WO2017111702A9 - Revêtement superhydrophobe durable - Google Patents

Revêtement superhydrophobe durable Download PDF

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Publication number
WO2017111702A9
WO2017111702A9 PCT/SG2016/050615 SG2016050615W WO2017111702A9 WO 2017111702 A9 WO2017111702 A9 WO 2017111702A9 SG 2016050615 W SG2016050615 W SG 2016050615W WO 2017111702 A9 WO2017111702 A9 WO 2017111702A9
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WIPO (PCT)
Prior art keywords
nanoadditive
substrate
coating material
organopolysiloxane
pmhs
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WO2017111702A1 (fr
Inventor
Hong Yan
Jianwei Xu
Qun YE
Hui Zhou
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Agency for Science Technology and Research Singapore
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Agency for Science Technology and Research Singapore
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Priority to SG11201805366VA priority Critical patent/SG11201805366VA/en
Priority to CN201680082334.5A priority patent/CN108699246A/zh
Publication of WO2017111702A1 publication Critical patent/WO2017111702A1/fr
Anticipated expiration legal-status Critical
Publication of WO2017111702A9 publication Critical patent/WO2017111702A9/fr
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring

Definitions

  • the present invention relates to a coating material for superhydrophobic coatings.
  • the present invention also relates to a method of fabricating such a coating material.
  • Superhydrophobic textiles are attractive because of their wide range of applications in surgical tools, medical devices, textiles (such as swimwear and military clothing), maritime industry and in environmental applications.
  • the main problem for commercialization of superhydrophobic textile is the high overall manufacturing cost, low mechanical strength and poor durability of coating materials on textile substrates. Therefore, current approaches are focused on how to use cost-effective materials to achieve superhydrophobicity with enhanced long-term durability.
  • mimicking hierarchical morphology of lotus leaf has been a main strategy to create superhydrophobic textiles, which involves either incorporating a coating layer with low surface energy or creating a special morphology or patterning on fibers, or both.
  • Perfluorinated materials have been widely applied for superhydrophobic coatings.
  • Perfluorinated materials have the characteristics of low cohesive energy, low surface free energy and low water uptake, which results in chemical resistance, corrosion resistance, low friction performance and weather resistance. For these reasons, they have been selected to be applied in superhydrophobic textile coating in modern industry. However, they are expensive and are hard to process in some cases.
  • their potential impact on health is uncertain, as perfluorinated materials have no known metabolic roles in mammals which may result in bioaccumulation, persist in the environment, and some may be reactive and toxic. Therefore applications of perfluorinated materials are limited.
  • Efforts have therefore been directed to develop non-fluorine containing materials for superhydrophobic textile coating, such as using metal oxide nanocomposite, precipitated calcium carbonate and carbon nanotube.
  • a cotton fabric coated with zinc oxide nanorods or zinc oxide crystallites can result in a superhydrophobic surface.
  • siloxane polymers such as polydimethylsiloxane (PDMS), poly(methylhydrosiloxane) (PMHS), or its copolymer which are non-toxic, low cost, easily fabricated, flexible and optically transparent. Coating a fibre with millions of tiny silicone filaments can result in a water-repellent clothing material.
  • PDMS polydimethylsiloxane
  • PMHS poly(methylhydrosiloxane)
  • its copolymer which are non-toxic, low cost, easily fabricated, flexible and optically transparent. Coating a fibre with millions of tiny silicone filaments can result in a water-repellent clothing material.
  • a superamphiphobic textile which is achieved through a two-step wet-chemistry coating technique, has been shown to exhibit remarkable multi-self healing ability against physical and chemical damages and exceptional liquid-repellency to low surface-tension liquids including ethanol.
  • most conventional methodologies require perfluoromaterials, poisonous chemicals, and delicate preparation procedures.
  • RGO reduced graphene -oxide
  • PDMS can be further applied to the cotton fibres coated with RGO to improve its surface wettability.
