiers and/or modifying materials. According to at least certain embodiments, the present invention relates to modifiers suitable for use in polymers and/or textile materials; a modified material; methods of making or using the surface modifying agent modified and/or functionalized polymers and/or textile materials; and/or methods of using surface modified or functionalized polymers and/or textile materials.

In accordance with at least certain embodiments, the present invention relates to a surface modifying agent comprising a suitable nitrene and/or carbene precursor capable of forming one or more nitrene and/or carbene functional groups by chemical reaction, optionally in the presence of heat and light. Potentially preferred nitrene precursors include materials such as, but not limited to, sulfonyl azide-containing styrenic monomers, polymers and copolymers that are capable of chemically reacting in the presence of heat or light to form one or more nitrene functional groups. At least particularly selected embodiments relate to a surface modifying agent, for example, a sulfonated styrene monomer, polymer, or copolymer, comprising one or more sulfonyl functional groups, such as sulfonyl azide functional groups, that are reactive and capable of chemically reacting with the surface of a polymer or textile material to introduce specific or desired chemical surface functionalization into the surface of the polymer or textile material.

The introduced modifications or functionalizations can alter the physical properties of the polymer and/or textile materials or can impart new utilities to these materials. For example, the functionalization may introduce properties such as hydrophilicity, hydrophobicity, oleophilicity, oleophobicity, etc. to the polymer and/or textile material, and/or the functionalization may alter the surface energy of the polymer or textile material to modify the polymer or textile material to make it suitable for a particular end-use application. In addition, certain surface modifications may provide specific functionalization for new functionalities. For example, the purpose of introducing functionalization may be to enable the material to be used in the case of interactions, e.g., in the case of its interaction with other materials such as other molecules. Further examples include, but are not limited to, the specific application of the modified or functionalized materials in the context of interaction with other materials, coatings, layers, and the like, particularly for use in battery separators, barrier fabrics, films, substrates, layers, fabrics, textiles, and/or for use in electrochemical cells or batteries, textiles, apparel, filtration, adsorption, testing, drug delivery, analyte sensing, medical devices, medical diagnostics, and the like.

Background

There are various methods for improving the physical or chemical properties of the surface of a polymer or textile material. Surface modification of certain known polymeric or textile materials tends to be temporary and does not permanently modify the polymeric and/or textile material substrate for a variety of end use applications.

One known method is the treatment or pretreatment of the surface of a polymer or textile material substrate, for example, with ultraviolet light (used alone without the use of a special surface modifier), plasma treatment, corona treatment or fluorooxidation. These treatments are harsh, particularly when used in thin films and certain polymeric species. The use of these methods may cause a risk of mechanical or chemical damage to the surface of the polymer matrix. In some cases, this damage will compromise the properties of the polymer matrix that is modified for the intended end use.

More generally, other known methods of surface treatment or pretreatment of polymeric or textile materials include, for example, coating a substrate of the polymeric or textile material with some functional material according to known procedures by means of coating, dip coating, spraying, and the like. These treatments lack durability and wear away from the surface of the polymeric or textile substrate over time, rendering the polymeric or textile substrate unsuitable for the intended end use after a period of use.

Thus, for at least some applications or uses, improved methods are needed to improve the physical and/or chemical properties of the surface of a polymer or textile material. In particular, there is a need for improved or innovative methods for permanently modifying polymer or textile material substrates to meet the requirements of a variety of end uses, surface modified polymer or textile materials, modified functionalized polymers, functional polymers, uses of the above materials, and the like.

Disclosure of Invention

In accordance with at least selected embodiments, the present invention provides novel improved or optimized methods for improving the physical and/or chemical properties of one or more surfaces of a polymeric material; provide improved or innovative methods for permanently modifying polymer matrices for a variety of end-use applications; surface-modified polymeric materials are provided; modified functionalized polymers, polymers provided with functionality, uses of these materials, and the like, or at least to address the above needs, are provided.

In accordance with at least certain embodiments, the present invention addresses the above needs and is directed to modified functionalized polymers, functional polymers and chemically modified substrates comprising the modified functionalized polymers, methods of modifying 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 these chemically modified substrates.

In addition, the present invention provides an improved method of utilizing surface modifying agents to improve the physical and/or chemical properties of one or more surfaces (or sides) of a polymeric or textile material, and/or an improved or innovative method to permanently modify the polymeric or textile material substrate for a variety of end use applications.

Further, the present invention provides an improved method of modifying a polymer and/or textile material with a surface modifying agent, a method of making and/or using a surface modifying agent to modify and/or functionalize a polymer and/or textile material, and/or a method of using a surface modified or functionalized polymer and/or textile material. In addition, the present invention provides an improved method of utilizing surface modifying agents to improve the physical and/or chemical properties of the surface of a polymer or textile material, and/or an improved or innovative method to permanently modify the polymer or textile material substrate for a variety of end use applications.

It may be desirable for the surface modifying agent to be one that is capable of reacting to form nitrene and/or carbene functional groups. The nitrene and/or carbene functional groups react with the surface to introduce the desired functionalization into the site. More preferably, the surface modifying agent is an agent capable of forming nitrene functional groups by reaction. The nitrene functional group reacts with the surface to introduce the desired modification or functionalization into the site. In porous surfaces, the introduced modification and/or functionalization may traverse the entire surface, uncover the pores, within the pores, at the surface and down to the interior of the pores, at only one surface, at both surfaces, etc.

At least selected embodiments relate to a method of preparing a surface modifying agent comprising a sulfonyl azide-containing styrenic monomer. The sulfonyl azide-containing monomers can chemically react in the presence of heat or ultraviolet light (UV) to form a chemical species known as nitrene. Nitrene is a reactive intermediate, and is an electrically neutral chemical species that carries only 6-valent electrons. Nitrenes are capable of reacting with certain substrates, including saturated hydrocarbons and other C-H or heteroatom bonds, by inserting the reactive nitrenes into one or more C-H or heteroatom bonds of the substrate. The nitrene groups on the polymer provide reactive sites where multifunctional nitrene precursors are activated and covalently inserted into one or more C-H or heteroatom bonds of the matrix to improve the chemical properties of the matrix.

At least selected embodiments relate to a method of making a composition comprising a surface modifying agent comprising a sulfonyl azide-containing polymer or copolymer. The sulfonyl azide-containing polymer or copolymer is capable of chemically reacting in the presence of heat and ultraviolet light to form a chemical species known as nitrene. Nitrene is a reactive intermediate, an electrically neutral chemical species that carries only 6 valence electrons. Nitrenes are capable of reacting with certain substrates, including saturated hydrocarbons and other C-H or heteroatom bonds, by inserting the reactive nitrenes into one or more C-H or heteroatom bonds of the substrate. The nitrene groups on the styrene polymer or copolymer provide active nitrene sites that covalently insert into one or more C-H or heteroatom bonds of the matrix to improve the chemical properties of the matrix.

In this way, the nitrene precursor functional group acts as a reactive site or cross-linking linker to link the sulfonyl azide-containing polymer or copolymer to the substrate to improve the chemical properties of the substrate. For example, when the substrate is a polymer or textile material, incorporation of the sulfonyl azide-containing polymer or copolymer can improve the chemical reactivity of the surface of the polymer or textile material, either alone or in admixture with one or more polymers, to provide a suitable interface for the desired application.

Drawings

FIG. 1 illustrates one embodiment of modifying or functionalizing a substrate surface to form a modified functionalized substrate, material, layer, base, membrane, separator, porous membrane, nonporous precursor membrane, or the like, in accordance with the present invention.

FIG. 2 shows another embodiment of modifying or functionalizing a substrate surface to form a modified and/or functionalized substrate, material, layer, base, membrane, separator, porous membrane, nonporous precursor membrane in accordance with the present invention.

FIG. 3 is a side or end view of a modified and/or functionalized substrate, material, layer, base, membrane, separator, porous membrane, nonporous precursor membrane, or the like, according to the present invention.

FIG. 4 is a two-sided or end view of a modified and/or functionalized substrate, material, layer, base, membrane, separator, porous membrane, nonporous precursor membrane, or the like, according to the present invention.

FIG. 5 is a side or end view of a modified and/or functionalized substrate, material, layer, base, membrane, separator, porous membrane, nonporous precursor membrane or related product comprising additional component D, such as a coating, layer, or the like, according to the present invention.

FIG. 6 is a two-sided or end view of a modified and/or functionalized substrate, material, layer, base, membrane, separator, porous membrane, nonporous precursor membrane or related product comprising additional component D, such as a coating, layer, or the like, according to the present invention.

Fig. 7 is an FTIR spectrum of a material made according to embodiments of the present invention.

Fig. 8 is a DSC curve for a material made according to various embodiments of the present invention.

Fig. 9 is a thermogravimetric analysis of a material made according to various embodiments of the present invention.

Detailed Description

At least selected embodiments of the present invention relate to surface modifiers for polymeric and/or textile materials, methods of making or using surface modifiers to modify or functionalize polymeric and textile materials, and/or methods of using surface modified or functionalized polymeric and/or textile materials, and/or products using or comprising surface modified or functionalized polymeric and/or textile materials. In addition, the present invention provides improved methods for improving the physical and/or chemical properties of one or more surfaces (or sides, or portions) of a polymeric or textile material using surface modifying agents, as well as improved or innovative methods for permanently modifying a polymeric or textile material substrate for a variety of end-use applications.

