Fluorine-free oil-proof coating and its production method and use

Abstract

The present application provides a fluorine-free oleophobic layer comprising one or more polydimethylsiloxane resin layers. The layer can be disposed on part or all of a substrate surface. Methods of making and using the layer are also provided.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is a divisional application of the Chinese invention patent application with application number 201880040346.0 (the application date of which is April 17, 2018, and the invention name is "Fluorine-free oil-proof coating and its production method and use"). The original application is a Chinese national phase application with international application number PCT / US2018 / 028029, which claims priority to U.S. provisional application 62 / 486,245 filed on April 17, 2017, and its disclosure is incorporated into this application by reference. Field of the Invention

[0003] The present disclosure generally relates to polymer-based oleophobic coatings. More specifically, the present disclosure relates to oleophobic coatings based on poly(dimethyl)siloxane (PDMS) resins. Background Art

[0004] The textile industry is under immense pressure to eliminate all hazardous chemicals from its products and supply chains. Fluorinated compounds are at the top of this list. Per- and polyfluorinated substances are attractive for use in many industrial applications and consumer products, such as carpets, clothing, and upholstery, due to their hydrophobic and oleophobic properties. Polyfluorinated compounds resist degradation and persist in the environment for a long time. They can bioaccumulate, and some have been linked to adverse health effects, at least in experimental animals.

[0005] Finding alternatives to fluorine-based compounds while maintaining the same level of performance and durability is not easy. Oil-repellent coatings can be used in a variety of consumer products and industrial applications (such as moisture protection and self-cleaning). Although there are many examples of superhydrophobic coatings, there has been limited progress in highly oleophobic coatings. Many superhydrophobic coatings have been shown to be oleophilic. In addition, in contrast to the superhydrophobic state, oleophobicity may vary significantly depending on the type of oil. A surface that is superoleophobic to certain oils (contact angle>150°) may be oleophilic to another oil with a lower surface tension.

[0006] The difficulty in modifying oleophobic coatings stems from fundamental limitations of the material. Since the surface tension of hydrocarbon oils is typically in the range of 20-36 mN / m, the surface tension of a smooth, oil-repellent substrate must be less than 20 mN / m according to Young's equation. 2 Specifically, olive oil has a surface energy of ~32 mN / m, and depending on their type, vegetable oils typically have surface energies as low as 30s mN / m. Mineral oils are The first oil used in the standard test for oleophobicity (level 1) has a surface energy of 31.5 mN / m. The requirement for low surface energy means that the most commonly used materials are not inherently oleophobic. Only a few fluorinated materials can meet this prerequisite for oleophobicity. In fact, all so-called superoleophobic coatings developed to date use fluorinated compounds with a large number of -CF2- and -CF3 groups, such as PTFE, perfluorosilanes and perfluoropolymers. Given the limitations of the inherent surface tension of the materials, essentially all previously developed highly oleophobic coatings are based on fluorinated materials with low surface energy.

[0007] With the development of superhydrophobic materials, appropriate surface roughness can be introduced to enhance oleophobicity. For example, re-entrant structures have been proposed to prepare oleophobic surfaces.

[0008] Table 1. Summary of previous work on highly oleophobic surfaces

[0009]

[0010]

[0011]

[0012]

[0013] While using these re-entrant structures reduces the substrate's surface tension requirements, fabrication of re-entrant structures (typically via photolithography combined with chemical etching) is difficult and costly, especially for flexible substrates. For practical industrial applications, essentially all previously developed highly oleophobic coatings are still based on fluorinated materials with extremely low surface energy.

[0014] Efforts to develop oleophobic coatings using non-fluorinated materials have been limited. Commonly used PDMS has a surface energy of approximately 22–24 mN / m. Consequently, PDMS finishing often fails to provide an effective oleophobic coating because the surface energy is not sufficiently low. Furthermore, PDMS finishing can present challenges with adhesion, uniformity, and mechanical properties, depending on the varying properties of the substrate.

[0015] Independent oleophobic membranes have been prepared using microfluidic silicone oil emulsion templates. The membranes have uniform honeycomb microcavities with narrow openings, which can be called reentrant structures. The membranes exhibit oil repellency and flexibility without the use of any fluorocarbons for surface modification or complex photolithographic processes. However, microcavity membranes have limited wear resistance. The thin top layer with narrow cavity openings is easily worn, which reduces the oleophobicity of the membrane and even makes it oleophilic (although the membrane can still be superhydrophobic) because its reentrant structure is lost. To generate a well-defined microcavity structure, fine solvent evaporation on a relatively uniform, flat substrate is used in the emulsion template process. This is more difficult for rough substrates (such as decorative fabrics) because capillary action causes uneven solvent evaporation. More importantly, the typical size of the microcavities is in the range of tens of micrometers, which is similar to or even larger than the diameter of many common fibers, limiting microfluidic emulsion templates to applications in textile finishing, not to mention process scale-up. A potential solution is to use the membrane as an additional oil-repellent film on the substrate. However, the feel and appearance of this oleophobic surface may be compromised.

[0016] Based on the foregoing, there exists an ongoing and unmet need to find alternatives to fluorine-based compounds used in textile and other industries while maintaining the same level of performance and durability. SUMMARY OF THE INVENTION

[0017] The present application provides a layer disposed on part or all of a surface (e.g., part or all of an outer surface) of a substrate (e.g., a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, etc.), the layer having a kinetic energy of less than or equal to 22 mJ / m 2 (For example, less than 22mJ / m 2 The present application also provides a method for preparing the layer and a use of the layer.

[0018] In one aspect, the present disclosure provides a layer (e.g., a molecularly rough layer) disposed on part or all of a surface (e.g., part or all of an outer surface) of a substrate, the layer having a strength of less than or equal to 22 mJ / m 2 (For example, less than 22mJ / m 2 ) surface tension. One or more layers may be one or more fluorine-free layers (e.g., one or more substantially fluorine-free layers). The layer may comprise multiple individual layers.

[0019] Layer can comprise one or more PDMS resins.For example, resin comprises multiple PDMS parts.For example, PDMS resin comprises crosslinkable groups, including but not limited to, acrylate, methacrylate, allyl, vinyl, thiol, hydroxyl, silanol, carboxylic acid, aldehyde, amine, isocyanate, azide, alkyne, epoxy, halide, hydrogen and combination thereof.Described crosslinkable groups can interact with described substrate (for example, covalently and / or non-covalently combine with described substrate) through one or more chemical bonds (for example, covalent bond, ionic bond, hydrogen bond, van der Waals interaction or its combination).In an example, PDMS resin comprises side group branched PDMS resin and straight chain PDMS resin.

[0020] The layer can be placed on part or all of the surface (or all of the surface or all of the outer surface) of the substrate. The substrate can have various sizes and shapes. The substrate can have various compositions. The substrate can be a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, etc. In an example, when the substrate is a fabric, the fabric is a natural fabric or is modified to be a super-hydrophilic, hydrophilic, hydrophobic or super-hydrophobic fabric.

[0021] In one aspect, the present application provides a method for preparing the layer described herein. The method is based on coating PDMS resin on a substrate.

[0022] In various examples, a method of forming a layer (e.g., a molecularly rough layer) disposed on a portion or all of an outer surface (e.g., all outer surfaces) of a substrate (e.g., a substrate described herein, such as a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, etc.), the layer having a molecularly rough layer having a strength of less than or equal to 22 mJ / m 2 Surface tension (e.g., less than 22 mJ / m 2 The method comprises: providing a substrate (e.g., a fabric); coating (e.g., by dipping or spraying) a portion or all of a surface (e.g., a portion or all of an outer surface) of the substrate (e.g., a fabric) with a PDMS resin (e.g., a side-group branched PDMS resin or a linear PDMS resin) (e.g., a PDMS resin of the present disclosure); and curing (e.g., thermally curing) the PDMS resin coating, wherein a surface tension of less than or equal to 22 mJ / m is formed on a portion or all of a surface (e.g., a portion or all of an outer surface) of the substrate (e.g., a fabric). 2 (For example, less than 22mJ / m 2 ) layer (e.g., a molecular rough layer).

[0023] In one aspect, the present disclosure provides an article comprising one or more layers described herein and / or one or more layers made by the methods described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more fully understand the nature and purpose of the present application, the following detailed description should be read in conjunction with the accompanying drawings.

[0025] Figure 1 Schematic diagrams showing (a) fiber structure, (b) T-shaped structure, and (c) other common concave corner structures.

[0026] Figure 2 A schematic diagram of the synthesis of a pendant-branched PDMS resin is shown, wherein X is selected from a -O-SiOX' group, wherein X' is independently selected from an alkyl group (eg, a methyl group) at each occurrence in the -O-SiOX' group.