  • the RGO and PDMS are not chemically bonded to each other, which means that the coating can only be used on limited types of materials under limited treatment methods. Such a coating may also have limited durability and resistance to abrasion, especially under repeated washing. Further, a high concentration of RGO is required when the textile requires to be first coated with RGO.
  • RGO reduced graphene -oxide
  • organopolysiloxanes for superhydrophobic textile coating, which shows long-term acid, alkaline and hot-water resistance as well as abrasion resistance.
  • RGO modified organopolysiloxanes coating materials were synthesized via aryl radical assisted addition reaction, followed by hydrosilyation to covalently bond a very small amount of RGO with organopolysiloxanes.
  • the RGO-modified organopolysiloxanes showed excellent properties, there were limitations in it, including the tedious preparation process of vinyl functionalized RGO and limited Si-H groups being available for reaction with the polymer matrix.
  • a polymeric coating material comprising a nanoadditive covalently bound to an organopolysiloxane, wherein the nanoadditive comprises a) a nanoadditive substrate and b) a linker covalently bound by a silyloxy moiety to the nanoadditive substrate at one end and said organopolysiloxane at the other end.
  • the coating material may be superhydrophobic and repel water.
  • the coating material may not comprise fluorine. That is, the coating material may be fluorine-free. This means that any adverse effect associated with the use of perfluorinated materials may be circumvented by the disclosed polymeric coating material.
  • the disclosed coating material may be biocompatible, as it does not contain perfluorinated materials which may be toxic.
  • the disclosed coating material may be provided in a more cost-effective manner.
  • the disclosed coating material may comprise zero- to two-dimensional nanoadditives, which may only be required in trace amounts ( ⁇ 0.5% wt%). This may avoid having to use large amounts of expensive nanoadditives, resulting in the coating material being more cost-effective.
  • the disclosed coating material may have high durability in harsh conditions.
  • the disclosed coating may have excellent long-term resistance to strong mineral acid, strong corrosive alkaline and hot water, whilst maintaining its superhydrophobic properties.
  • the disclosed coating material may retain its superhydrophobic properties even after greater than 500 (or 7 days of) washings or after strong etching.
  • only a small amount of the disclosed coating material may be necessary to confer the superhydrophobic properties to the textile substrate, to confer resistance to strong corrosive acid, strong corrosive alkaline, hot water or chemical abrasion.
  • the nanoadditive substrate and the organopolysiloxane of the disclosed coating material may by covalently bonded.
  • the advantageous properties of the disclosed coating material may be due to the strong covalent linkage present between the nanoadditive substrate and the organopolysiloxane.
  • a method for making a coating material comprising the steps of a) reacting a silane reagent, preferably a vinyl trialkoxy silane, with a nanoadditive substrate, which is optionally surface functionalized with hydroxyl groups, b) covalently bonding the reaction product to an organopolysiloxane or its precursors optionally in the presence of a catalyst.
  • a silane reagent preferably a vinyl trialkoxy silane
  • the disclosed method provides a facile method for the synthesis of hybrid composites of nanoadditives and polysiloxanes. Further advantageously, the method facilitates mass production of the coating material as it is suitable for scaling up compared to conventional methods.
  • the use of the coating material as defined above for coating a substrate preferably natural or man-made fibers.
  • a method of coating a substrate, preferably a fiber comprising the steps of: a) dissolving a coating material as defined above in a solvent to form a coating solution; b) immersing said substrate in the coating solution; and c) removing said substrate from the coating solution.
  • the disclosed method facilitates easy coating of a substrate with the coating material as defined above. Further advantageously, the method allows the coating material to be applied to various natural or man-made fibers to achieve similar superhydrophobicity. Further advantageously, no further processing is required of the substrate after the coating process, making the application of the coating material straight forward and efficient.
  • a coated substrate obtainable by any of the methods as defined above having superhydrophobic properties.