At least selected embodiments relate to methods of preparing surface modifying agents that may be used to modify or functionalize the surface of a polymer and/or textile substrate. In certain embodiments, the surface modifying agent comprises a pre-moiety capable of forming nitrene or carbene functional groups, reactive sites, and/or crosslinking sitesAnd (3) a body. In a particular embodiment, the surface modifying agent comprises a sulfonyl azide-containing styrenic monomer, polymer, or copolymer. The sulfonyl azide functional monomer is capable of reacting chemically under suitable conditions, for example, in the presence of heat or ultraviolet light, to form a chemical species known as nitrene. Nitrene (R-: N:) is a reactive intermediate, and is an electrically neutral chemical species carrying only 6-valent electrons. Nitrene can react with a polymeric and/or textile substrate by an insertion reaction, inserting itself into the C-H or heteroatom bonds of the substrate. Step 1 of the following figure shows that when exposed to uv light or heat, R-N ═ N⁺＝N^-Is represented by (usually also R-N)₃To (b) form nitrene R-N, nitrogen being a by-product.

Step 1:

step 2:

in step 2 of the above figure, the nitrene may then react with a portion of the alkyl or aryl group, inserting itself into the exemplified C-H bond to form R-N-CH 2-R'. The nitrene intermediate is covalently inserted into the R' -CH in the example₃To improve the chemical properties of the hydrocarbon matrix in the case of the carbon-hydrogen composite.

Certain embodiments of the present invention relate to the use of R-S ═ O₂-N₃A process for the preparation of the sulfonyl azide-containing monomers shown, which is capable of forming nitrene intermediates upon exposure to heat or ultraviolet light. The nitrene intermediate can chemically react with the substrate and insert itself into one or more C-H or heteroatom bonds to improve the chemical properties of the substrate. When the sulfonyl azide-containing monomer is activated to a nitrene intermediate and inserted into one or more C-H or heteroatom bonds of the polymer or textile material, it is capable of modifying the chemical reactivity of the polymer or textile material surface depending on the chemical nature of the sulfonate-functionalized monomer. One such example is sulfonationStyrene azide monomer 4-styrene sulfonyl azide:

further, when the 4-styrenesulfonyl azide is exposed to ultraviolet light or heat, it can itself intercalate into one or more C-H or heteroatom bonds of the polymer or textile material and can improve the chemical reactivity of the surface of the polymer or textile material. Polymers comprising sulfonyl azide-bearing monomers are activated to produce a plurality of nitrene intermediates that insert themselves into a plurality of C-H or heteroatom linkages distributed across the surface of the polymer or textile material and alter the chemical reactivity of the surface of the polymer or textile material to varying degrees depending on the composition of the sulfonyl azide-containing polymer reacted with the surface of the polymer or textile material substrate.

Further embodiments relate to methods of making surface modifying agents comprising a small molecule, such as a sulfonyl azide-containing small molecule. When the sulfonyl azide-containing small molecule is converted to a nitrene functional group upon exposure to heat and ultraviolet light, it is capable of inserting itself into a C-H or heteroatom bond of a polymer or textile material and of modifying the chemical reactivity or other interfacial properties of the surface of the polymer or textile material depending on the chemical reactivity of the selected sulfonyl azide-containing molecule. In essence, nitrene precursors introduce the chemical functionality of the attached functional groups and alter the chemical reactivity or interfacial properties of the polymer or textile material surface depending on the selected functionality. Examples of sulfonyl azide-containing molecules that can modify the surface of simple aliphatic carbohydrates can be represented as:

further, when one or more sulfonyl azide-containing molecules or polymers undergo a chemical reaction under exposure to heat and ultraviolet light to form one or more nitrenes, the one or more nitrenes react at each C-H or heteroatom bond site of the matrix through an insertion reaction, and the chemical functionality or interfacial properties of the polymer or textile material are altered to a greater degree depending on the number of inserted nitrenes groups. In this way, multiple nitrene precursors can act as reactive sites or cross-linkers to link sulfonyl azide-containing molecules or polymers to the matrix to improve the chemical properties of the matrix. For example, where the substrate is a polymer or textile material, the incorporation of one or more sulfonyl azide-containing polymers can improve the chemical reactivity of the surface of the polymer or textile material, making it suitable for the intended end use.

In addition to combining the two monomers, one method of forming such sulfonyl azide-containing polymers is through post-polymerization modification of materials such as polyvinyl sulfonate or sodium polystyrene sulfonate. As shown below, such polymers can be readily converted to sulfonyl azides by common chemical modification techniques.

Another embodiment of the present disclosure relates to a method of making a surface modifying agent comprising a sulfonyl azide-containing polymer. Generally, in the various embodiments described, the surface modifying agent may be represented as component B (where component B contains a crosslinking or reactive species, such as nitrene groups from nitrene precursor species, for functionalizing the polymer or textile material), or as component A + B (where component B is defined above and component A is a functional polymer or functional group of a type designed to match the polymer or textile material to introduce a particular formulation, characteristic, chemical property, etc. into the polymer or textile matrix). Further, in various embodiments, component B may comprise only one monomer X comprising a monomer that is a precursor to the reactive nitrene or carbene functional group. In yet other embodiments, component B may comprise monomer X + monomer Y, monomer Y being some other monomer that may reduce the overall cost of the raw materials (relative to component B comprising only monomer X) or impart some property or functionality to the polymer or textile substrate.

By way of example, a sulfonyl azide-containing polymer can be prepared by polymerizing the following monomer X,

sulfonated styrene azide monomers, prepared in a homopolymer system. In such a homopolymer system, component B, the surface modifier, contains only one monomer X (non-monomers X + Y) using the nomenclature described above. In other embodiments, the sulfonyl azide-containing polymer may be prepared by polymerization of monomer X, a sulfonated styrene azide monomer, with other monomer Y (which may be multiple) inclusion, where monomer Y does not contain a nitrene (or carbene) precursor species. Some examples of monomer Y include sodium salts of styrene, pentafluorostyrene or sulfonated styrene, said monomers being represented respectively as follows:

the advantage of this process is that the resulting sulfonyl azide-containing polymer can be more easily tailored to the desired properties by adding orthogonal functional groups or alternative surface properties, which will facilitate further formulation planning.

Further, examples of the other monomer Y are as follows:

r ═ H, methyl, ethyl, isopropyl, butyl, hexyl, epoxypropyl where the first and second examples of monomer Y are methacrylate and acrylate monomers, respectively, which can alter the physical properties (e.g., glass transition temperature) of the surface modifier depending on the choice of R group, and the third example is an anhydride, which is an active chemical species that provides conditions for further orthogonal chemical reactions. Examples of other monomers Y include, but are not limited to, 2-vinylpyridine, 4-vinylpyridine and/or N-vinylpyrrolidone.

Further examples shown below are copolymers resulting from copolymerization of an azide-containing sulfonyl styrene monomer (monomer X, in the amount "n" shown below) with a second monomer containing R groups having a specific chemical functionality (monomer Y, in the amount "m" shown below), which may be, but is not limited to, any of the following:

polymer X-Y

The prepared sulfonyl azide-containing copolymer can form a nitrene intermediate through chemical reaction under the condition of being exposed to heat or ultraviolet light. The nitrene reacts with the polymer or textile substrate through an insertion reaction, the nitrene functional group inserting itself into one or more C-H or heteroatom bonds of the substrate. In addition, the ratio of the repeating units n and m in the sulfonyl azide copolymer is not less than 0.1 and not more than n/(n + m) and not more than 0.75. Expressed another way, i.e., in certain embodiments, the molar ratio of azide in the monomer [ n/(n + m) ] is 10-75% by percentage. In certain preferred embodiments, the molar ratio of azide in monomer [ n/(n + m) ] is from 10 to 40%, in other preferred embodiments the molar ratio of azide in monomer [ n/(n + m) ] is from 15 to 30%, and in more preferred embodiments the molar ratio of azide in monomer [ n/(n + m) ] is from 20 to 25%.

Thus, in some embodiments, one or more nitrene functional groups serve as reactive sites or cross-linkers to link the sulfonyl azide-containing copolymer component B (here comprising monomers X + Y) or components a-B to the substrate (the polymer or textile substrate here may also be represented by component C) to improve the chemical properties of the substrate. For example, when the sulfonyl azide copolymer contains pentafluorostyrene as the R group, the R group being in the "Y" monomer, the insertion of one or more nitrenes into the carbohydrate matrix or the polymer or textile material can reduce the surface energy of the surface of the polymer or textile material.

Examples of sulfonyl azide-containing functionalized materials having alternative functionalities are dansyl azides, which are formed from the reaction of dansyl chloride with sodium azide as shown below:

one of the notable chemical properties of dansyl azides is that they fluoresce when a sulfur atom is bound to a nitrogen. Thus, dansyl azides can be used as biomarkers for proteins. When dansyl azide reacts in the presence of ultraviolet light or heat to form a nitrene, which becomes covalently bound to the polymer or textile matrix, the matrix will become permanently fluorescent, indicating that covalent attachment of one or more nitrene groups of the dansyl azide to one or more C-H bonds of the polymer or textile matrix has occurred. Subsequent washes can verify the durability of the dansyl fluorophore on the substrate. The lower panel shows the formation of nitrenes under the action of UV light or heat and the subsequent reaction of the nitrenes with a polymer or textile matrix, here with R' -CH₃And (4) showing.