[0027] Figure 3 A schematic diagram of the synthesis of a linear PDMS resin is shown. The number of repeating units (ROSi) of the PDMS can be 0 or greater. In various examples, the number of repeating units n is 10 to 400 (e.g., n is 50) and / or the value of m is at least 1 (e.g., 1 to 50,000, 1 to 25,000, or 1 to 10,000).

[0028] Figure 4 Shown are the deposition of one- and two-sided oleophobic coatings using composite nanofluids by dip coating (top) and spray coating (bottom).

[0029] Figure 5 Shown are SEM images of oleophobic cotton fabric modified with nanofluid using a dip-pad-dry-cure process; a) pristine oleophobic fabric, and b) oleophobic fabric after washing 30 times.

[0030] Figure 6 A comparison of the oil stain resistance of pristine cotton fabric (left) and nanofluid-modified oleophobic cotton fabric (right) is shown. A drop of vegetable oil (dyed with Oil Red O dye for clarity) was deposited on both fabrics.

[0031] Figure 7 An example of a branched side group PDMS resin is provided. The PDMS resin comprises a PDMS polymer having a PDMS backbone. The PDMS polymer can be formed using a multifunctional precursor (e.g., a bifunctional precursor having at least two acrylate groups). The PDMS resin can be colorless.

[0032] Figure 8Examples of PDMS resins are provided. PDMS resins provide examples of branched side group PDMS resins. PDMS resins comprise PDMS polymers having a PDMS backbone and PDMS side chains. The PDMS polymers can be formed using multifunctional precursors (e.g., precursors having at least three vinyl groups).

[0033] Figure 9 Shown is a substrate for the synthesis of oleophobic coatings via a graft-from backbone approach.

[0034] Figure 10 SEM images of fabric samples are shown: (a) pristine fabric and (b) oleophobic fabric prepared by atom transfer radical polymerization grafting from the backbone.

[0035] Figure 11 Photos of oleophobic fabrics made from different materials are shown. Detailed Description of the Invention

[0036] Although the subject matter to be protected is described with certain examples and / or embodiments, other embodiments, including embodiments that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, and method steps may be performed without departing from the scope of this disclosure.

[0037] The present invention discloses a range of values. The range shows a lower limit and an upper limit. Unless otherwise specified, the range includes all values ​​(lower limit or upper limit) reaching the minimum value and the range between the values ​​of the range.

[0038] The present application provides a layer disposed on part or all of a surface (e.g., part or all of an outer surface) of a substrate (e.g., a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, etc.), the layer having a kinetic energy of less than or equal to 22 mJ / m 2 (For example, less than 22mJ / m 2 )'s surface tension.

[0039] As used herein, the term "moiety" refers to a portion (substructure) or functional group of a molecule. For example, a moiety is a portion (substructure) or functional group of a precursor or PDMS resin. In various examples, a "moiety" refers to a chemical entity having one end that can be covalently bonded to another chemical species (e.g., a group) or multiple (e.g., two) ends that can be covalently bonded to other chemical species. Examples of moieties include, but are not limited to:

[0040] Moieties may be referred to as groups.

[0041] Unless otherwise indicated, the term "aliphatic" as used herein refers to a saturated or branched or unbranched hydrocarbon moiety / group that optionally contains one or more degrees of unsaturation. Moieties having unsaturation include, but are not limited to, alkenyl groups / moieties, alkynyl groups / moieties, and cyclic aliphatic groups / moieties. For example, an aliphatic group can be C1 to C 40 (For example, C1 to C 30 , C1 to C 12 , C1 to C 10 , or C1 to C5) aliphatic groups / moieties (e.g., alkyl), including all carbon integers and carbon number ranges therebetween. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, and the like. The aliphatic group / moiety may be unsubstituted or substituted with one or more substituents. Examples of substituents include, but are not limited to, various substituents such as halogens (-F, -Cl, -Br, and -I), other aliphatic groups (e.g., alkenes, alkynes), aryls, alkoxides, carboxylates, carboxylic acids, ether groups, hydroxyls, isocyanates, and the like, and combinations thereof.

[0042] In various embodiments, the present application provides layers that incorporate low surface energy materials with engineered surface roughness. Surface roughness can be engineered, for example, by exploiting the molecular structure of the base polymer or by stamping. Examples of molecular roughness include, but are not limited to, the use of branched or rigid segment-containing copolymers, copolymer self-assembly, microphase separation of polymer blends, and combinations thereof. Patterning of PDMS can be accomplished using techniques developed for microcontact printing and soft lithography.

[0043] In one aspect, the present application provides a layer (e.g., a molecularly rough layer) disposed on part or all of an outer surface (e.g., the entire outer surface) of a substrate, the layer having a strength of less than or equal to 22 mJ / m 2 (For example, less than 22mJ / m 2 ) surface tension. One or more layers can be one or more fluorine-free layers (e.g., one or more substantially fluorine-free layers). The layer can comprise multiple individual layers. In one example, the layer is disposed on part or all of the surface of the substrate.

[0044] In one example, a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, etc. comprises a fluorine-free layer (e.g., a molecularly rough layer) disposed on part or all of an outer surface (e.g., all outer surfaces) of the fabric, the layer having a fluorine-free layer of less than or equal to 22 mJ / m 2 (For example, less than 22mJ / m 2 )'s surface tension.

[0045] The surface tension of the layer is less than 22, 21, 20, 19 or 18 mJ / m2 For example, a layer with 12–22 mJ / m 2 12–20 mJ / m 2 or 12–18 mJ / m 2 surface tension.

[0046] The layer can have various thicknesses. In various examples, the layer has a thickness of a few nanometers to a few hundred micrometers. In other various examples, the layer has a thickness of 10 nm to 300 micrometers or 50 nm to 100 micrometers.

[0047] Layer can comprise one or more PDMS resins.For example, resin comprises multiple PDMS parts.For example, PDMS resin comprises crosslinkable groups, includes but not limited to, one or more acrylates, methacrylates, allyl groups, vinyl groups, thiols, hydroxyls, silanols, carboxylic acids, aldehydes, amines, isocyanates, azides, alkynes, epoxies, halides, hydrogen and combinations thereof. Crosslinkable groups can interact with substrate (for example, covalently and / or non-covalently combine with substrate) through one or more chemical bonds (for example, covalent bonds, ionic bonds, hydrogen bonds, van der Waals interactions or combinations thereof). In an example, PDMS resin comprises side group branched PDMS resin and straight chain PDMS resin.

[0048] PDMS resin can comprise various PDMS polymers and / or PDMS copolymers (e.g., random copolymers). PDMS resin can comprise one or more polymer chains. The polymer chains can have various structures. The resin can comprise a combination of PDMS polymers and / or PDMS copolymers. In various examples, the PDMS resin comprises one or more poly(dimethylsiloxanes), each poly(dimethylsiloxane) comprising one or more poly(dimethylsiloxane) moieties (e.g., linear or branched poly(dimethylsiloxane) moieties). The moieties can be terminal moieties, such as groups. Optionally, the poly(dimethylsiloxane) independently comprises one or more side groups having the following structure:

[0049] (For example wherein L is a linking group), wherein R, at each occurrence in the poly(dimethylsiloxane), is independently selected from an alkyl group and an -O-SiOR' group, wherein R', at each occurrence in the -O-SiOR' group, is independently selected from an alkyl group (e.g., a methyl group). In various examples, the PDMS resin comprises one or more polymers, each polymer comprising one or more backbones selected from the group consisting of linear or branched poly(dimethylsiloxane), hydrocarbon polymers (e.g., polyethylene, polypropylene, polybutylene, etc.), polyacrylate polymers, poly(methacrylates), poly(styrenes), poly(vinyl esters), poly(allyl ethers), polyesters, polyurethanes, polyureas, polyamides, polyimides, polysulfones, and combinations thereof. Optionally, at least one pendant group has the following structure:

[0050] (For example, wherein L is a linking group), wherein R is independently selected at each occurrence from an alkyl group and a -O-SiOR' group, wherein the R' group is an alkyl group, wherein the layer is disposed on part or all of the outer surface of the substrate. The linking group can be a group comprising an alkyl group, an aryl group, a silyl moiety, and the like, and combinations thereof (e.g., a -CH2- group, a -CH2CH2- group, a -CH2CH2CH2- group, Group, Group, group, -Si(CH3)2O-, -CH2O- group, -CH2CH3O- group, -CH2N- group, -CH2SO2- group, wherein n is 0-40 including all integer values ​​and ranges therebetween). Examples of linking groups are described herein.

[0051] The PDMS resin may comprise a polymer having a molecular weight of 140 g / mol or greater (e.g., 400 g / mol or greater, or 600 g / mol or greater). A polymer molecular weight greater than 140 g / mol (e.g., greater than 400 g / mol, 600 g / mol, 1000 g / mol, 3000 g / mol, or 4000 g / mol) may be required to achieve a desired layer thickness. In one example, the molecular weight is less than or equal to 10,000 g / mol.