  • the physicochemical properties, the colour or the hand feel of the substrate coated with the disclosed coating material may not change.
  • the coating material may be stain resistant which means that any substrate coated with the disclosed coating material may be easily washed.
  • the coating material may be applied across a wide range of substrates, including cotton, polyester, nylon and nomex, while maintaining the superhydrophobic properties. Even further advantageously, similar superhydrophobic properties may be conferred to the substrate, even if the properties of the substrates themselves are different. More advantageously, the permeability of the original substrate may be maintained even after coating the substrate with the disclosed coating material.
  • a polymer nanoadditive composite comprising a nanoadditive covalently bound to an organopolysiloxane, wherein the nanoadditive comprises a) a nanoadditive substrate and b) a linker covalently bound by a silyloxy moiety to the nanoadditive substrate at one end and said organopolysiloxane at the other end; and wherein the organopolysiloxane comprises one or more non-terminal units of formula (III) in the polymer chains
  • R 1 is independently selected from hydrogen, Ci to Ci 0 -alkyl, Ci to Ci 0 -alkenyl, Ci to Cio-alkyl- C 6 to Ci 0 -aryl or C 6 to Ci 0 -aryl; and R 1 is preferably methyl; and X is the bond to the linker.
  • Fig.l is a schematic representation of silane hydrolysis followed by condensation on a hydrated surface.
  • FIG. 2 is a schematic representation of the silylation-polymerization procedure of PMHS with various vinyl-functionalized nanoadditives.
  • Fig. 3 is a schematic representation of the silylation-polymerization procedure of PMHS with various vinyl-functionalized nanoadditives.
  • FIG. 3 refers to a photograph of (a) original clay and (b) vinylsilane-functionalized clay in (A) water and (B) THF.
  • FIG. 4 refers to FTIR spectra of (a) octavinyl POSS and (b) PMHS @POSS.
  • Fig. 5 refers to FTIR spectra of (a) octavinyl POSS and (b) PMHS @POSS.
  • FIG. 5 refers to FTIR spectra of (a) SiNPs, (b) vinylsilane-functionalized SiNPs and (c) PMHS @ SiNPs.
  • Fig. 6 refers to FTIR spectra of (a) rough carbon nanotubes (CNT), (b) vinylsilane- functionalized CNT and (c) PMHS @CNT.
  • FIG. 7 refers to FTIR spectra of (a) rough clay, (b) vinylsilane-functionalized clay and (c) PMHS @Clay.
  • Fig. 8 refers to FTIR spectra of (a) rough clay, (b) vinylsilane-functionalized clay and (c) PMHS @Clay.
  • FIG. 8 refers to FTIR spectra of (a) GO, (b) vinylsilane-functionalized GO and (c) PMHS @GO.
  • FIG. 9 refers to FTIR spectra of (a) RGO, (b) vinylsilane-functionalized RGO and (c) PMHS @RGO.
  • FIG. 10 is a TEM micrograph of vinylsilane-functionalized SiNPs.
  • FIG. 11 refers to TEM micrographs of (a) GO and (b) vinylsilane-functionalized GO.
  • Fig. 12 refers to TEM micrographs of (a) GO and (b) vinylsilane-functionalized GO.
  • FIG. 12 is a TEM micrograph of vinylsilane-functionalized RGO.
  • FIG. 13 refers to TEM micrographs of samples of (A) rough clay and (B) vinylsilane- functionalized clay.
  • Fig. 14 refers to TEM micrographs of samples of (A) rough clay and (B) vinylsilane- functionalized clay.
  • FIG. 14 refers to images showing wetting behavior of a water drop on cotton fabric coated with the coating materials that are embodiments of the present application.
  • the images show 5 uL drops of water on (A) PMHS @POSS, (B) PMHS @SiNPs, (C) PMHS @CNT, (D) PMHS @ Clay, (E) PMHS @ GO and (F) PMHS @RGO.