In certain embodiments, dansyl azide is applied as a coating to a polypropylene film substrate via a hexane solution and then the film substrate is exposed to ultraviolet light, resulting in the film being strongly fluorescent, yet not diminished after washing with solvents (e.g., acetone) and/or water, indicating that one or more molecules are covalently bound to the surface of the polypropylene film substrate via nitrene intermediates.

As a further example, when the sulfonyl azide-containing copolymer contains sulfonate functionality (which as previously shown can be monomer Y), the incorporation of the nitrene intermediate onto the polymer or textile indicates a significant enhancement in the surface energy of the treated material. The increase or decrease in surface energy of the polymer or textile material may alter the chemical characteristics of the polymer or textile material surface, increasing or decreasing the chemical reactivity of the surface with other agents, such as dyes, modifiers, water repellents, antimicrobials, oils, perfumes, and the like.

Further examples of chemical modifications of the polymeric or textile material matrix material include, but are not limited to: the polymer or textile substrate surface is rendered hydrophilic, hydrophobic, oleophilic, or oleophobic by copolymerizing a sulfonyl azide-containing monomer with a monomer or polymer selected for its chemical functionality. For example, when a sulfonyl azide-containing monomer is polymerized with a copolymer containing hydrophilic, hydrophobic, oleophilic, or oleophobic functional groups, the chemical nature of the hydrophilic, hydrophobic, oleophilic, or oleophobic functional groups chemically bonds to the polymer or textile substrate surface.

Further, according to selected embodiments of the present invention, when a sulfonyl azide-containing monomer or polymer defined as component B is combined with a copolymer, monomer, polymer or other functional group defined as component A, components A-B can be formed, and components A-B can be used as a coating applied to the surface of a polymer or textile material (where the polymer or textile material can also be represented by component C). When the polymer or textile material coated surface is exposed to heat or ultraviolet light, one or more nitrene reactive groups are formed on component a-B (or component B), which can be covalently bonded to component a-B (or component B) to the surface of the polymer or textile material (component C) to form a modified matrix a-B-C (or B-C).

In some embodiments, component B is comprised of a material that generates nitrene and/or carbene groups when activated by heat or light, which contains either monomer X or monomer X + Y. For example, in FIG. 1, component B contains monomers X and Y. In fig. 1, component B is bound to the surface of the polymer or textile material (component C) by reaction of nitrene to alter the chemical reactivity of the polymer or textile material (component C) for a variety of end uses.

As shown in fig. 2, a similar approach involves binding 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 variety of end uses. In the embodiment shown in FIG. 2, component B contains monomer X, rather than monomer X + Y.

When the sulfonyl azide is exposed to ultraviolet light to form a nitrene group, the nitrene group can pass through one to form a by-product N₂The addition reaction of (a) initiates an insertion reaction into a C-H or other heteroatom bond. When component B or component AB can also act as a labeling reagent when exposed to optimized uv light in a selected wavelength range, with the modified azide with its own newly generated reactive nitrene end group. Reaction of the nitrene group at a site on the surface of the matrix material inserts the functionalized component AB (or component B) into the polymer or textile matrix component C and introduces a new desired labelling function into component C.

Furthermore, the insertion reaction has the advantage that chemical radicals are not allowed to diffuse beyond the insertion site. This is important for polyolefin matrices such as Polyethylene (PE) or polypropylene (PP), because PE and PP are susceptible to crosslinking or degradation once free radicals are introduced into the polyolefin backbone.

In this manner, the surface of a substrate material, such as a polymer or textile material, can be modified or marked in a desired chemical manner and the desired surface properties tailored to meet a wide variety of end uses by virtue of the chemical reactivity of the nitrene groups. One such example is the modification of the surface energy and/or hydrophobicity and/or oleophilicity of polyolefin, e.g., polypropylene, surfaces by changing the surface, which is generally chemically inert, to an active surface.

Most polyolefins are "nonfunctional" in their own right and they are not readily susceptible to chemical modification without significantly affecting the mechanical or chemical stability of the material. The nitrene-based intermediate provides conditions for unfunctional polyolefin modification without significant damage or degradation that many conventional surface modification approaches can produce. In some cases, such damage or degradation will impair the properties of the polymer matrix that is modified for its intended end use.

At least certain selected embodiments of the present invention relate to modified functionalized polymers, functional polymers, and chemically modified substrates comprising modified functionalized polymers; a method of modifying a functionalized polymer and/or a method of using a modified functionalized polymer to chemically react with a surface of a substrate; and/or methods of using these chemically modified substrates. At least certain embodiments relate to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers into chemically modified porous, microporous, and nonporous polymer matrices and methods of using the modified matrices. In at least selected embodiments, the carbene group R-C or nitrene group R-N are reactive intermediates capable of performing heteroatom insertion reactions. Carbene or nitrene intermediates may be formed by a variety of thermal and photochemical reactions. Examples of nitrene precursors are aryl azides, acyl azides, azide formates, phosphoryl azides, phosphoryl groups, or sulfonyl azides. Examples of carbene precursors are alkyl halides, diazoalkanes, diazoketones, diazoacetates, beta-keto-alpha-diazoacetates, aliphatic azos or bicyclic ethyleneimines. In some embodiments, a carbene material may be generated by an alpha-elimination reaction with one or more of the carbene precursors.

At least certain selected embodiments of the present invention satisfy the need for modifying the surface of a porous polymeric substrate. At least selected embodiments of the present invention meet the above-described needs and/or relate to a modified porous polymer film substrate; a method of making a modified polymeric porous film substrate; and/or methods of using the modified polymeric porous film substrate; chemically modified polyolefin microporous films, methods of making modified polyolefin microporous films; and/or methods of using the modified polyolefin microporous films; chemically modified polyolefin microporous battery separator or battery separator film, a method of making a modified polyolefin microporous battery separator or battery separator film; and/or methods of using the modified polyolefin microporous battery separator or battery separator film; chemical modification of polyolefin microporous battery separators or separator films to form carbon-carbon or nitrogen-carbon covalent bonds with polyolefins by reaction of modified functionalized polymers containing carbene or nitrene intermediates with the carbon-hydrogen bonds of polyolefins; a method for improving the hydrophilicity or wettability of a polyolefin microporous battery separator or separator film in a lithium ion rechargeable battery; and/or a method of introducing cross-linking in a polyolefin microporous battery separator or separator film, and the like.

According to at least selected possible preferred embodiments of the present invention, chemical modification of at least a portion of the surface of the polyolefin microporous separator or membrane may be accomplished by carbon-hydrogen bonding of functionalized polymers or copolymers containing carbene and/or nitrene intermediates with, for example, polyolefins. This chemical reaction or treatment based on functionalized polymers or copolymers containing carbene and/or nitrene intermediates provides a means to more permanently improve the wettability of polyolefin microporous separators in lithium ion rechargeable batteries. In addition, the functionalized polymer or copolymer containing carbene and/or nitrene intermediates reacts with the C-H bonds of at least one skin layer of the polyolefin microporous separator film to introduce cross-linked functionality into the polyolefin to improve the high temperature stability of the polyolefin microporous separator or film.

In accordance with at least certain selected embodiments, the present invention satisfies the need for surface modification of porous polymer matrices. At least selected embodiments of the present invention meet the above-described needs and are directed to a modified porous polymer film substrate; methods of making modified polymeric porous film substrates and methods of using modified polymeric porous film substrates. In particular, the present invention relates to chemically modified microporous polyolefin films; a method of making a chemically modified polyolefin microporous film and a method of using a chemically modified polyolefin microporous film. More particularly, the present invention relates to chemically modified polyolefin microporous waterproof/breathable textile films; a method for making chemically modified polyolefin microporous waterproof/breathable textile film and a method for applying chemically modified polyolefin microporous waterproof/breathable textile film. In accordance with at least selected preferred embodiments, the present invention relates to the chemical modification of polyolefin microporous waterproof/breathable textile films by reaction of modified functionalized polymers containing carbene or nitrene intermediates with the carbon-hydrogen bonds of polyolefins; methods of reducing surface energy or introducing oleophobicity into a waterproof/breathable textile film to increase the ability of the waterproof/breathable textile to resist soil damage and/or to increase the durability of the film's waterproofness, and the like.

In accordance with at least certain selected embodiments, the present invention meets the need for surface modification of polymeric textile fibers. At least selected embodiments of the present invention meet the needs and are directed to modified polymeric textile fibers; a method of making a modified polymeric textile fiber and a method of using a modified polymeric textile fiber. In particular, the present invention relates to chemically modified polyolefin textile fibers; a method of making chemically modified polyolefin textile fibers and a method of using chemically modified polyolefin textile fibers. More particularly, the present invention relates to chemically modified polyolefin textile fibers; a method of making chemically modified polyolefin textile fibers and a method of using chemically modified polyolefin textile fibers. In accordance with at least selected preferred embodiments, the present invention relates to the chemical modification of polyolefin textile fibers by reaction of a modified functionalized polymer containing a carbene or nitrene intermediate with carbon-hydrogen bonds of a polyolefin; methods of reducing surface energy or introducing oleophobicity into the waterproof/breathable textile fibers to increase the ability of the waterproof/breathable textile fibers to resist soil damage and/or increase the durability of the film's waterproofness, and the like.