[0052] PDMS resin can be side group branched PDMS resin.Side group branched PDMS resin can comprise main chain, and described main chain comprises multiple aliphatic moieties and / or aliphatic groups (for example, alkanediyl / alkenediyl moiety and / or alkanediyl / alkenediyl groups) and multiple side groups (for example, PDMS side groups).In an example, side group branched PDMS resin is the resin formed by the polymerization reaction of one or more alkylsilyl compounds being referred to as precursor (for example, monomer), and described alkylsilyl compounds comprises one or more aliphatic moieties and / or aliphatic groups (for example, alkanediyl / alkenediyl moiety and / or alkanediyl / alkenediyl groups).For example, side group branched PDMS resin is the resin formed by the polymerization of precursor (for example three (trialkylsiloxy) silyl alkyl acrylate) and one or more cross-linked precursors forming side group, and described cross-linked precursor can be cross-linked with substrate (for example, alkyl propylene oxygen base alkyl trialkoxy silane). The crosslinking precursor may be a comonomer having, for example, one or more hydroxyl, silanol, epoxy, carboxyl, aldehyde, amino or isocyanate crosslinkable groups or combinations thereof. A single aliphatic moiety and / or aliphatic group (e.g., an alkanediyl / alkenediyl moiety and / or an alkanediyl / alkenediyl group) is independently present at each occurrence and is comprised of from C1 to C 40 (e.g., C1–C 30 , C1–C 10 or C1-C5) (including all integers of carbon and ranges therebetween). In one example, the side-branched PDMS resin is a resin formed by the polymerization of tris(trimethylsiloxy)silylpropyl methacrylate and vinyltrimethoxysilane. See, for example, Figure 2 The molar ratio of tris(trialkylsiloxy)silylalkylacrylate to alkylacryloxyalkyltrialkoxysilane (e.g., tris(trimethylsiloxy)silylpropylmethacrylate to vinyltrimethoxysilane) is typically greater than 1. In one example, the ratio is 3 to 20.

[0053] Examples of cross-linkable moieties include, but are not limited to:

[0054]

[0055] and combinations thereof, where R 3is a hydrocarbon of 1 to 40 carbons, including all integer carbon values ​​and ranges therebetween (e.g., methylene, ethylene, propylene, phenyl, diphenyl, naphthyl, etc.), n is 0-600, including all values ​​and ranges therebetween, and X is a crosslinkable group including, but not limited to, acrylate, methacrylate, allyl, vinyl, thiol, hydroxyl, silanol, carboxylic acid, aldehyde, amine, isocyanate, azide, alkyne, epoxy, halide, hydrogen, and combinations thereof. In various examples, the crosslinkable moiety is a crosslinkable moiety when one or more crosslinkable groups react (e.g., with a crosslinkable group of a different polymer chain, the same polymer chain, a substrate, or a combination thereof).

[0056] The PDMS resin can be a linear PDMS resin. The linear PDMS resin can comprise a main chain comprising a plurality of PDMS aliphatic moieties and / or aliphatic groups (e.g., alkanediyl / alkenediyl moieties and / or alkanediyl / alkenediyl groups) and optionally a plurality of side groups (e.g., PDMS side groups). For example, the PDMS resin is a linear PDMS resin having a substrate-binding group (e.g., a resin formed by polymerization of PDMS terminated with reactive functional groups (e.g., amine-terminated), a phenol (e.g., bisphenol A), and paraformaldehyde; PDMS terminated with silanol, epoxy, carboxyl, aldehyde, isocyanate, thiol, vinyl, hydrogen, and hydroxyl groups). See, for example, Figure 3 The aliphatic portion and / or aliphatic group (e.g., alkanediyl / alkenediyl portion and / or alkanediyl / alkenediyl group) of the reactive functional group terminated PDMS and / or the PDMS terminated with silanol, epoxy, carboxyl, aldehyde, isocyanate, thiol, vinyl, hydrogen and hydroxyl or a combination thereof can be independently at each occurrence a C1 to C 40 (e.g. C1–C 30 , C1–C 10 In various examples, the repeating units of the PDMS polymer (e.g., R2OSi-) (e.g., Figure 3 In various examples, the number of repeating units is from 0 to 400, including all integers of repeating units and ranges therebetween. In various examples, the number of repeating units in the PDMS polymer (e.g., Figure 3 In various examples, the number of repeating units in the PDMS polymer (e.g., Figure 3 In various examples, the number of repeating units in the PDMS polymer (e.g., Figure 3In various examples, m) is 5-50,000, 5-25,000, or 5-10,000. In various examples, m is 2,000. In various examples, n can be 0-400. In various examples, n is 50.

[0057] Any phenol can be used. Examples of suitable phenols include, but are not limited to, phenols comprising at least two hydroxyl groups and one or more short (e.g., C1 to C5 or C1 to C4) alkyl groups attached to one or more benzene rings or having an aromatic ring (e.g., a hydroxylated C5 to C4) alkyl group. 16 The hydroxyl group is directly attached to an aromatic group / moiety, such as hydroxylated naphthalene, hydroxylated pyrene, hydroxylated anthracene, etc. In one example, the phenol is bisphenol A.

[0058] The film may comprise nanoparticles (e.g., silica nanoparticles). The nanoparticles may be multifunctional nanoparticles. "Multifunctional nanoparticles" refers to nanoparticles having more than one functional group fixed thereto, for example, silanol groups are fixed thereto to improve compatibility with PDMS resin and trimethylsiloxy groups are fixed thereto to reduce surface energy. The silica nanoparticles and the resin and / or substrate may have covalent bonds and / or hydrogen bonds from the surface functional groups of these nanoparticles.

[0059] The nanoparticles can be metal, carbon, metal oxide, or semi-metal oxide (e.g., silica) nanoparticles. The nanoparticles can be surface functionalized with low surface energy groups (e.g., trimethylsiloxy, methyl, tert-butyl, benzoxazine, PDMS groups, etc.). The nanoparticles can have various morphologies. In various examples, the nanoparticles are spherical, nanoplate, nanotube, nanorod, nanowire, a hierarchical structure generated by such nanoparticles, or a combination thereof. In one example, the layer comprises a plurality of silica nanoparticles (e.g., Ludox HS silica, or other commercially available colloidal silica particles). The nanoparticles can be present in various amounts. In various examples, the nanoparticles are present in the layer in an amount of 0–95 wt % based on the total weight of the layer, including all integer wt % values ​​and ranges therebetween. In one example, the nanoparticles are present in the layer in an amount of 20–40 wt %. The interaction between the silica nanoparticles and the resin or fabric / fiber can be in the form of covalent bonds and / or hydrogen bonds involving the surface functional groups of the nanoparticles.

[0060] The layer can be placed on part or all of the outer surface (or all of the outer surface) of the substrate. The substrate can have various sizes and shapes. The substrate can have various compositions. Examples of substrate materials include, but are not limited to, fabrics, fibers, filaments, glass, ceramics, carbon, metals, wood, polymers, plastics, paper, films, concrete, bricks, etc.

[0061] The substrate can be a natural fabric or a fabric modified to be superhydrophilic, hydrophilic, hydrophobic or superhydrophobic. The fabric can be cotton, PET (polyethylene terephthalate), a mixture (e.g., cotton / PET blends, etc.), nylon, polyester, spandex, silk, wool, viscose, cellulose fibers (e.g., ), acrylic, polypropylene, or blends thereof. The fabric may be leather. The fabric may have a woven (e.g., plain, twill, satin weave, etc.), knitted (e.g., single jersey, double jersey, embossed, mesh, etc.), or non-woven (e.g., felt, fiber mattress, membrane, film, leather, paper, etc.) structure.

[0062] The substrate may comprise one or more reentrant structures. Non-limiting examples of reentrant structures include fibrous structures (e.g., non-limiting examples of fibrous structures such as Figure 1 a), T-shaped structures (e.g., non-limiting examples of fiber structures such as Figure 1 b) and derivative structures such as trapezoidal, matchstick, hoodoo-like / inverseopal, and mushroom structures (non-limiting examples of derivative structures are Figure 1 c). The substrate may comprise two or more different (e.g., different in one or more characteristics, such as one or more dimensions, one or more types of reentrant structures, etc.) reentrant structures. For example, Figure 1 As shown, the oleophobic properties of a layer placed on a substrate having these structures can be determined by the capillary length, overhang radius R, microstructure spacing D, and local texture angle ψ. Compared to a fibrous structure, a T-shaped structure can improve oil repellency because it can maximize these parameters simultaneously. In one embodiment, the substrate does not include any reentrant structures.