  • FIG. 15 refers to SEM images of cotton textile (A) uncoated, (B) coated with PMHS @SiNPs, (C) coated with PMHS @POSS, and (D) coated with PMHS @Clay.
  • FIG. 16 refers to images showing the wetting behaviour of a water drop on various comcemtial textile substrates (1) knit, (2) nonwoven and (3) woven.
  • the images show drops on textiles (A) uncoated, (B) coated with PMHS @POSS, (C) coated with PMHS @Silica, (D) coated with PMHS @CNT, (E) coated with PMHS @GO, (F) coated with PMHS @RGO, and (G) coated with PMHS @Clay.
  • FIG. 17 is a graphical representation of a superhydrophobic textile-coating of PMHS @nanoadditive on the textile substrate.
  • Fig. 18 is a graphical representation of a superhydrophobic textile-coating of PMHS @nanoadditive on the textile substrate.
  • FIG. 18 refers to (A) an image showing the stain-resistant behavior of a cotton glove (a) uncoated and (b) coated with PMHS @Clay, (B) an image showing the colour of the substrate (a) before coating and (b) after coating with PMHS @ Clay, (C) an image showing the antibacterial behavior of a textile substrate (a) uncoated and (b) coated with PMHS @ Clay and (D) the self-cleaning ability of a textile substrate (a) uncoated and (b) coated with PMHS @ Clay.
  • FIG. 19 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @Clay after being immersed in acid solution for (A) 1 week, (B) 2 weeks, (C) 3 weeks and (D) 4 weeks.
  • FIG. 20 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @ Clay after being immersed in alkaline solution for (A) 1 week and (B) 2 weeks.
  • Fig. 21 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @ Clay after being immersed in alkaline solution for (A) 1 week and (B) 2 weeks.
  • FIG. 21 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @Clay after washing for (A) 1 day, (B) 2 days, (C) 5 days and (D) 7 days.
  • Fig. 22 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @Clay after washing for (A) 1 day, (B) 2 days, (C) 5 days and (D) 7 days.
  • Fig. 22 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @Clay after washing for (A) 1 day, (B) 2 days, (C) 5 days and (D) 7 days.
  • Fig. 22 refers to images showing the wetting behaviour of a water drop on a cotton textile substrate coated with PMHS @Clay after washing for (A) 1 day, (B) 2 days, (C) 5 days and (D) 7 days.
  • Fig. 22 refers to images showing the wetting behaviour of
  • FIG. 22 refers to SEM images showing the morphology of cotton textile substrate coated with PMHS @Clay after washing for (A) 1 day, (B) 2 days, (C) 5 days and (D) 7 days.
  • Alkyl as a group or part of a group refers to a straight or branched aliphatic hydrocarbon group, preferably a C ⁇ -C ⁇ 2 alkyl, more preferably a Ci-Cio alkyl, most preferably Q-Ce unless otherwise noted.
  • suitable straight and branched Q-Ce alkyl substituents include methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, t-butyl, hexyl, and the like.
  • the group may be a terminal group or a bridging group.
  • Alkenyl as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched preferably having 2-12 carbon atoms, more preferably 2-10 carbon atoms, most preferably 2-6 carbon atoms, in the normal chain.
  • the group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z.
  • Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl.
  • the group may be a terminal group or a bridging group.
  • Aryl as a group or part of a group denotes (i) an optionally substituted monocyclic, or fused polycyclic, aromatic carbocycle (ring structure having ring atoms that are all carbon) preferably having from 5 to 12 atoms per ring.
  • aryl groups include phenyl, naphthyl, and the like; (ii) an optionally substituted partially saturated bicyclic aromatic carbocyclic moiety in which a phenyl and a C5 7 cycloalkyl or C5 7 cycloalkenyl group are fused together to form a cyclic structure, such as tetrahydronaphthyl, indenyl or indanyl.