At least certain objects, embodiments, aspects, and/or examples of the present invention relate to surface-modified polymeric materials, modified functionalized polymers, functional polymers, chemically modified substrates comprising modified functionalized polymers; methods of making and/or applying surface-modified polymeric materials, modified functionalized polymers, functional polymers, and/or chemically modified substrates comprising modified functionalized polymers; a method of modifying a functionalized polymer and/or a method of using a modified functionalized polymer to chemically react with a surface of a substrate; and/or methods of using such chemically modified substrates. At least certain embodiments relate to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers into chemically modified porous and/or nonporous polymer matrices and/or methods of using the modified matrices. At least selected embodiments relate to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers into chemically modified porous and/or nonporous polymer matrices and/or methods of using the modified matrices. At least certain embodiments relate to modifying certain functionalized polymers such that they induce a change in the surface properties of the matrix. In accordance with at least selected possible preferred embodiments, the present invention relates to chemically modifying a functionalized polymer (component a) with a carbene and/or nitrene crosslink modifier (component B, which may comprise monomer X or monomer X + Y) to form a modified functionalized polymer a-B having carbene or nitrene functionality, the polymer a-B being capable of reacting with the surface of a substrate and causing a change in the surface property of the substrate to meet a predetermined application. According to at least selected possibly preferred embodiments, the present invention relates to the covalent modification of the surface of a polymer (component C) to form a modified matrix a-B-C by binding a functionalized polymer (component a) with a carbene and/or nitrene crosslink modifier (component B, which may comprise monomer X or monomer X + Y). Such modification can alter the chemical reactivity of the polymer surface, providing the modified substrate with a functionality specifically designed for the intended end use or application.

The modified substrate according to the present invention is illustrated in conjunction with the accompanying drawings, such as fig. 3-6. In fig. 3, a modified matrix a-B-C comprises component C (a polymer or textile matrix) that is modified by combining component a (a functional polymer, fluoropolymer, label, etc.) with component B (carbene and/or nitrene crosslink modifier). Component a imparts one or more desired properties (e.g., fluorescent markings, hydrophobicity, hydrophilicity, etc.) to the modified substrate, and component B provides reactivity to bind with certain functional species such as component a to modify the surface of component C. In fig. 4, two modified matrices comprise component C (a polymeric or textile matrix) modified by component B comprising monomers X and Y. In fig. 4, monomer X provides nitrene and/or carbene reactivity to modify the surface of component C and monomer Y provides some property or function desired for the system.

FIG. 5 shows a modified matrix A-B-C-D in which an additional component D is added to the system. In fig. 5, component D may be a coating, such as a ceramic coating. Component C may be some polymeric material or a textile matrix that is not normally associated with component D. By modifying the surface of component C by the combination of functional polymer A (also represented by component A) and modifier component B, component D can more readily and durably attach to the surface of component C than if the modifier of the invention were not used. Similarly, in FIG. 6, two modified substrates are shown, to which system an additional component, component D, has been added. In fig. 6, component D may 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 can be more easily and durably attached to the surface of component C than in the case where the modifier of the present invention is not used.

At least certain objects, embodiments, aspects, and/or examples of the present invention relate to improved or new methods of permanently modifying a polymer matrix to meet various end uses or applications; a surface-modified polymeric material; a modified functionalized polymer; a functional polymer; the use of these materials; and the like.

At least certain embodiments of the present invention meet the present need and/or relate to novel improved or modified surface-modified polymeric materials; a modified functionalized polymer; a functional polymer; and/or a chemically modified matrix comprising a modified functionalized polymer; and/or chemically modifying a substrate comprising a functionalized polymer; and/or a method of modifying a functionalized polymer and/or a method of using a modified functionalized polymer to chemically react with a surface of a substrate; and/or methods of using these chemically modified substrates.

In particular, certain embodiments relate to modifying certain functionalized polymers so that they are capable of causing changes in the surface properties of the substrate. In accordance with at least selected preferred embodiments, the present invention preferably relates to chemically modifying a functionalized polymer (component a or a functional or functionalized component a) with a nitrene (or carbene) crosslinking modifier (component B, which may comprise monomer X or monomer X + Y) to form a modified functionalized polymer a-B, which is capable of chemically modifying the surface of a polymer matrix and causing a change in the surface properties of the polymer matrix to meet an intended use.

In accordance with at least certain embodiments, the present invention relates to a method of preparing a surface modifying agent, which in some embodiments comprises a sulfonated styrene monomer, polymer, or copolymer containing nitrene or carbene precursor functional groups capable of being activated by heat or ultraviolet light to chemically react to form nitrene and/or carbene entities. At least selected embodiments relate to a surface modifying agent comprising a sulfonated styrene monomer, polymer, or copolymer; such surface modifying agents contain nitrene entities which are capable of chemically reacting with the surface of the polymer or textile material to impart specific or desired chemical surface functionality to the polymer or textile material.

At least certain embodiments relate to a method of copolymerizing a monomer X and a monomer Y to form a component B comprising monomers X + Y, the monomer Y comprising certain functional groups capable of altering the surface energy and/or chemical properties of a polymer or textile material (component C). In addition, some embodiments relate to combining component a with a modified styrene sulfonyl azide monomer, polymer or copolymer to form a modified functionalized a-B, the component a containing functional groups specifically selected to achieve a predetermined function such as hydrophilicity, hydrophobicity, oleophilicity or oleophobicity and/or selected to alter the surface energy of the polymer or textile material, the functionalized a-B being capable of reacting with heat or light (e.g., ultraviolet light) to form a modified styrene sulfonyl nitrene monomer, polymer or copolymer bearing nitrene functional groups capable of chemically reacting with a saturated hydrocarbon monomer represented as component C to form a polymer or textile material a-B-C to meet a predetermined end use application.

When the aliphatic or aryl azide is exposed to ultraviolet light to form a nitrene functional group, the nitrene functional group is capable of forming a by-product N through one₂The addition reaction of (2) initiates an insertion reaction of inserting a C-H bond. The modified azide with its own reactive nitrene end group is capable of assuming the role of a crosslinking and labeling reagent when exposed to optimized ultraviolet light in a selected wavelength range. When the modified aliphatic or aryl azides also contain specific chemical groups with functionalities such as hydrophilic, hydrophobic, oleophilic, or oleophobic, the reaction of R-N: nitrene groups at saturated C-H sites on the surface of the matrix material inserts the functionalized component A-B into the polymeric or textile matrix component C and introduces the novel desired chemical functionality into component C.

Nitrene (R-: N:) is a nitrogen analogue of carbene, carrying only 6 valence electrons. Nitrenes and carbenes are reactive intermediates that are uniquely reactive with both functional and nominally non-functional substrates. Although there may be methods of modifying polymer substrates with specific functionalities, the present invention provides a method suitable for modifying those polymer substrates that are not functional, i.e., those polymer substrates that do not contain functional groups. Most polyolefins are "nonfunctional" in their own right and they are not readily susceptible to chemical modification without significantly affecting the mechanical or chemical stability of the material. The nitrene-based intermediate provides conditions for the modification of non-functional polyolefins without the severe degradation that many conventional surface modification approaches typically produce. Moreover, the use of the nitrene-based intermediates of the present invention can be applied to almost all polymer matrices without regard to chemical modification to a particular functional group. The reactive nitrene-based intermediate of the present invention has the advantage of being able to insert itself into the carbon-hydrogen chemical bond of the polyolefin polymer matrix. The specific chemical reactivity of nitrene-based intermediate component B provides a means of adding selected functionalities to a polymer or textile substrate.

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 is shown below wherein a polystyrene sulfonyl azide polymer is copolymerized with an R-group modified polystyrene polymer having an R-group in a preferred 'n/n + m' ratio of 0.1. ltoreq. n/n + m. ltoreq.0.75. The R functional groups of the three modified polystyrene polymers, styrene, 2,3,4,5, 6-pentafluorostyrene and 4-styrene sulfonate, are shown below:

according to one embodiment of the present invention, a modifier component B with multiple nitrene intermediates or precursors can be mixed with one or more predetermined functionalized components A to form a specific chemical species, herein designated as "multiple reactive site-modified functionalized polymers A-B". Such polymers a-B are further capable of reacting with a specified polymer matrix, which may be a natural polyolefin, or some other synthetic or naturally extracted polymeric material, in the proper proportions and formulation conditions to add a specific, desired chemical functionality to the polymer matrix to tailor the chemical structure of the polymer matrix for a desired end use.