[0063] The layer can be placed on a fabric having a super-hydrophilic layer, the super-hydrophilic layer being placed on a portion of the outer surface of the fabric. Non-limiting examples of super-hydrophilic layers can be found in U.S. Patent Application No. 14 / 122,535 (Wang et al., "Antifouling Ultrafiltration and RO / FO Membranes"), the disclosure of which is incorporated herein by reference for super-hydrophilic layers and methods of making super-hydrophilic layers. In one example, the layer described in the present disclosure and the super-hydrophilic layer are placed on opposite sides of the fabric.

[0064] The super-hydrophilic layer can comprise a plurality of super-hydrophilic nanoparticles. The hydrophilic nanoparticles are silicon dioxide nanoparticles that have been surface functionalized with an alkylsiloxane linking group. In various examples, the surface of the super-hydrophilic layer has a contact angle less than 30 degrees, 25 degrees, 20 degrees, 15 degrees, 10 degrees or 5 degrees. The super-hydrophilic layer can be formed by nanoparticles prepared by methods known in the art.

[0065] The layer is oleophobic. The layer can be lipophobic and oleophobic. The layer can be lipophobic, oleophobic and hydrophobic. "Oleophobic" means that the molecules exhibit the physical property of being repelled by oil. The oleophobicity or oil repellency of the layer can be determined by In various examples, the layer passed the test for one or more oils (e.g., One or more oils listed in Test Method 118-2013) Test Method 118-2013. Lipophobicity, sometimes also called lipophobia, is a chemical property of a compound that means "repulsion of fat," literally "fear of fat." Lipophobic compounds are insoluble in fats or other non-polar solvents; for example, water is lipophobic.

[0066] In one aspect, the present application provides methods for making the layers described herein. In various embodiments, the methods are based on coating a PDMS resin onto a substrate, which can be referred to as a graft-to method. In various other embodiments, the PDMS resin is formed by in situ polymerization, which can be referred to as a graft-from method.

[0067] In various examples, a method of forming a layer (e.g., a molecularly rough layer) disposed on a portion or all of an outer surface (e.g., the entire outer surface) of a substrate (e.g., a substrate described herein, such as a textile fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, etc.), the layer having a kinetic energy of less than or equal to 22 mJ / m 2 The surface tension (e.g., containing cured PDMS resin) is less than 22 mJ / m 2 The method comprises: providing a substrate (e.g., a fabric); coating (e.g., by dipping or spraying) a portion or all of a surface (e.g., a portion or all of an outer surface) of the substrate (e.g., a fabric) with a PDMS resin (e.g., a side-group branched PDMS resin or a linear PDMS resin) (e.g., a PDMS resin described herein); and curing (e.g., thermally curing) the PDMS resin coating, wherein a surface tension of less than or equal to 22 mJ / m is formed on a portion or all of a surface (e.g., a portion or all of an outer surface) of the substrate (e.g., a fabric). 2(For example, less than 22mJ / m 2 ) layer (e.g., a molecular rough layer).

[0068] Curing can result in crosslinking (e.g., forming one or more covalent bonds) between one or more polymer chains of the layer and / or between one or more polymer chains and the substrate. Crosslinking can form crosslinked moieties (e.g., forming crosslinked moieties by reaction of one or more crosslinkable moieties).

[0069] Various coating methods can be used. Examples of coating methods include, but are not limited to, spraying, dipping, floating knife coating, direct roller coating, filling, calendar coating, foam coating, and painting.

[0070] The PDMS resin can be (e.g., contain) a mixture of nanoparticles, PDMS resin, and optionally a solvent. Such a resin can be referred to as a "composite nanofluid." In various embodiments, a substrate is coated with the composite nanofluid. Nanoparticles are believed to increase the surface roughness of a layer. In addition, nanoparticles can enhance the mechanical durability and strength of a layer (e.g., a fabric having a layer disposed on at least a portion or all of its outer surface (e.g., its entire outer surface)).

[0071] One or more layers can be formed by in situ polymerization. For example, the layer is grown by polymerization initiated by a substrate (e.g., one or more groups placed on the substrate). For example, the polymerization is free radical polymerization. In various examples, the free radical polymerization is an active polymerization, for example, atom transfer radical polymerization (ATRP).

[0072] Examples of in situ polymerization include contacting a substrate comprising a plurality of functional groups capable of initiating polymerization of a methylsiloxane precursor (e.g., comprising one or more functional groups disposed on its surface) with a reaction mixture. groups, etc. or combinations thereof), the reaction mixture comprises one or more methylsiloxane precursors, and

[0073] (i) one or more free radical initiators (e.g., halide initiators such as Azo free radical initiators, such as azobisisobutyronitrile (AIBN); peroxides, such as benzoyl peroxide; alkoxyamines, such as 2,2,6,6-tetramethylpiperidin-1-yl)oxy; chain transfer agents, such as cyanomethyl [3-(trimethoxysilyl)propyl] trithiocarbonate, etc., or combinations thereof); or

[0074] (ii) one or more activators, the activators comprising one or more metal catalysts (e.g., Cu(I), Cu(II), Fe(II), Fe(III), Co(II), etc., and combinations thereof) and one or more amines (e.g., diethylenetriamine, triethylenetetramine, N,N-bis(2-pyridylmethyl)amine, tris[2-aminoethyl]amine, 1,4,8,11-tetraazacyclotetradecane, 2,2′-bipyridine, 4,4′-di(5-nonyl)-2,2′-bipyridine, N,N,N′,N′-tetramethylethylenediamine, N-propyl(2-pyridyl)methylamine, 2,2′:6′,2″-tripyridine, 4, 4',4"-tris(5-nonyl)-2,2':6',2"-tripyridine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N-bis(2-pyridylmethyl)octylamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris[2-(dimethylamino)ethyl]amine, tris[(2-pyridyl)methyl]amine, 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, etc., and combinations thereof), wherein a layer comprising an initiator layer and / or a poly(dimethylsiloxane) layer is formed, and the layer is disposed on the surface of the substrate.

[0075] The substrate may be pretreated prior to coating. In one example, nanoparticles are deposited and / or grown on part or all of the outer surface (e.g., the entire outer surface) of the substrate. In various examples, the method includes forming a layer comprising a plurality of nanoparticles on all or part or all of the outer surface (e.g., the entire outer surface) of the fabric prior to forming the layer described herein. In various examples, the forming comprises coating (e.g., by dipping or spraying) part or all of the outer surface of the fabric with a silica sol (e.g., a silica sol formed by hydrolyzing one or more tetraalkoxysilanes (e.g., in an alcohol / water solution) (e.g., under alkaline conditions) and drying the coated fabric. Combinations of tetraalkoxysilanes may be used. Examples of tetraalkoxysilanes include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropyl orthosilicate, tetrabutyl orthosilicate, and combinations thereof. The silica sol may also be formed by acidifying sodium silicate.

[0076] In one example, a method comprising pretreating a substrate further comprises contacting the dry fabric with silica nanoparticles (eg, a suspension of silica nanoparticles).

[0077] The substrate can be cleaned before use. In one example, the substrate (e.g., a fabric or a fabric having a plurality of nanoparticles disposed thereon) is cleaned (e.g., plasma cleaned, oxidized, rinsed with a solvent (e.g., water) and / or other solvent (e.g., an organic solvent)) before coating with the silica sol.

[0078] The coating and curing can be repeated as many times as desired. Repeated coating and curing may be required to provide a layer with a desired thickness. In various examples, the coating and curing are repeated 1 to 20 times, including all integers repeated therebetween.

[0079] In various examples, the method further comprises forming additional surface roughness on the film.The surface roughness can be formed by, for example, nanofabrication, electrospinning, forced spinning, extrusion, mechanical stamping, abrasion, etching, or a combination thereof.

[0080] In one aspect, the present application provides an article comprising one or more layers described herein and / or one or more layers made by the method of the present application.

[0081] Examples of articles include, but are not limited to, textiles, clothing (such as clothing, e.g., children's clothing, adult clothing, industrial workwear, etc.) such as shirts, jackets, pants, hats, ties, coats, shoes, etc., food packaging, eyeglasses, displays (e.g., touch screens), scanners (e.g., fingerprint scanners), aircraft coatings, sporting goods (e.g., tents, uniforms, etc.), building materials (e.g., windows), windshields.

[0082] The articles can be used in a variety of industries. Examples of industries include, but are not limited to, aerospace, automotive, building and construction, food processing, and electronics.

[0083] The steps of the methods described in the various embodiments and examples disclosed herein are sufficient to perform the methods described herein. Thus, in various examples, the methods are essentially composed of a combination of the steps of the methods disclosed herein. In various other examples, the methods are composed of such steps.