  • the group may be a terminal group or a bridging group.
  • an aryl group is a C 6 -C 18 aryl group.
  • Alkylaryl means an alkyl-aryl— group in which the aryl and alkyl moieties are as defined herein. Preferred alkylaryl groups contain a C 1 10 alkyl moiety.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the aryl group.
  • PHMS@POSS means "vinylsilane functionalized POSS cross-linked with PHMS”
  • PMHS @SiNP, PMHS @CNT, PMHS @Clay, PMHS @RO, PMHS @RGO should be construed accordingly.
  • PDMS/PMHS means a copolymer of PDMS and PHMS.
  • PDMS PMHS @POSS therefore means "vinylsilane functionalized POSS cross- linked with a copolymer of PDMS and PMHS.
  • zero-dimensional (0D) nanostructures such as nanoparticles
  • One- dimensional (ID) nanomaterials such as nanorods, nano wires, nanobelts and nanotubes
  • ID two dimensions on the nanoscale
  • 2D Two-dimensional nanomaterials
  • nanosheet and nanoplate have one dimension on the nanoscale, typically below 100 nm.
  • the word “substantially” does not exclude “completely” e.g. a composition which is "substantially free” from Y may be completely free from Y. Where necessary, the word “substantially” may be omitted from the definition of the invention.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range. Certain embodiments may also be described broadly and generically herein.
  • Hybridization of nanoadditive and polymer matrices represent a class of emerging materials that are promising for superhydrophobic textile coating as they integrate both inherent characteristics of organic polymer matrix and nanoadditives.
  • many studies have suggested that the performance of hybrid superhydrophobic materials may be limited by two factors:
  • RGO Organopolysiloxanes-reduced graphene oxide
  • PMHS poly(methylhydrosiloxane)
  • a series of nanoadditives from zero-dimensional polyhedral oligomeric silsesquioxanes (POSS) and nanoparticles silica nanoparticles (SiNPs), one dimensional carbon nanotube (CNT) and two dimensional graphene oxide (GO), reduced graphene oxide (RGO) and clay have been treated with a silane reagent, for example, tetraethoxysilane (TEOS) first, followed by reacting with PMHS to give rise to zero- to two- dimensional nanoadditive modified PMHS polymers.
  • a silane reagent for example, tetraethoxysilane (TEOS)
  • the nanoadditives such as POSS, SiNPs, GO, RGO, and clay have tunable dimensions and diverse morphologies provide many opportunities for different applications.
  • the nanoadditives are easily synthesized at scale, thus avoiding multistep procedures of polymerization onto textile surfaces.
  • the nanoadditive modified polymeric materials may be able to form a thin film on the textile substrate, which may be stable over a long period even at harsh conditions.
  • these nanoadditives were designed for use as crosslinking agents for the formation of polymeric coating materials.
  • the overall process for immobilization of the vinyl group on nanoadditives via silanization is illustrated in Fig. 1.
  • Group R is a nonhydrolyzable organic radical (a substituted vinyl group) that facilitates bonding with organic resins and polymers.
  • the silanol group usually is a hydrolyzable group, typically trimethoxysilyl or triethoxysilyl, which is involved in the reaction with the nanoadditive substrate. Therefore, in the present disclosure, hydrolysis of trimethoxysilyl groups followed by condensation with silanol groups resulted in covalent attachment of vinyl groups onto nanoadditives surface.
  • PDMH reacted with vinyl functionalized nanoadditives comprising SiNP, POSS, CNT GO, RGO, and clay to offer polymer composites as shown in Figure 2.
  • the nanoadditive modified PDMH was directly used for textile coating without any further treatment.
  • the variety of the crosslinking nano-agents may provide opportunities to form dense crosslinking polymeric materials, and thus to create high performance superhydrophobic textile coatings.
  • the ability to allocate active components grafted into the polymeric network may offer an opportunity to improve material stability and subsequently optimize performance.