A modified functionalized polyazabine sulfonate monomer, polymer or copolymer is capable of obtaining a durable covalent modification of a polymer matrix surface by inserting itself into one or more C-H bonds of the polymer matrix surface by a chemical reaction, in particular an insertion reaction. Polystyrene sulfonated nitrene monomers, polymers or copolymers containing multiple nitrene-forming entities can be incorporated into polyolefin polymer matrices at multiple sites on the surface of the polyolefin via insertion reactions into one or more C-H bonds to form the final functionalized material (polyolefin matrix a-B-C). The resulting composite (polyolefin matrix A-B-C) has not only bulk properties similar to the polyolefin matrix, but also surface properties of the polysulfonated styrene monomer, polymer or copolymer. For example, the modified polyolefin surface may exhibit a surface energy that is much higher than that of the conventional polyolefin depending on the quality and degree of modification. In addition, the modified polyolefin surface may exhibit a higher or lower degree of hydrophilicity, hydrophobicity, oleophilicity, or oleophobicity.

In accordance with at least selected embodiments of the present invention, the polyolefin polymer matrix may be a microporous polyolefin film matrix whose surface has been chemically modified to have the functionality of components A-B, e.g., to have a higher or lower degree of hydrophilicity, hydrophobicity, oleophilicity, or oleophobicity, or to have a different surface energy. Microporous polyolefin films tend to draw large amounts of grease into their pores. The treatment and modification based on the functionalized components a-B of the present invention can be used to modify the hydrophilic surface of the microporous polyolefin membrane to absorb less or repel the absorption of grease, thereby creating a modified microporous polyolefin membrane matrix for novel separation or filtration of a variety of materials.

An example of an end-use application achieved by altering the lipophilicity of the microporous polyolefin film with the functional components a-B is a "waterproof/breathable" garment, and waterproof garment garments comprising microporous polyolefin films can greatly enhance the comfort of the garment by making it more breathable and allowing moisture from the wearer's body to evaporate through the facing of the waterproof garment. This function is commonly referred to as a "waterproof/breathable" jacket. Many "waterproof/breathable" garments comprise non-porous materials that rely on molecular transport of water molecules to achieve breathability. There is therefore a need to provide improved breathability by incorporating truly porous films to allow water vapor molecules to evaporate into the air by diffusion, thereby greatly enhancing breathability and increasing wearer comfort. One disadvantage of some microporous membranes is that they can become soiled by natural body oils or other oils, resulting in a reduction in the water resistance of the membrane. This disadvantage can be overcome by modifying the surface of the microporous membrane according to the invention, for example, by rendering the membrane surface oleophobic against natural body or other oils with a fluorine-containing compound.

In accordance with at least selected embodiments of the present invention, there is also the use of a functionalized component A-B 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 through the use of durable water repellent ("DWR") coatings and finishes. These DWR coatings and finishes are less durable and can wear out from repeated cleaning and/or use. Some textile fibers and/or fabrics, such as those made of acrylic, are not easily treated with DWR coatings and are often not useful in applications where water and/or stain resistance is a high requirement. At least certain methods or embodiments of the present invention may be used to modify polymeric textile fibers and/or fabrics, for example, by durably rendering the polymeric textile fibers and/or fabrics water and/or soil repellent with a fluorine-containing compound.

Furthermore, in accordance with at least selected embodiments of the present invention, the functionalized components A-B may be used to reduce the surface energy of polyolefins used in the walls of certain perfume container devices. Some perfume container devices operate by controlling the permeation of perfume substances through one or more walls of the perfume container device. Perfume container devices will typically comprise a polyolefin, often made of polyethylene. However, the rate of perfume release through the polyethylene film wall of a perfume container device is limited by the non-porous nature of the polyolefin film. Therefore, the size of the perfume container device must be increased and/or the concentration of perfume in the perfume container device must be increased in order to obtain a desired perfume release rate (thus resulting in increased costs).

There is a need for a more economical perfume container device that can contain less perfume while achieving the desired perfume release rate. For this reason, the use of a microporous polymer surface as the material of the wall of the perfume container device or container will promote the movement of perfume through the wall of the membrane of the perfume container device at a faster rate. However, the use of microporous polyolefin films in perfume container device applications is limited because perfume oils are prone to leakage from the film walls of the container. This disadvantage can be overcome by modifying the surface energy of the microporous film using the present invention, for example, by rendering the walls of the film or perfume container device oleophobic and preventing perfume grease leakage through the use of fluorine-containing functionalized polymers A-B.

In accordance with at least selected embodiments of the present invention, the modified functionalized polymer A-B is capable of modifying a polymer matrix having a lower or higher surface energy-without the modified functionalized polymer A-B-that would normally resist direct bonding of the desired chemical material. Alternatively, the modified functionalized polymer A-B may covalently modify a polymer matrix having a polarity-in the absence of the modified functionalized polymer A-B-that would normally limit and/or prevent direct bonding of the desired chemical material. Furthermore, the modified functionalized polymers A-B are capable of modifying a polymer matrix whose surface has hydrophilic or hydrophobic-surface properties, which would normally limit or prevent the desired chemical materials from directly bonding without the modified functionalized polymers A-B. Alternatively, the modified polymer A-B can modify a polymer matrix whose surface has oleophilic or oleophobic-surface properties that would normally limit or prevent direct bonding of the desired chemical material without the modified functionalized polymer A-B.

At least certain embodiments relate to the modification of certain functionalized polymers for the addition of bio-extracted polymers and small molecules for end-use applications that may require biological detection or analytical testing. Proteins, DNA, RNA, naturally occurring polysaccharides, or other biologically relevant substances may be used for such applications. In these embodiments, the modification may be carried out by modifying certain functionalized polymers with a single carbene and/or carbene component B or a mixture of multifunctional carbene and/or carbene components B. In addition, at least certain embodiments relate to modifying the surface of a polymer matrix with a mixture of multifunctional carbene and/or nitrene precursor components B that have been reacted with a desired component a, such as a functional synthetic polymer, a small molecule, a bioactive surface modifier, and the like.

Modification of the surface of the polymer matrix can be used to alter its functionality. For example, a nominally chemically inert polymer matrix can be modified by brushing the surface of the matrix with functional groups added by component a or modified functional components a-B, which are designed to participate in a secondary post-treatment to modify the polymer matrix. The modification changes the functionality of the polymer matrix to achieve the intended end use application. One example of such a post-treatment reaction is a textile end-use application where the surface of the textile substrate has reacted with modified components a-B, and thus is amenable to standard textile dyeing chemicals and procedures to produce significantly different end effects.

The polymer matrix (e.g., component C) can include any synthetic or natural polymer or copolymer, such as olefinic, styrenic, colloidal silica, urethane, acrylate, ester, vinyl, cellulose, amide, aramid, ether, or copolymers and mixtures thereof. In addition, the polymer matrix may also be a crosslinked network material, such as a phenolic resin or a rubbery material such as butadiene, isoprene and neoprene. Furthermore, the polymer matrix may be a halogen-containing polymer such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), and/or polyvinyl chloride (PVC).

The chemical structure of the modified functional sulfonated styrene monomer, polymer or copolymer, designated as component AB, contains the surface functional groups (e.g., component a) required by the polymer matrix (component C) in the end use application. The functional polymer a or component a may comprise a polymer similar to the polymer matrix. In addition, the functional polymer a or component a may include polyamines, polyols, polyamides and mixtures or copolymers thereof.

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. In particular, the present invention relates to chemically modified polyolefin microporous films, methods of making chemically modified polyolefin microporous films, and methods of using chemically modified polyolefin microporous films. More particularly, the present invention relates to chemically modified polyolefin microporous battery separators or battery separator films, methods of making chemically modified polyolefin microporous battery separators or battery separator films, and methods of using chemically modified polyolefin microporous battery separators or battery separator films.

In accordance with at least selected preferred embodiments, the present invention relates to the chemical modification of polyolefin microporous battery separators or separator films by chemical reaction of carbene or nitrene intermediates with carbon-hydrogen bonds of polyolefins; a method for improving the hydrophilicity or wettability of a polyolefin microporous battery separator or separator film in a lithium ion rechargeable battery; a method of introducing crosslinking into a polyolefin microporous battery separator or separator film, and the like.

In accordance with 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 membrane is accomplished by chemical reaction of carbene and/or nitrene intermediates with the carbon-hydrogen bonds of the polyolefin. Such carbene and/or nitrene intermediate based chemical reactions or treatments provide a more permanent method of improving the wettability of polyolefin microporous separators in lithium ion rechargeable batteries. In addition, the reaction of the preferred carbene and/or nitrene intermediate with the C-H bond of at least one skin layer of the polyolefin microporous separator film may introduce cross-linking functionality into the polyolefin to increase the heat resistance of the polyolefin microporous separator or film.

A typical battery separator or separator may be a single, multi-layer or multi-layer composite battery separator made of one, or more, or multi-layer composite polyolefin porous films or films. The microporous membrane may be a symmetric membrane or an asymmetric membrane. The film may be made from one or more polyolefin polymers or blends, including but not limited to: polyethylene (PE, including LDPE, LLDPE and HDPE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polymethylpentene (PMP), any blends and mixtures thereof. The film may be made by any suitable process including, but not limited to, a dry-stretch process (also known as the CELGARD process) or a solvent process (also known as the gel extrusion process or the phase separation process or the wet process) or a web (or hole) process (in which the film is cast onto chilled rolls with a pattern embossed on the film, and then the embossed film is stretched (MD/TD) to form large holes along the embossed pattern). The film has a thickness of about 75 microns or less. The film preferably has the properties required for use as a battery separator in a battery, such as a lithium battery, more preferably a rechargeable lithium ion battery, and the like. The chemically modified film of the invention can be used as the outer layer of a three-layer film (e.g., PP/PE/PP or PE/PP/PE) or other multi-layer film or separator such as a three-layer shutdown separator.