[0084] The following statements provide embodiments and / or examples of layers described herein (e.g., having a strength of less than or equal to 22 mJ / m 2 (e.g. 12-22 mJ / m 2 ), methods described herein (e.g., methods of making layers described herein), and articles described herein (e.g., articles comprising one or more layers described herein):

[0085] Statement 1. A layer (e.g., a molecularly rough layer) according to the present disclosure has a strength of less than or equal to 22 mJ / m 2 (e.g., 12–22 mJ / m 2 ) and is placed on part or all of the outer surface (e.g., the entire outer surface) of the substrate.

[0086] Statement 2. A layer (e.g., a layer disposed on a substrate) comprising one or more PDMS resins, each PDMS resin comprising:

[0087] i) one or more poly(dimethylsiloxanes), each poly(dimethylsiloxane) comprising one or more poly(dimethylsiloxane) moieties (e.g., linear or branched poly(dimethylsiloxane) moieties), and

[0088] Optionally, the poly(dimethylsiloxane) independently comprises one or more pendant groups having the structure:

[0089] (For example, Wherein L is a linking group, wherein the linking group can be a group comprising an alkyl group, an aryl group, a silyl moiety, and the like and combinations thereof (e.g., a -CH2- group, a -CH2CH2- group, a -CH2CH2CH2- group, Group, Group, groups, -Si(CH3)2O-, -CH2O- groups, -CH2CH3O- groups, -CH2N- groups, -CH2SO2- groups, wherein n is 0-40 including all integer values ​​and ranges therebetween)), wherein R, at each occurrence in the poly(dimethylsiloxane), is independently selected from alkyl groups and -O-SiOR' groups, wherein R', at each occurrence in the -O-SiOR' group, is independently selected from alkyl groups (e.g., methyl);

[0090] and / or

[0091] ii) one or more polymers, each polymer comprising:

[0092] one or more backbones selected from the group consisting of linear or branched poly(dimethylsiloxane), hydrocarbon polymers (e.g., polyethylene, polypropylene, polybutylene, etc.), polyacrylate polymers, poly(methacrylate), poly(styrene), poly(vinyl ester), poly(allyl ether), polyester, polyurethane, polyurea, polyamide, polyimide, polysulfone, and combinations thereof, and

[0093] Optionally, at least one side group having the structure:

[0094] (For example Wherein L is a linking group, wherein the linking group can be a group comprising an alkyl group, an aryl group, a silyl moiety, and the like, and combinations thereof (e.g., a -CH2- group, a -CH2CH2- group, a -CH2CH2CH2- group, Group, Group, groups, -Si(CH3)2O-, -CH2O-, -CH2CH3O-, -CH2N-, -CH2SO2-, where n is from 0 to 40, including all integer values and the ranges therebetween)), where R is independently selected from alkyl and -O-SiOR' groups each time it appears, where the R' group is an alkyl group, and where the layer is placed on part or all of the surface of the substrate.

[0095] Statement 3. The layer according to statement 2, wherein the one or more poly(dimethylsiloxanes) comprise a linear poly(dimethylsiloxane) portion, a branched poly(dimethylsiloxane) portion, or a combination thereof.

[0096] Statement 4. The layer according to any one of the foregoing statements, wherein the PDMS resin is a linear PDMS resin (e.g., a PDMS resin with a group binding to the substrate) (e.g., a resin formed by polymerization of amine-terminated PDMS, phenol, and paraformaldehyde, the phenol having a hydroxyl group and a short alkyl group attached to the benzene ring (<C5) or a hydroxyl group directly attached to an aromatic ring (such as bisphenol A); PDMS terminated with silanol, epoxy, carboxyl, aldehyde, isocyanate, thiol, vinyl, hydrogen, hydroxyl, or a combination thereof). See, for example, Figure 3 . For example, the alkyl portion of an amine-terminated PDMS precursor or PDMS terminated with silanol, epoxy, carboxyl, aldehyde, isocyanate, thiol, vinyl, hydrogen, hydroxyl, or a combination thereof is independently C1 to C 40 , including all integers of carbon and the ranges therebetween (e.g., C1 to C 30 , C1 to C 10 , or C1 to C5).

[0097] Statement 5. The layer according to any one of statements 2 - 4, wherein the one or more poly(dimethylsiloxanes) are: where R 2 is independently selected from H, a hydrocarbon group having 1 to 40 carbons, or -O-SiOR' groups each time it appears, where the R' group is an alkyl group (e.g., C1 to C 40 , C1 to C 30 , C1 to C 10 , or C1 to C5); and n is 0–400 and m is 1–50,000.

[0098] Statement 6. The layer according to any one of statements 2 - 6, wherein at least one of the one or more poly(dimethylsiloxanes) or a linear or branched poly(dimethylsiloxane) has one or more crosslinkable groups.

[0099] Statement 7. A layer according to any of Statements 2-6, wherein the crosslinkable group is selected from acrylate, methacrylate, allyl, vinyl, thiol, hydroxyl, silanol, carboxylic acid, aldehyde, amine, isocyanate, azide, alkyne, epoxy, halide, hydrogen, and combinations thereof.

[0100] Statement 8. A layer according to any one of Statements 2-7, wherein the side-branched PDMS is formed by polymerization of one or more tris(trialkylsiloxy)silylvinyl compounds (e.g., tris(trialkylsiloxy)silylalkylacrylates, such as tris(trialkylsiloxy)silylmethacrylate, etc.) and trimethoxysilanevinyl compounds (e.g., alkylacryloxyalkoxytrimethoxysilane, etc.), wherein the alkyl moiety (e.g., the alkyl moiety and / or the alkyl group) is independently C1 to C2 at each occurrence. 40 Alkyl moiety. See, for example, Figure 2 .

[0101] Statement 9. A layer according to any of Statements 2-8, wherein the molar ratio of tris(trialkylsiloxy)silylalkyl acrylate to vinyl silane (e.g., tris(trimethylsiloxy)silylpropyl methacrylate to vinyltrimethoxysilane) used to produce the PDMS resin or a portion of the PDMS resin derived from these precursors is higher than 1 (e.g., 3-20).

[0102] Statement 10. A layer according to any one of Statements 2-9, wherein each occurrence of said alkyl moiety is independently C1 to C 30 , C1 to C 10 an alkyl moiety or a C1 to C5 alkyl moiety.

[0103] Statement 11. A layer according to any one of Statements 2-10, wherein the pendant groups are selected from:

[0104]

[0105] And optionally, the pendant groups are covalently bonded to the poly(dimethylsiloxane) resin or backbone via a linking group.

[0106] Statement 12. A layer according to any of Statements 2-11, wherein the poly(dimethylsiloxane) has the following structure:

[0107]

[0108] wherein n is 0-600, m is 0-3, and X is a crosslinkable group including, but not limited to, acrylate, methacrylate, allyl, vinyl, thiol, hydroxyl, silanol, carboxylic acid, aldehyde, amine, isocyanate, azide, alkyne, epoxy, halide, hydrogen, and combinations thereof.

[0109] Statement 13. A layer according to any of Statements 2-12, wherein the number of R2OSi (e.g., C2H6OSi) repeat units of the one or more poly(dimethylsiloxane) moieties or the linear or branched poly(dimethylsiloxane) backbone is from 0 to 400.

[0110] Statement 14. A layer according to any one of Statements 2 to 13, wherein the number of repeating units of the PDMS (e.g., C2H6OSi) is greater than 2, preferably 10 to 400. In addition to grafting into the backbone (graft-to) method (e.g., dip coating, spray coating, emulsion / foam coating, etc.), it can also be grafted from the backbone (graft-from) method (e.g., Figure 9 The coating is applied to the substrate as shown. The initiator can be a reversibly deactivated free radical generator, such as a compound containing one or more organic halide moieties (e.g., alkyl halides), or one or more alkoxyamine moieties, or a suitable chain transfer agent, such as one or more thiocarbonylthio moieties. The monomer can be one or more alkylsilyl compounds containing one or more aliphatic moieties and / or aliphatic groups.

[0111] Statement 15. The layer of any one of Statements 2-14, wherein said layer is cured.

[0112] Statement 16. A layer according to any of Statements 2-15, wherein the layer further comprises at least one cross-link (e.g., more than 2, more than 5, more than 10 cross-links, or more than 25 cross-links) between two polymer chains of the PDMS resin (which can be the same or different polymer chains of the PDMS resin), and / or at least one cross-link (e.g., more than 2, more than 5, more than 10 cross-links, or more than 25 cross-links) between a polymer chain of the PDMS resin (which can be the same or different polymer chains of the PDMS resin) and a substrate.

[0113] Statement 17. A layer according to any one of Statements 2-16, wherein said layer further comprises one or more cross-linking moieties selected from:

[0114]

[0115] and combinations thereof, where R 3is a hydrocarbyl group having from 1 to 40 carbons, including all integer carbon values ​​and ranges therebetween (eg, methylene, ethylene, propylene, phenyl, biphenyl, naphthyl, etc.), and wherein n is 0-600, including all values ​​and ranges therebetween.