  • the disclosed polymeric coating material may comprise a nanoadditive covalently bound to an organopolysiloxane, wherein the nanoadditive comprises a) a nanoadditive substrate and b) a linker covalently bound by a silyloxy moiety to the nanoadditive substrate at one end and said organopolysiloxane at the other end.
  • the organopolysiloxane may comprise hydrophobic groups, which are preferably selected from alkyl, alkenyl, alkylaryl or aryl, most preferably Ci to Ci 0 -alkyl, Ci to Ci 0 -alkenyl, Ci to Ci 0 - alkyl-C 6 to Ci 0 -aryl or C 6 to Ci 0 -aryl.
  • the alkyl may be linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
  • the alkenyl may be linear or branched ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
  • the aryl may be phenyl, naphthyl, tetraphenylnaphthyl, indenyl or indanyl.
  • the alkylaryl may be 2-methylbenzene, 3- methylbenzene, 4-methylbenzene, 2-ethylbenzene, 3-ethylbenzene, 4-ethylbenzene, 2- propylbenzene, 3-propylbenzene, 4-propylbenzene, 2-butylbenzene, 3-butylbenzene, 4- butylbenzene, 2-pentylbenzene, 3-pentylbenzene, 4-pentylbenzene, 2-hexylbenzene, 3- hexylbenzene, 4-hezylbenzene, 2-heptylbenzene, 3-heptylbenzene, 4-heptylbenzene, 2- octylbenzene, 3-octylbenzene, 4-octylbenzene, 2-nonylbenzene, 3-nonylbenzene, 4- nonylbenzene, 2-decylbenzene, 3-decylbenz
  • the content of nanoadditive substrate may be less than about 3 % by weight, preferably less than about 0.5 % by weight and most preferably between about 0.005 and 0.5 % by weight, of the organopolysiloxane.
  • the content of the nanoadditive substrate may be in the range of about 0.001% by weigh to about 5% by weight, about 0.001% by weight to about 0.005% by weight, about 0.001% by weight to about 0.01% by weight, about 0.001% by weight to about 0.05% by weight, about 0.001% by weight to about 0.1% by weight, about 0.001% by weight to about 0.5% by weight, about 0.001% by weight to about 1% by weight, about 0.001% by weight to about 3% by weight, about 0.005% by weight to about 0.01% by weight, about 0.005% by weight to about 0.05% by weight, about 0.005% by weight to about 0.1% by weight, about 0.005% by weight to about 0.5% by weight, about 0.005% by weight to about 1% by weight, about 0.005% by weight to about 0.5% by weight, about 0.005% by weight to about 1% by weight, about 0.005% by weight to about 3% by weight, about 0.005% by weight to about 5% by weigh, about 0.01% by weight to about 0.05% by weight
  • the polymeric organopolysiloxane prior to covalent bonding to the linker, may comprise repetitive silicon-hydrogen moieties.
  • the polymeric organopolysiloxane, prior to covalent bonding to the linker, may comprise one or more, preferably from 3 to 200, units of formula (I) or (la) in the polymer chains
  • R 1 at each occurrence, is independently selected from Ci to Ci 0 -alkyl, Ci to Ci 0 - alkenyl, Ci to Cio-alkyl- C 6 to Ci 0 -aryl or C 6 to Cio-aryl; and R 1 is preferably methyl.
  • the polymeric organopolysiloxane, prior to covalent bonding to the linker, may comprise one or more units of formula (I) or (la) in the polymer chains.