Polyolefins are a class or group of thermoplastics from monoolefins. Polyolefins generally include polyethylene, polypropylene, polybutylene, polymethylpentene, and copolymers thereof. Polyolefin articles generally include fibers and films, as well as microporous films and microporous hollow films. "microporous" refers to an article having a plurality of pores with a physical diameter of 1 micron or less. Hydrophobic polyolefin refers to a polyolefin having a surface energy equal to or less than the surface energy of polyethylene.

In accordance with at least certain embodiments, the polyolefin article is rendered more hydrophilic or more wettable by chemically modifying at least a portion of the surface, such as by chemical reaction of the microporous separator or film through carbene and/or nitrene intermediates with carbon-hydrogen bonds of the polyolefin. In addition, the reaction of the preferred carbene and/or nitrene intermediates with the C — H bonds of at least one skin layer of the polyolefin article may be used to introduce cross-linking to the polyolefin to improve high temperature stability, strength, and the like. The hydrophilic polyolefin article described above can be used in any application where a hydrophilic polyolefin is required or preferred, for example, air filtration, air purification, water filtration, water purification, medical equipment, separation equipment, semiconductor manufacturing, battery cell separators, ultrafiltration equipment, and the like.

For batteries or battery separators, chemical treatments are applied to one or both surfaces of the microporous polyolefin film. The treated separator is particularly suitable for use in lithium ion secondary batteries. For separation, filtration, purification and purification devices, especially devices using microporous polyolefin hollow fibers or flat sheet membranes, higher flow rates can be obtained by using modified materials.

Chemical modification of carbon-hydrogen and other bonds in polyolefins has presented difficulties as a means of permanently improving the hydrophobicity of polyolefins, since the number of effective chemical reactions is limited. Carbon-hydrogen bonds are very stable, which makes it difficult to permanently modify polyolefins such as polypropylene and polyethylene. Polyolefins such as polypropylene and polyethylene are commonly used in microporous separator films in lithium ion rechargeable batteries. One important performance characteristic of polyolefin microporous films is their easy wetting by nonaqueous electrolyte solvents commonly used in lithium ion rechargeable batteries. Currently, various surfactants are used as coatings to modify the hydrophobicity of polyolefin microporous separator films and enhance their wettability with nonaqueous electrolyte solvents. Certain surfactant coatings can only provide temporary wettability because they are only physically adsorbed onto the surface of polyolefin microporous separator films.

Carbene and/or nitrene surface treatments can also be achieved by a wide variety of small molecule functional groups. Hydroxy acids, alcohols, thiols, amines (primary, secondary, tertiary, and quaternary), guanidinium salts, ethers, esters, and carbonates are functional groups that can impart hydrophilicity to the polyolefin microporous separator film.

The obvious enhancement of the wettability of the polyolefin microporous separator film to the strong polar electrolyte can be obtained by chemical modification of the polypropylene microporous separator film of the invention, and the polypropylene microporous separator film is suitable for the electrolyte which can be used for lithium ion rechargeable batteries in a wide range at present and in the future.

For example, the wettability of the matrix can be greatly improved based on the substitution of molecular additives. Perfluoro groups can impart superhydrophobicity, while polyethylene glycol additives can enhance water wettability. Polydimethylsiloxane may be used to enhance the tactile feel of the material to make the substrate more comfortable to the touch. In addition, surface or bulk crosslinking and treatment of materials containing multifunctional carbene and/or nitrene precursors can result in enhanced cross-directional toughness of the web.

Carbene and/or nitrene intermediates, which participate in many chemical reactions, may also be inserted into a specific structure in order to introduce cross-linking in the polyolefin microporous separator film. An additional benefit that is obtained is increased battery safety in enhancing the cross-web strength of the microporous polyolefin separator film, since the crosslinks in the polyolefin material will hold the polymer molecules together.

For example, binding molecules of greater than a single carbene and/or nitrene precursor can be added to a polyolefin microporous separator film after pore formation, creating a crosslinked surface. Crosslinking of the surface of polyolefin microporous separator films can play an important role in high temperature end use applications. By creating a lightly crosslinked surface, the temperature at which the structural integrity of the polyolefin microporous separator membrane is lost can be increased and can be adjusted to a specific temperature range depending on the crosslink density. This is achieved because the cross-linked material can support the melted host material without cross-linking. As the surface crosslink density increases, the ability of the exoskeleton to support the structural integrity of the polyolefin microporous separator film is also increased.

In addition, crosslinking molecules larger than the combination of individual carbene and/or nitrene precursors can be added to the polyolefin polymer resin during extrusion to form a nonporous precursor separator film. The precursor separator film is stretched to form the pores of the microporous polyolefin film, thereby resulting in a microporous polyolefin film having improved tensile strength and melt integrity at elevated temperatures.

In at least selected embodiments, the separator may be a nonwoven material, such as comprised of fibers, that has been chemically modified to increase the high temperature melt integrity and/or increase the wettability of the nonwoven material.

In accordance with at least certain objects of the present invention, there are provided novel, improved or modified surface-modified polymeric materials, modified functionalized polymers, functional polymers, chemically modified substrates comprising modified functionalized polymers; methods of making and/or applying surface-modified polymeric materials, modified functionalized polymers, functional polymers, and/or chemically modified substrates comprising modified functionalized polymers; a method of modifying a functionalized polymer and/or a method of using a modified functionalized polymer to chemically react with a surface of a substrate; and/or methods of using such chemically modified substrates. At least certain embodiments relate to modified functionalized polymers, functional polymers, and methods of modifying functional polymers to chemically modified porous and/or nonporous polymer substrates and/or methods of using these modified substrates. At least selected embodiments relate to modified functionalized polymers, functional polymers, and methods of modifying functional polymers to chemically modified porous and/or microporous polymer substrates and/or methods of using these modified substrates. At least selected embodiments or objects relate to modified functionalized polymers, functional polymers, and methods of modifying functionalized polymers into chemically modified porous and/or microporous polymer matrices and methods of using the modified matrices. At least certain embodiments or objects relate to modifying certain functionalized polymers to cause a change in the surface properties of the substrate. In accordance with at least selected possibly preferred embodiments, the present invention relates to chemically modifying a functionalized polymer with a carbene and/or nitrene crosslink modifier to form a modified functionalized polymer that is capable of chemically modifying the surface of a substrate and which causes a change in the surface properties of the substrate to meet a predetermined end use application. According to at least selected possible preferred embodiments, the present invention relates to the covalent modification of a polymer surface (component C) with a carbene and/or nitrene crosslink modifier (component B, which may comprise monomer X or monomer X + Y) and a functionalized polymer (component A) to form the final material, i.e., a modified functionalized polymer material or matrix A-B-C. The modification can alter the chemical reactivity of the polymer surface, giving the modified substrate a functionality specifically designed for the intended end use or application.

The present invention relates to novel, improved or modified copolymer materials, films, substrates, and the like, and novel improved or modified methods for permanently modifying the physical and/or chemical properties of one or more surfaces, faces, or portions of a polymeric substrate to meet various end uses or applications. For example, an improved method employs carbene and/or nitrene modifiers to chemically modify a functionalized polymer to form a chemical species that can chemically react with and change the chemical reactivity of the surface of the polymer matrix. The method involves an intercalation reaction or mechanism to modify the polymer matrix to increase or decrease surface energy, polarity, hydrophilicity or hydrophobicity, oleophilicity or oleophobicity, etc., thereby improving the compatibility of the polymer matrix with the coating, material, adjacent layers, etc. In addition, the invention can be used to produce chemically modified films, fibers, hollow fibers, textiles, and the like. For example, the present invention can be used to produce a polyolefin microporous battery separator or film having improved hydrophilicity or wettability, a crosslinked structure in the polyolefin, or the like, which can enhance high-temperature stability, or the like.

Embodiments of the present invention relate to a polymer comprising a polymerized arylsulfonyl azide or copolymer thereof. In the above embodiments, the arylsulfonyl azide may be a styrene sulfonyl azide. In addition, arylsulfonyl azides may be copolymerized with vinyl monomers. In the above case, the vinyl monomer may be hydrophilic or hydrophobic. And the vinyl monomer may be styrene sulfonate or a salt thereof. Meanwhile, the vinyl monomer may be selected from substituted styrene, acrylic acid, methacrylic acid, vinylpyridine, vinylpyrrolidone, acrylamide, methacrylamide, salts thereof, and the like. Further, the vinyl monomer may be substituted with a reactive group.