[0116] Statement 18. The layer of any one of Statements 2-17, wherein said layer comprises a plurality of nanoparticles disclosed herein (eg, silica nanoparticles such as Ludox HS silica and other commercially available colloidal silica particles).

[0117] Statement 19. The layer of Statement 18, wherein said plurality of nanoparticles is selected from the group consisting of silica nanoparticles.

[0118] Statement 20. The layer of any of Statements 18 or 19, wherein the weight percentage of the nanoparticles is 1-98 wt% (eg, 1-95 wt% or 1-50 wt%) based on the total weight of the layer.

[0119] Statement 21. The layer according to any one of Statements 18-20, wherein the weight percentage of the nanoparticles can be 0-95 wt%, preferably 20-40 wt%.

[0120] Statement 22. A layer according to any of the preceding statements, wherein said substrate is a substrate disclosed herein.

[0121] Statement 23. A layer according to any of the preceding statements, wherein said layer has a thickness of 10 nm - 300 microns (eg, 50 nm - 100 microns).

[0122] Statement 24. A layer according to any of the preceding statements, wherein said substrate is a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, or the like.

[0123] Statement 25. A layer according to statement 24, wherein the fabric is selected from the group consisting of cotton, PET, cotton / PET blends, nylon, polyester, spandex, silk, wool, viscose, cellulosic fibers, acrylic, polypropylene, blends thereof (e.g., a blend of two or more yarns that can be formed into a fabric, including cotton, PET, cotton / PET blends, nylon, polyester, spandex, silk, wool, viscose, cellulosic fibers, acrylic, polypropylene yarns used as the fabric material), leather, and combinations thereof.

[0124] Statement 26. The layer of Statement 25, wherein said substrate is a fabric having a superhydrophilic layer disposed on a portion of an outer surface of said fabric.

[0125] Statement 27. A layer according to any one of Statements 2-26, wherein said layer exhibits less than or equal to 22 mJ / m 2 surface tension.

[0126] Statement 28. A layer according to any one of Statements 2-27, wherein the layer has a value less than or equal to 22 mJ / m 2 The surface tension layer and the super hydrophilic layer are placed on opposite sides of the fabric.

[0127] Statement 29. A layer according to any of the preceding statements, wherein said substrate and / or layer is fluorine-free.

[0128] Statement 30. A layer according to any of the preceding statements, wherein said layer has been subjected to Test Act 118-2013 (e.g., one or more oils listed in Test Method 118-2013).

[0129] Statement 31. A method of forming the present disclosure (e.g., having less than 22 mJ / m 2 A method for forming a layer (e.g., a molecularly rough layer) (e.g., a layer comprising a cured PDMS resin) disposed on a portion or all of an outer surface (e.g., the entire outer surface) of a substrate (e.g., a fabric), the method comprising:

[0130] providing the substrate (e.g., the fabric);

[0131] coating (e.g., by spraying, dipping, floating knife coating, direct roller coating, filling, calendar coating, or foam coating) a portion or all of the outer surface (e.g., the entire outer surface) of the substrate with a PDMS resin (e.g., a side-group branched PDMS resin or a linear PDMS resin) (e.g., a PDMS resin disclosed herein, e.g., the PDMS resin of any of Statements 4-13) or a composite nanofluid;

[0132] The PDMS resin coating or the coating formed by the composite nanofluid is cured (e.g., thermally cured), wherein the layer (e.g., molecular rough layer) described in the present disclosure is formed on a portion or the entire outer surface (e.g., the entire outer surface) of the substrate (e.g., the surface tension is less than 22 mJ / m 2 layer).

[0133] Statement 32. A method of forming a layer of the present disclosure disposed on part or all of an outer surface of a substrate, the method comprising:

[0134] coating part or all of the outer surface of the substrate with a poly(dimethylsiloxane) (PDMS) resin or a composite nanofluid; and

[0135] The PDMS resin coating or the coating formed of the composite nanofluid is cured at a temperature (e.g., maintaining the coating at a temperature of -30 to 200° C., such as 20 to 160° C., for example, for 1 second to 2 weeks) and heating the coating, wherein the layer described in the present disclosure is formed on part or all of the outer surface of the substrate.

[0136] Statement 33. The method of any one of Statements 31 or 32, wherein said PDMS resin comprises:

[0137] i) one or more poly(dimethylsiloxane) resins comprising one or more poly(dimethylsiloxane) moieties (e.g., linear or branched poly(dimethylsiloxane) moieties),

[0138] Wherein, optionally, the poly(dimethylsiloxane) resin comprises one or more side groups having the following structure:

[0139] (For example, wherein L is a linking group), wherein R, at each occurrence in the poly(dimethylsiloxane), is independently selected from an alkyl group and an -O-SiOR' group, wherein R', at each occurrence in the -O-SiOR' group, is independently selected from an alkyl group (e.g., a methyl group);

[0140] and / or

[0141] ii) comprising one or more polymers comprising:

[0142] a backbone selected from the group consisting of linear or branched poly(dimethylsiloxane), hydrocarbon polymers (e.g., polyethylene, polypropylene, polybutylene, etc.), polyacrylate polymers, poly(methacrylate), poly(styrene), poly(vinyl ester), poly(allyl ether), polyester, polyurethane, polyurea, polyamide, polyimide, polysulfone, and combinations thereof, and

[0143] At least one side group having the following structure:

[0144] (For example, wherein L is a linking group), wherein R at each occurrence is independently selected from an alkyl group and a -O-SiOR' group, wherein the R' group is an alkyl group.

[0145] Statement 34. The method of any one of Statements 31-33, wherein the composite nanofluid comprises PDMS resin, one or more nanoparticles, and optionally, a solvent (e.g., toluene, xylene, a hydrocarbon containing 4 to 16 carbons, such as hexane), chloroform, tetrahydrofuran, and combinations thereof.

[0146] Statement 35. The method of any one of Statements 31-34, wherein the substrate is a substrate disclosed herein.

[0147] Statement 36. The method of any one of Statements 31-35, wherein said substrate is a fabric, a fiber, a filament, a glass, a ceramic, carbon, a metal, a wood, a polymer, a plastic, a paper, a film, concrete, a brick, or the like.

[0148] Statement 37. The method of any one of Statements 31-36, wherein the substrate is a fabric having a superhydrophilic layer disposed on all or at least a portion of the outer surface of the fabric (e.g., adjacent to a surface formed with a layer of the present disclosure (e.g., having a hydrophilicity of less than or equal to 22 mJ / m 2 The surface tension of the layer) is on one side opposite to the fabric side).

[0149] Statement 38. The method of any one of Statements 31-37, wherein said substrate is fluorine-free.

[0150] Statement 39. The method of any one of Statements 31-38, wherein said forming comprises coating (e.g., by dipping or spraying) part or all of the outer surface of said substrate with a silica sol (e.g., a silica sol formed by hydrolyzing (e.g., under alkaline conditions) one or more tetraalkoxysilanes (e.g., in an alcohol / water solution) and drying said coated fabric. Examples of tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropylorthosilicate, tetrabutylorthosilicate, and combinations thereof. Silica sol can also be formed by acidifying sodium silicate.

[0151] Statement 40. The method of Statement 39, wherein said coating is spray coating, dip coating, floating knife coating, direct roller coating, filling, calendar coating, foam coating, or a combination thereof.

[0152] Statement 41. The method of any one of Statements 31-40, further comprising contacting the dry substrate with nanoparticles (eg, silica nanoparticles, eg, a suspension of silica nanoparticles).

[0153] Statement 42. The method of any one of Statements 31-41 further comprising pretreating the substrate.

[0154] Statement 43. The method of any one of Statements 31-42, comprising forming a layer of the present disclosure (e.g., having a 2 Before forming a layer having a surface tension greater than 0.05 mm / s, a layer is formed on all or part of or all of the outer surface (e.g., the entire outer surface) of the substrate.

[0155] Statement 44. A method according to any one of Statements 31-43, wherein the pretreatment is a chemical treatment (e.g., plasma treatment, solvent cleaning, oxidation treatment, hydrolysis treatment, etc. and combinations thereof), a physical treatment (e.g., sanding treatment, etc.), a primer treatment (e.g., using a primer, such as a sol, the sol containing one or more sol-gel precursors and an epoxy primer, containing one or more acrylate groups, methacrylate groups, allyl groups, vinyl groups, thiol groups, hydroxyl groups, silanol groups, carboxylic acid groups, carboxylate groups, aldehyde groups, amine groups, isocyanate groups, azide groups, epoxy groups, halide groups, hydrogen groups, etc. and combinations thereof), or a combination thereof.