  • the polymeric organopolysiloxane, prior to covalent bonding to the linker may comprise from 1 to 300 units, from 1 to 3 units, from 1 to 10 units, from 1 to 20 units, from 1 to 50 units, from 1 to 100 units, from 1 to 200 units, from 3 to 10 units, from 3 to 20 units, from 3 to 50 units, from 3 to 100 units, from 3 to 200 units, from 3 to 300 units, from 10 to 20 units, from 10 to 50 units, from 10 to 100 units, from 10 to 200 units, from 10 to 300 units, from 20 to 50 units, from 20 to 100 units, from 20 to 200 units, from 20 to 30 units, from 50 to 100 units, from 50 to 200 units, from 50 to 300 units, from 100 to 200 units, from 100 to 300 units or from 200 to 300 units of formula (I) or (la) in the polymer chains.
  • R 1 may be preferably selected from alkyl, alkenyl, alkylaryl or aryl, most preferably Ci to Ci 0 - alkyl, Ci to Cio-alkenyl, Ci to Ci 0 -alkyl-C 6 to Cio-aryl or C 6 to Cio-aryl.
  • R 1 When R 1 is alkyl, the alkyl may be linear or branched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
  • R 1 When R 1 is alkenyl, the alkenyl may be linear or branched ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl.
  • R 1 When R 1 is aryl, the aryl may be phenyl, naphthyl, tetraphenylnaphthyl, indenyl or indanyl.
  • R 1 is alkylaryl
  • the alkylaryl may be 2-methylbenzene, 3-methylbenzene, 4-methylbenzene, 2-ethylbenzene, 3- ethylbenzene, 4-ethylbenzene, 2-propylbenzene, 3-propylbenzene, 4-propylbenzene, 2- butylbenzene, 3-butylbenzene, 4-butylbenzene, 2-pentylbenzene, 3-pentylbenzene, 4- pentylbenzene, 2-hexylbenzene, 3-hexylbenzene, 4-hezylbenzene, 2-heptylbenzene, 3- heptylbenzene, 4-heptylbenzene, 2-octylbenzene
  • the polymeric organopolysiloxane may be poly(methylhydrosiloxane) (PMHS).
  • PMHS may have more reactive sites (Si-H groups) which facilitates more durable coating materials as it is able to form stronger linkages between the polymer matrix and the nanoadditives.
  • the poly(methylhydrosiloxane) may be of representative formula (II)
  • n is an integer selected so that the poly(methylhydrosiloxane) has a molecular weight range of about 390 to about 10,000.
  • n may be an integer selected so that the poly(methylhydrosiloxane) has a molecular weight range of about 350 to about 15,000, about 350 to about 390, about 350 to about 500, about 350 to about 1000, about 350 to about 5000, about 350 to about 10,000, about 390 to about 500, about 390 to about 1000, about 390 to about 5000, about 390 to about 10,000, about 390 to about 15,000, about 500 to about 1000, about 500 to about 5000, about 500 to about 10,000, about 500 to about 15,000, about 1000 to about 5000, about 1000 to about 10,000, about 1000 to about 15,000, about 5000 to about 10,000, about 5000 to about 15,000 or about 10,000 to about 15,000.
  • the nanoadditive substrate, prior to being linked to the organopolysiloxane may be surface- functionalized with vinyl groups, preferably by using
  • the nanoadditive substrate may be a particle of 10 nm to 10 ⁇ size.
  • the nanoadditive substrate may be a particle of about 5 nm to about 15 ⁇ , about 5 nm to about 10 nm, about 5 nm to about 50 nm, about 5 nm to about 100 nm, about 5 nm to about 500 nm, about 5 nm to about 1 ⁇ , about 5 nm to about 5 ⁇ , about 5 nm to about 10 ⁇ , about 10 nm to about 50 nm, about 10 nm to about 100 nm, about 10 nm to about 500 nm, about 10 nm to about 1 ⁇ , about 10 nm to about 5 ⁇ , about 10 nm to about 10 ⁇ , about 10 nm to about 15 ⁇ , about 50 nm to about 100 nm, about 50 nm to about 500 nm, about 10 nm to about 1 ⁇ , about 10 nm to about 5 ⁇ ,
  • the nanoadditive substrate may be selected from the group consisting of carbon nanotubes, graphene oxides and reduced graphene oxides, clay, silica-dioxide nanoparticles or a polyhedral oligomeric silsesquioxane.