In various other embodiments, the modified substrate comprises a surface modifying agent, wherein the modifying agent comprises a base polymer comprising a polymerized arylsulfonyl azide or copolymers thereof, wherein at least one azide of the base polymer has reacted with a carbon atom of the substrate to form a sulfonamide-crosslinking group. In the above embodiments, the azide is reacted with the carbon atom by exposing the first polymer and the substrate to ultraviolet light. In the above embodiments, the substrate may be selected from polymers, woven substrates, fibers, polyolefin materials, polypropylene materials, polyethylene materials, porous polymer substrates, nonporous polymer substrates, microporous polymer substrates, porous hollow fibers, nonporous hollow fibers, porous battery separators or membranes, microporous polymer membranes, chemically modified polymer substrates, polymer skins, mixtures and combinations thereof, and the like.

Other embodiments of the invention relate to a method of modifying a substrate comprising combining the substrate with a polymer comprising polymerized arylsulfonyl azide or copolymers thereof. In the method, the matrix may be combined with the polymer in the presence of ultraviolet light and/or heat. Further, in the embodiment, the polymer may be a copolymer whose vinyl monomer is substituted with a reactive group, and the method further includes a step of reacting with the reactive group, thereby modifying the surface of the substrate.

According to at least selected oleophobic related embodiments:

1. the polymer surface (film, fiber or host material) may be modified with a mixture of a multifunctional carbene and/or nitrene precursor (component B, which may contain monomer X or monomer X + Y) and a desired functional synthetic monomer or polymer (component a).

a. The polymer surface may be any synthetic or natural polymers and copolymers, including but not limited to the following polymer classes: olefinic, styrenic, silica gel, urethane, acrylate, ester, vinyl, cellulose, amide, aramid, ether, and the like. The polymer surface may also be a crosslinked network material such as a phenolic resin or a rubbery material such as butadiene, isoprene and neoprene. In addition, modifications of other halogen-containing polymer/polymer surfaces such as PTFE, PVDF, PVDC and PVC can also be carried out.

b. Component a may be a material commonly found in hydrophobic or oleophobic treatment applications. Such as fluorinated acrylic copolymer systems, which are used extensively in textile treatment, or chitin-based materials, can provide suitable oil resistance. In addition, component a may be a composite material with additional nanoparticles to create a nano-scale roughness for enhanced oil resistance.

c. Component B may be a monofunctional material (f ═ 1), or in other embodiments, a multifunctional material (f >2.0), with tailored pendant functional groups to generate carbene and/or nitrene species in situ.

2. The amount of the mixture of components A and B to be applied can be derived from organic or aqueous solutions, and the surface modification of the polymer surface is further generated by heat treatment or exposure to UV light.

a. The modification may be applied to the surface in an amount sufficient to achieve the desired surface properties for the intended application. The typical utilization rate can be 0.05g/m²To 1.0g/m²And possibly on the surface area of the substrate, the viscosity of the solvent and-

Or effective rate (cure rate).

b. The ratio of components a and B is variable to produce optimum characteristics. Typical A/B usage ratios may range from 1.0 to 200.0, depending on the desired surface properties and reactivity of A and B.

In accordance with at least selected objects and embodiments, the present invention provides or relates to:

a modified polymer matrix, a surface modified polymeric material, a modified functionalized polymer, a functional polymer or a chemically modified matrix containing a modified functionalized polymer as described or illustrated herein.

The above invention, wherein the modified polymer matrix is a chemically modified polymer matrix.

The above invention wherein the modified polymer matrix is at least one of a porous polymer matrix, a non-porous polymer matrix, a porous hollow fiber, a non-porous hollow fiber, a porous battery separator or film, a membrane, a chemically modified polymer matrix, a fiber, a textile, a polyolefin material, a polyolefin blend, a polypropylene material, a polyethylene material, a polymer skin, mixtures and combinations thereof, and the like.

The above invention wherein the modified polymer matrix is chemically modified by a chemical reaction between at least one carbene and nitrene intermediate and the carbon-hydrogen bond of the polymer matrix at the site covalently bonding to at least one modified functionalized polymer.

Methods of making and methods of using modified polymer matrices, surface modified polymeric materials, modified functionalized polymers, functional polymers or chemically modified matrices containing modified functionalized polymers, membranes, hollow fibers, textiles, composites, layers, surfaces, chemically modified polyolefin microporous films, chemically modified polyolefin microporous battery separators or battery separator films, ribbed materials, mixtures thereof; a method for improving the wettability of a polyolefin microporous battery separator in a lithium ion rechargeable battery; a method of introducing crosslinks to a polyolefin microporous separator; and/or a method as described or illustrated herein.

The above method comprising chemically modifying a polyolefin microporous battery separator membrane by a chemical reaction that takes place using at least one carbene and nitrene intermediate and a polymer matrix carbon-hydrogen bond; the polyolefin microporous battery separator suitable for the lithium ion rechargeable battery has improved wettability; at least one step of the cross-linking, etc., introduced to the polyolefin microporous battery separator.

In a battery separator, the improvement comprising a polyolefin microporous film chemically modified on at least a portion of at least one surface.

The above separator wherein the chemically modified polyolefin has a surface energy equal to or greater than that of polyethylene.

The above separator wherein said chemical modification increases the surface energy of the polyolefin to at least 48 dynes/cm.

The above separator wherein said polyolefin microporous film is chemically modified to increase the surface energy of said film.

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

In a battery comprising an anode, a cathode, an electrolyte, and a separator, the improvement comprising the above-described separator.

In a textile comprising a polyolefin microporous film, the improvement comprising a polyolefin microporous film having a portion of said at least one surface chemically modified.

The textile product wherein the surface modification of said chemically modified polyolefin film comprises a cellulosic material for secondary standard textile treatments such as dyeing or other processing steps.

The textile as described above, wherein the chemically modified polyolefin film has a surface energy equal to or less than polytetrafluoroethylene.

The textile product wherein said chemical modification reduces the surface energy of the polyolefin film to a maximum of about 20 dynes/cm.

A textile laminate comprising at least one layer of synthetic or natural fibers in combination with the above polyolefin film.

An oleophobic modified polyolefin textile film comprising a polyolefin microporous film that has been chemically modified to reduce its surface energy, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, and blends, mixtures, and copolymers thereof; wherein the chemically modified polyolefin comprises an oleophobic polymer or combination of polymers, and the like.

A microporous polymer film having at least one surface or portion thereof chemically modified to provide a durable chemical modification by covalently bonding at least one modified functionalized polymer at the site through a chemical reaction between at least one carbene and nitrene intermediate and the polymer matrix carbon-hydrogen bonds, the chemical modification providing at least one of the following properties: increased wettability, reduced wettability, hydrophilicity, hydrophobicity, oleophobicity, lipophilicity, stain resistance to biological materials, resistance to organic solvents, resistance to methanol, ethanol, 1-propanol, acetone, and/or other polar solvents, and resistance to aliphatic and/or aromatic type solvents.

Non-limiting examples

EXAMPLE 1 Synthesis of- -4-styrenesulfonyl azide monomer

In example 1, 4-styrenesulfonyl azide monomer was synthesized. Specifically, 34.4g of thionyl chloride (290mmol) was added to a flask and cooled in an ice bath. 10g of sodium 4-styrenesulfonate (48.4mmol) were added to cooled thionyl chloride in portions with stirring. The solution was observed to thicken to a slurry as the solids were added. To a 20mL sample was added 60mL of DMF and the mixture was stirred to form a homogeneous solution. The solution was stirred in the ice bath for 45 minutes to bring it to room temperature and then stirring was continued for 1-2 hours. The reaction product was poured into ice (ca. 200g) upon completion and the mixture was extracted with ethyl acetate (3x50mL), the sulfonyl chloride layer was collected, dried over magnesium sulfate and concentrated to 7.24g sulfonyl chloride as a light yellow orange oil.

The sulfonyl chloride (35.1mmol) from the step was dissolved in acetone and placed in an ice bath. 20mL of ionized water was added, followed by addition of 2.39g of sodium azide (36.9mmol) in portions over 5 minutes. The reaction was stirred for 5 days to completion at which time the solution was washed with ethyl acetate (3 × 20 mL). The resulting organic portion was collected, dried over magnesium sulfate, and concentrated to a pale yellow oil (yield 7.21 g). The pale yellow oil constitutes the 4-styrenesulfonyl azide monomer.

EXAMPLE 2 Synthesis of a styrene-based Polymer containing 4-styrenesulfonyl azide monomer

The sulfonyl azide monomer (1.5g, 7.1mmol) from example 1 above was charged to a flask along with various desired comonomers (described in more detail below) (7.1mmol) and a chain transfer agent. The chain transfer agent used here was 2-cyano-2-propyldodecyltrithiocarbonate (28mg,0.08 mmol). An initiator (here, 4, 4' -azo (4-cyanovaleric acid)) (42mg, 0.15mmol) was separately dissolved in DMF solution (3mL) and added to the polymerization flask. The polymerization flask was then sealed with a rubber septum and the solution sparged with nitrogen for 5 minutes. Next, the polymerization reaction flask was placed in a thermostatic bath at 60 ℃ for 5 hours. After the polymerization reaction has proceeded, the reaction is terminated by exposure to oxygen and the sulfonyl azide polymer is recovered by precipitation with a suitable solvent.

Comonomers polymerized with sulfonyl azide monomers include 2,3,4,5, 6-pentafluorostyrene, styrene, and 4-styrene sulfonate. In the case of polymerization with 4-styrenesulfonate, DMF is added to aid in the dissolution of the solid 4-styrenesulfonate.