[0156] Statement 45. The method of any one of Statements 31-44, wherein said pretreatment comprises coating a portion or all of the outer surface of said substrate with a non-metallic oxide (e.g., silicon oxide, etc.), a metal oxide (e.g., aluminum oxide, titanium oxide, iron oxide, copper oxide, etc., and combinations thereof), or a combination thereof (e.g., a layer comprising a non-metallic oxide, a metal oxide, or a combination thereof). For example, the coated substrate (e.g., a silica sol-coated substrate) comprises one or more functional groups, such as acrylate groups, methacrylate groups, allyl groups, vinyl groups, thiol groups, hydroxyl groups, silanol groups, carboxylic acid groups, carboxylate groups, aldehyde groups, amine groups, isocyanate groups, azide groups, alkynyl groups, epoxy groups, halide groups, hydride groups, and combinations thereof, which can increase the crosslink density between the coated substrate and said layer.

[0157] Statement 46. The method of any one of Statements 31-45, wherein said substrate is cleaned (eg, plasma cleaned) prior to coating with said silica sol.

[0158] Statement 47. The method of any one of Statements 31-46, wherein said substrate has a plurality of nanoparticles disposed thereon.

[0159] Statement 48. The method of any one of Statements 31-47, further comprising contacting said substrate (e.g., which may comprise a dried and / or cured layer) with silica nanoparticles. Some or all of said nanoparticles (e.g., silica nanoparticles, etc.) may be covalently attached to said substrate, bound to and / or aggregated with other nanoparticles, or a combination thereof. In various instances, some or all of said nanoparticles form reentrant structures.

[0160] Statement 49. The method of any one of Statements 31-48, wherein the coating and curing (eg, the coating and curing of any one of Statements 8-16) are repeated a desired number of times (eg, 1-20 times).

[0161] Statement 50. The method of any one of Statements 31-49, further comprising adding additional surface roughness to said layer (eg, by nanofabrication, electrospinning, forced spinning, extrusion, mechanical stamping, abrasion, etching, or a combination thereof).

[0162] Statement 51. A method (e.g., an in situ method) of forming a layer comprising poly(dimethylsiloxane) disposed on part or all of an outer surface of a substrate (e.g., a layer of the present disclosure), the method comprising:

[0163] A substrate comprising a plurality of functional groups capable of initiating polymerization of a dimethylsiloxane precursor (e.g., comprising one or more functional groups disposed on its surface) is contacted with the reaction mixture. groups, etc., or a combination thereof), the reaction mixture comprises one or more dimethylsiloxane precursors, and

[0164] (i) one or more free radical initiators (e.g., halide initiators such as Azo free radical initiators, such as azobisisobutyronitrile (AIBN); peroxides, such as benzoyl peroxide; alkoxyamines, such as 2,2,6,6-tetramethylpiperidin-1-yl)oxy; chain transfer agents, such as cyanomethyl [3-(trimethoxysilyl)propyl] trithiocarbonate, etc., or combinations thereof); or

[0165] (ii) one or more activators, the activators comprising one or more metal catalysts (e.g., Cu(I), Cu(II), Fe(II), Fe(III), Co(II), and the like, and combinations thereof) and one or more amines (e.g., diethylenetriamine, triethylenetetramine, N,N-bis(2-pyridylmethyl)amine, tris[2-aminoethyl]amine, 1,4,8,11-tetraazacyclotetradecane, 2,2′-bipyridine, 4,4′-di(5-nonyl)-2,2′-bipyridine, N,N,N′,N′-tetramethylethylenediamine, N-propyl(2-pyridyl)methylamine, 2,2′:6′,2″-tris(2-pyridyl)amine, Pyridine, 4,4',4"-tris(5-nonyl)-2,2':6',2"-tripyridine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N-bis(2-pyridylmethyl)octylamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris[2-(dimethylamino)ethyl]amine, tris[(2-pyridyl)methyl]amine, 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, and the like, and combinations thereof), wherein a layer comprising a poly(dimethylsiloxane) layer disposed on a surface of the substrate is formed.

[0166] Statement 52. The method of Statement 51, wherein said substrate is a fabric, fiber, filament, glass, ceramic, carbon, metal, wood, polymer, plastic, paper, film, concrete, brick, or the like.

[0167] Statement 53. The method of any one of Statements 51 or 52, wherein said substrate has a plurality of nanoparticles disposed thereon.

[0168] Statement 54. The method of any one of Statements 51-53, wherein said substrate is fluorine-free.

[0169] Statement 55. The method of any one of Statements 51-54, further comprising pretreating the substrate.

[0170] Statement 56. A method according to any one of Statements 51-55, wherein the pretreatment is a chemical treatment (e.g., plasma treatment, solvent cleaning, oxidation treatment, hydrolysis treatment, etc. and combinations thereof), a physical treatment (e.g., sanding treatment, etc.), a primer treatment (e.g., using a primer, such as a sol, the sol containing one or more sol-gel precursors and an epoxy primer, containing one or more acrylate groups, methacrylate groups, allyl groups, vinyl groups, thiol groups, hydroxyl groups, silanol groups, carboxylic acid groups, carboxylate groups, aldehyde groups, amine groups, isocyanate groups, azide groups, alkynyl groups, epoxy groups, halide groups, hydrogen groups, etc. and combinations thereof), or a combination thereof.

[0171] Statement 57. The method of any one of Statements 51-56, wherein the pretreatment comprises coating a portion or all of the outer surface of the substrate with a non-metallic oxide (e.g., silicon oxide, etc.), a metal oxide (e.g., aluminum oxide, titanium oxide, iron oxide, copper oxide, etc., and combinations thereof), or a combination thereof (e.g., a layer comprising a non-metallic oxide, a metal oxide, or a combination thereof). For example, the coated substrate (e.g., a silica sol-coated substrate) comprises one or more functional groups, such as acrylate groups, methacrylate groups, allyl groups, vinyl groups, thiol groups, hydroxyl groups, silanol groups, carboxylic acid groups, carboxylate groups, aldehyde groups, amine groups, isocyanate groups, azide groups, alkynyl groups, epoxy groups, halide groups, hydrogen groups, and combinations thereof, which can increase the crosslink density between the coated substrate and the layer.

[0172] Statement 58. The method of any of Statements 51-57, further comprising contacting the substrate with silica nanoparticles, wherein the substrate can comprise poly(dimethylsiloxane). Some or all of the nanoparticles (e.g., silica nanoparticles, etc.) can be covalently attached to the substrate, combined with and / or aggregated with other nanoparticles, or a combination thereof. In various examples, some or all of the nanoparticles form reentrant structures.

[0173] Statement 59. The method of any one of Statements 51-58, wherein said contacting is repeated 1-20 times.

[0174] Statement 60. The method of any of Statements 51-59, further comprising adding additional surface roughness to said layer.

[0175] Statement 61. The method of any one of Statements 51-60, wherein additional surface roughness is added to said layer by nanofabrication, electrospinning, forced spinning, extrusion, mechanical stamping, abrasion, etching, or a combination thereof.

[0176] Statement 62. An article comprising one or more layers described herein, such as, for example, one or more layers formed by the method of any one of Statements 31-61.

[0177] Statement 63. An article comprising one or more fabrics comprising a layer (e.g., a molecularly rough layer) as described herein disposed on part or all of the outer surface (e.g., the entire outer surface) of a substrate disclosed herein (e.g., having a molecular roughness of less than 22 mJ / m 2 a layer having a surface tension of 0.05 μm) (e.g., a layer of any one of Statements 1-30 or a layer made by the method of any one of Statements 31-61).

[0178] Statement 64. The article of any one of Statements 62 or 63, wherein said article is an article described herein.

[0179] Statement 65. The article of any one of Statements 62-64, wherein the article is a textile, clothing, food packaging, eyeglasses, a display, a scanner, an aircraft coating, sporting goods, a building material, a window, a windshield, a corrosion-resistant coating, an anti-icing coating, or a cooler (e.g., a condenser for cooling vapor such as water vapor), a lamp (e.g., a traffic light, a headlight, a desk lamp, etc.).

[0180] The following examples are presented to illustrate the present disclosure. They are not intended to be limiting in any way.

[0181] Example 1

[0182] This example provides a description of the films described herein.

[0183] Methods and Results: We describe fluorine-free oleophobic coatings based on molecularly roughened PDMS surfaces. In some formulations, surface roughness is achieved by adding nanoparticles. Surface energies equal to or less than 18 mN / m are shown, which results in a 118 with up to a Class 3 oleophobic surface. The coating is robust enough to withstand repeated wash / rinse cycles (30 cycles) and treatment with various organic solvents (e.g., acetone, ethanol, etc.).