Example 3 general activation of sulfonyl azide polymers to form nitrenes

Reaction with substrate under ultraviolet irradiation

Formulation and activation of the sulfonyl azide material is achieved by dissolving the appropriate polymer needed for surface modification in acetone. In the normal case: the weight ratio of the azide to the functional polymer is 1:1 to 1: 10. The solution is applied to a substrate and the solvent is stripped. The resulting film and substrate were exposed to a high intensity long wave uv spot for 15-45 seconds and rinsed again with acetone to remove the physisorbed materials. In some cases, treatment with UV light at a wavelength of 254nm gives good results.

Active sulfonyl azide polymers were studied using a variety of analytical approaches. By way of example, FIG. 7 is a FTIR spectrum of a polymer formed from a sulfonyl azide monomer having a monomer content of about 50% and a 4-styrene sulfonate monomer having a monomer content of about 50%. By way of example only, FIG. 7 shows a range of 2000 and 2500cm^-1The peak between, which may be related to the azide component of the polymer.

Further, FIG. 8 is a DSC plot of a polymer formed from a sulfonyl azide monomer having a monomer content of about 50% and a 4-styrene sulfonate monomer having a monomer content of about 50%. This calorimetry plot shows, for example, that water is liberated at 100 ℃ and then nitrene activation and nitrogen loss are well above 190 ℃. This temperature may be considered the activation temperature of the nitrene in this particular embodiment.

FIG. 9 is a thermogravimetric analysis of a polymer formed from a sulfonyl azide monomer having a monomer content of about 50% and a 4-styrenesulfonate monomer having a monomer content of about 50%. This analysis of the polymer shows that the decomposition of the polymer at various temperatures, and the formation of nitrene can also be collected from the figure. For example, it can be seen that nitrene formation at various temperatures is associated with weight loss of the polymer.

EXAMPLE 4 reactive dyeing of Polypropylene nonwoven Material

Poly (sodium styrenesulfonate-co-styrene sulfonyl azide) was synthesized with 37% sulfonyl azide monomer content, and 210mg was dissolved in 12.5g of water at 70 ℃. To this solution was added 440mg of a 50 wt% branched polyethyleneimine solution (BPEI). Next, 2.98g of acetone was added for wetting. Applying the solution to polypropyleneEthylenic nonwoven (100 grams per square meter (gsm)), after contacting the solution, the substrate is dried in a convection oven at 110 ℃ for about 5 minutes. Exposing the dried substrate to 0.2J/cm²254nm ultraviolet light. The material was then contacted with a 5mg/mL solution of Drimaren Navy reactive dye. The samples produced showed that the nonwoven was not uniformly dyed, but was durable. The effect was improved by adding an additional 440mg of BPEI solution, resulting in a permanent uniform blue color on the nonwoven. Untreated portions of the nonwoven material were also exposed to the above-described dye liquor, but were not dyed in the process.

EXAMPLE 5 durable oil resistance of Polypropylene nonwoven

Poly (sodium styrenesulfonate-co-styrene sulfonyl azide) was synthesized with 50% sulfonyl azide monomer composition, and 102mg was dissolved in 3mL of water and 1mL of acetone along with 1.5mL of TG-8731(20 wt%, Daikin) fluoropolymer. The polypropylene nonwoven (45gsm) was treated with this solution and dried in a convection oven at 115 ℃ for about 5 minutes. The substrate was dried, i.e., exposed to long wave uv light for 5 minutes. After uv treatment, the sample was placed in a stirred acetone bath to strip the non-covalently bound material. The samples were dried at 115 ℃ for 5 minutes and tested for dodecane repellency after rinsing with acetone. All 4 samples showed repellency to dodecane after the acetone stripping step. The control sample showed no protection from dodecane throughout the process.

In accordance with at least selected embodiments, aspects, objects, etc., the present invention is directed to novel improved or optimized surface modifying agents; a material made or modified by the modifying agent; and/or methods of making and/or using the modifying agent and/or modifying material; and/or novel improved or preferred polymers and/or textile materials, separators, garments, fabrics, etc., incorporating the modifiers, modifying materials, layers, substrates, precursors, etc. In accordance with at least certain embodiments, the present invention relates to surface modifiers for polymers and/or textile materials; a modified material; and/or methods of making and/or using the surface modifying agent to modify and functionalize a polymer and/or textile material; methods of using surface modifying agents or functionalized polymers and/or textile materials.

In accordance with at least certain embodiments, the present invention relates to a surface modifying agent comprising a suitable nitrene and/or carbene precursor capable of forming one or more nitrene and/or nitrene functional groups by chemical reaction, optionally in the presence of heat and light. Potentially preferred nitrene precursors include materials such as polystyrene sulfonyl azide monomers, polymers or copolymers that are capable of forming one or more nitrene and/or nitrene functional groups by chemical reaction, optionally in the presence of heat and light. At least particularly selected embodiments relate to a surface modifying agent comprising a sulfonated styrene monomer, polymer or copolymer comprising one or more sulfonyl azide functional groups, which are reactive and capable of chemically reacting with the surface of a polymer or textile material to impart or introduce specific or desired chemical surface functionalization to the surface. At least certain possibly preferred embodiments relate to a surface modifying agent comprising a sulfonated styrene monomer, polymer or copolymer containing one or more sulfonyl functional groups capable of chemically reacting with the surface of a polymer or textile material to impart or introduce specific or desired chemical surface functionalization to said polymer or textile material.

The introduced modifications or functionalizations can alter the physical properties of polymeric and/or textile materials or provide these materials with new utility. For example, the functionalization may introduce properties such as hydrophilicity, hydrophobicity, oleophilicity, oleophobicity, and/or the functionalization may alter the surface energy of the polymer or textile material to modify the polymer or textile material for a particular end use. In addition, certain surface modifications may provide specific functionalization for new uses. For example, the purpose of introducing functionalization may be to enable the material to be used in the case of interactions, for example, in the case of its interaction with other substances such as other molecules. Further examples include, but are not limited to, the specific application of the modified or functionalized materials in the context of interaction with other materials, coatings, layers, and the like, particularly for use in battery separators, barrier fabrics, films, substrates, layers, fabrics, textiles, and/or for use in electrochemical cells or batteries, textiles, apparel, filtration, adsorption, testing, drug delivery, analyte sensing, medical devices, medical diagnostics, and the like.

This invention relates generally to U.S. provisional patent application No. 61/508,725, No. 7/18/2011, U.S. provisional patent application No. 13/551,883, No. 7/18/2012, and U.S. provisional patent application No. 61/547,812, No. 10/17/2011, the entire contents of each of which are incorporated herein by reference.

In accordance with at least selected embodiments, aspects, objects, etc., the present invention is directed to novel improved or optimized surface modifying agents; a material made or modified by the modifying agent; methods of making and/or using the modifying agents and/or modifying materials; and/or novel improved or preferred polymeric and/or textile materials, separators, garments, fabrics, etc. incorporating the modifiers, modifying materials, layers, substrates, precursors, etc.; to a process for polymeric and/or textile materials, modified materials, making and/or using said surface modifying agent to modify and functionalize polymeric and/or textile materials, and/or using a surface modifying agent or functionalized polymeric and/or textile materials; to a surface modifying agent comprising a suitable nitrene and/or carbene capable of forming one or more nitrene and/or nitrene functional groups by chemical reaction, optionally in the presence of heat and light; to possibly preferred nitrene precursors, including, but not limited to, materials such as sulfonyl azide-containing styrene monomers, polymers or copolymers, which are capable of forming one or more nitrene functional groups selectively by chemical reaction in the presence of heat and light; to a surface modifying agent comprising, for example, a sulfonated styrene monomer, polymer or copolymer comprising one or more sulfonyl functional groups, such as sulfonyl azide functional groups, which are reactive to chemically react with the surface of a polymer or textile material to introduce specific or desired chemical surface functionalization to the surface of the polymer or textile material; to altering the physical properties of polymeric or textile materials or to impart new utility to such materials; the functionalization introduces properties such as hydrophilicity, hydrophobicity, oleophilicity, oleophobicity, etc. into the polymer and/or textile material, and/or the functionalization can alter the surface energy of the polymer or textile material to modify the polymer or textile material for specific end uses; providing specific functionalization for new uses; the purpose of introducing functionalization may be to enable the material to be used in the case of interactions, for example, in the case of its interaction with other substances such as other molecules. Further examples include, but are not limited to, the specific application of the modified or functionalized materials in the context of interaction with other materials, coatings, layers, and the like, particularly for use in battery separators, barrier fabrics, films, substrates, layers, fabrics, textiles, and/or for use in electrochemical cells or batteries, textiles, apparel, filtration, adsorption, testing, drug delivery, analyte sensing, medical devices, medical diagnostics, and the like.

Other objects, embodiments, aspects or embodiments of the invention are shown or described in the drawings, detailed description or claims. Many other modifications and/or variations of the present invention are possible to those skilled in the art in light of the teachings herein. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

The terms "comprises/comprising" and the terms "having/including" as used herein with respect to the present invention specify the presence of stated features, integers, steps or components but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

For the sake of clarity, certain features of the invention are described in the context of separate embodiments, which may likewise be provided in the context of a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable combination.