[0184] Synthesis of PDMS resin

[0185] Two different PDMS-based resins were synthesized:

[0186] Side-branched PDMS resin (shown in Figure 2 Schematic diagram: Tris(trimethylsiloxy)silylpropyl acrylate (10 mmol), vinyltrimethoxysilane (1 mmol), and azobisisobutyronitrile (0.1 mmol) were dissolved in dry xylene (20 mL) at room temperature and purged with N2 for 5 minutes. The monomer solution was then heated to 65°C and maintained at this temperature for 24 hours.

[0187] Linear PDMS resin ( Figure 3 ): In a 500 mL round-bottom flask, amine-terminated PDMS (10 mmol), bisphenol A (10 mmol), and paraformaldehyde (40 mmol) were dissolved in 150 mL of chloroform. The mixture was heated under reflux for 6 hours to obtain a clear, light yellow solution. After removing the solvent in vacuo, the viscous residue was dissolved in dichloromethane and washed five times with saturated aqueous NaHCO3 and distilled water. The washed solution was dried under vacuum to obtain a viscous, light yellow liquid product.

[0188] Fabric pretreatment

[0189] 1 cm x 1 cm cotton or PET fabrics were washed with ethanol and dried in an oven at 80°C for 10 minutes. Separately, a silica sol was prepared by alkaline hydrolysis of tetraethoxysilane (10 mmol) in an ethanol / water solution (75 mL, 80% v / v) in the presence of ammonium hydroxide (2.75 mL). The fabrics were plasma cleaned, then immersed in the sol for 5 minutes and dried at room temperature. This process was repeated three times. Finally, the fabrics were immersed in a suspension of Ludox HS silica (~5 wt.%) and then dried in an oven at 80°C overnight.

[0190] Manufacturing of fluorine-free oleophobic fabric

[0191] At room temperature, the PDMS resin synthesized above was used to coat the substrate by dip coating or spray coating ( Figure 4 ), a thin layer of fluorine-free oleophobic coating was applied to the pretreated fabric. The cotton fabric was coated three times and then dried in an oven at 100°C overnight. An oleophobic PET fabric was prepared in the same manner, except that the coating was cured at 200°C for 1 hour.

[0192] Example 2

[0193] This example provides a description of the films described herein.

[0194] Figure 7 Examples of branched side group PDMS resins are provided. The PDMS resin comprises a PDMS polymer having a PDMS backbone. The PDMS polymer can be formed using a multifunctional precursor (e.g., a bifunctional precursor having at least two acrylate groups). The PDMS resin can be colorless.

[0195] Figure 8 Examples of PDMS resins are provided. PDMS resins provide examples of branched side group PDMS resins. PDMS resins comprise PDMS polymers having a PDMS backbone and PDMS side chains. PDMS polymers can be formed using multifunctional precursors (e.g., precursors having at least three vinyl groups).

[0196] Example 3

[0197] This embodiment provides a method for forming the layers described in this application.

[0198] In addition to graft-to methods (e.g., dip coating, spray coating, emulsion / foam coating, etc.), the coating can also be applied to the substrate by graft-from methods (e.g., Figure 9 As shown). The initiator can be a reversibly deactivated free radical generator, such as a compound containing one or more organic halide moieties (e.g., alkyl halides), or one or more alkoxyamine moieties, or a suitable chain transfer agent, such as one or more thiocarbonylthio moieties. The monomer can be one or more alkylsilyl compounds containing one or more aliphatic moieties and / or aliphatic groups. Alkyl halides are effective in initiating polymerization reactions.

[0199] A method for oleophobic coating by grafting from a backbone chain via atom-transfer radical polymerization (ATRP).

[0200] A synthetic example: First, a cleaned fabric sample ( Inches) and then dried under N2. The dried fabric was soaked in 30 mL of tetrahydrofuran (THF) solution of 2-bromo-2-methylpropionyl bromide (2 mmol), trimethylamine (1 mmol) and a catalytic amount of 4-dimethylaminopyridine at room temperature for 24 hours, followed by rinsing with THF and ethanol. The fabric functionalized with the ATRP initiator was then soaked in a DMF solution of alkylsilyl monomer, CuBr and N,N',N",N"-pentamethyldiethylenetriamine for 24 hours, with a molar ratio of CuBr / PMDETA of 0.5-1. The coated fabric obtained was then washed with THF and dried to produce a fabric with an oleophobic coating.

[0201] The SEM images of the original and oleophobic fabrics are shown in Figure 10 A uniform coating on the fabric surface was observed. Figure 11 Photos of oleophobic fabrics made from different materials can be seen in the .

[0202] While the present disclosure has been shown and described with reference to particular embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as described herein.

Claims

1. An article comprising one or more fabrics comprising a layer disposed on part or all of an outer surface of the fabric, wherein the layer has a strength of less than or equal to 22 mJ / m 2 The surface tension of the layer comprises one or more PDMS resins, each PDMS resin comprising one or more polymers, each polymer comprising: One or more backbones selected from the group consisting of: poly(dimethylsiloxane), and A plurality of side groups, the plurality of side groups being covalently bonded to the main chain via a linking group, wherein at least a portion of the plurality of side groups has the following structure:

2. The article of claim 1, wherein the layer is an oleophobic layer.

3. The article of claim 1, wherein the linking group is selected from the group consisting of an alkyl group, an aryl group, a silyl moiety, or a combination thereof.

4. The article of claim 1, wherein the linking group is independently selected at each occurrence from the group consisting of: a -CH2- group, a -CH2CH2- group, a -CH2CH2CH2- group, Group, Group, group, -Si(CH3)2O-, -CH2O- group, -CH2CH3O- group, -CH2N- group, -CH2SO2- group, wherein n is independently 0-40 at each occurrence.

5. The article of claim 1, wherein the fabric is woven or non-woven.

6. The article of claim 1, wherein the fabric is selected from the group consisting of nylon, polyester, spandex, silk, wool, viscose, cellulosic fiber, acrylic, polypropylene, leather, or combinations thereof.

7. The article of claim 6, wherein the fabric is selected from cotton or polyethylene terephthalate.

8. The article of claim 1, wherein the layer comprises one or more polymer chains and at least one crosslink between two polymer chains.

9. The article of claim 1, wherein the layer comprises one or more polymer chains and at least one crosslink between the polymer chains and the fabric.

10. The article according to claim 8 or 9, wherein the at least one cross-linking moiety is selected from: and their combinations, where R 3 is a hydrocarbon group having 1 to 40 carbon atoms and n is 0-600.

11. The article of claim 1 , wherein the fabric comprises an oleophobic coating disposed partially or fully on an outer surface of one side of the fabric, and a superhydrophilic layer disposed partially or fully on an outer surface of an opposite side of the fabric.

12. The article of claim 1, wherein the fabric is a natural fabric or a fabric modified to be superhydrophilic, hydrophilic, hydrophobic, or superhydrophobic.

13. The article of claim 1, wherein the layer further comprises a plurality of nanoparticles.

14. A method of forming a layer comprising one or more layers of polydimethylsiloxane resin, the layer being disposed on part or all of the outer surface of a fabric, and wherein the layer has a strength of less than or equal to 22 mJ / m 2 The surface tension of the substrate, the method comprising: providing the fabric; coating a portion or all of the outer surface of the fabric with a PDMS resin or a composite nanofluid, wherein the composite nanofluid comprises a mixture of nanoparticles, a PDMS resin, and optionally, a solvent; and curing the PDMS resin coating or the coating formed of the composite nanofluid, wherein the layer is formed on a portion or all of the outer surface of the fabric, The PDMS resin comprises: One or more backbones selected from the group consisting of: poly(dimethylsiloxane), and A plurality of side groups, the plurality of side groups being covalently bonded to the main chain via a linking group, wherein at least a portion of the plurality of side groups has the following structure:

15. The method of claim 14, wherein the linking group is selected from the group consisting of an alkyl group, an aryl group, a silyl moiety, or a combination thereof.

16. The method of claim 14, wherein the linking group is independently selected at each occurrence from: a -CH2- group, a -CH2CH2- group, a -CH2CH2CH2- group, Group, Group, group, -Si(CH3)2O-, -CH2O- group, -CH2CH3O- group, -CH2N- group, -CH2SO2- group, wherein n is independently 0-40 at each occurrence.

17. The method of claim 14, wherein the fabric is selected from the group consisting of nylon, polyester, spandex, silk, wool, viscose, cellulosic fiber, acrylic, polypropylene, leather, or combinations thereof.

18. The method of claim 17, wherein the fabric is selected from cotton or polyethylene terephthalate.

19. The method of claim 14, wherein the layer is an oleophobic layer.

20. The method of claim 19, wherein the fabric further comprises a super-hydrophilic layer disposed on part or all of the outer surface of the fabric on the opposite side of the oleophobic layer.

21. The method of claim 19, further comprising adding additional surface roughness to the oleophobic layer.

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