  • nanoadditives may be used in the coating material.
  • the nanoadditive may be zero-dimensional, one -dimensional or two-dimensional.
  • the silyloxy linker, before forming the covalent bonds, may comprise a nonhydrolyzable moiety, preferably a vinyl group, and a silyloxy moiety.
  • this may ensure selective bonding of the nanoadditive to organopolysiloxane. Further advantageously, this may ensure that the resultant coating has long-term resistance to strong acid, base and hot water, as less chemical reactions would take place in the absence of hydrolysable groups.
  • the silyloxy moiety may be covalently bound to the nanoadditive substrate via a silyl-ether bridge.
  • the silyl-ether bridge may provide a strong chemical bond between the nanoadditive and the polymer matrices which in turn significantly increases the mechanical and physical properties of the coating material.
  • the nonhydrolyzable moiety preferably a vinyl group, may be covalently bound to the polymeric organopolysiloxane.
  • a method for making a coating material may comprise the steps of a) reacting a silane reagent, preferably a vinyl trialkoxy silane, with a nanoadditive substrate, which is optionally surface functionalized with hydroxyl groups, b) covalently bonding the reaction product to an organopolysiloxane or its precursors optionally in the presence of a catalyst.
  • a silane reagent preferably a vinyl trialkoxy silane
  • the silane reagent may be any reagent comprising a silane.
  • the vinyl trialkoxy silane may be vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropyloxysilane or vinyl tributyloxysilane.
  • the catalyst may be selected from group 10 elements.
  • the group 10 element may be nickel, palladium or platinum.
  • the catalyst may comprise platinum.
  • the catalyst may be platinum(0)-l,3- divinyl-1, 1,3,3- tetramethyl-disiloxane, catalysts used in classical Pt-catalysis such as Speier's or Karstedt's catalysts, catalysts used in Rh-based catalysis such as [Rh(cod) 2 ]BF 4 or [RhCl(nbd)] 2 , or catalysts used in Ru-based catalysts such as Wilkinson's catalyst, Grubbs' 1 st generation cacatalyst, [Ru(benzene)Cl 2 ] 2 or [Ru(p-cymene)Cl 2 ] 2), [Cp*Ru(MeCN) 3 ]PF 6 .
  • the organopolysiloxane may be PMHS, and the nanoadditive substrate may be vinylsilane functionalized.
  • the reaction between the organopolysiloxane and the nanoadditive substrate may be easily controlled without the need to introduce complicated intermediates.
  • the use of the coating material as defined above may be for coating a substrate, preferably natural or man-made fibers.
  • the substrate may be a textile.
  • the textile may be a flexible material consisting of a network of natural or man-made (artificial) fibers.
  • the natural or man-made fibers may comprise hair, fur, skin, silk, wool, flax, cotton, grass, rush, hemp, sisal, coir, straw, bamboo, pulpwood, rice, nettle, jute, modal, lacebark, acetate, seaweed, lyocells, asbestos, basalt, glass, metal, polyester, aramid, acrylic, nylon, spandex, olefin, ingeo, lucrex, milk or carbon.
  • the coating material may be used on a variety of different substrates, yet confer the same superhydrophobic properties to the substrate when the substrate is coated with the coating material.
  • a method of coating a substrate, preferably a fiber may comprise the steps of: a) dissolving a coating material as defined above in a solvent to form a coating solution; b) immersing said substrate in the coating solution; and c) removing said substrate from the coating solution. The method may further comprise the step of (d) drying the substrate from step (c) to remove the solvent.
  • the solvent used may be any solvent that is capable of dissolving the coating material as defined above.
  • the solvent used may preferably be selected from the group consisting of toluene, dichloromethane and chloroform.
  • a coated substrate may be obtainable by any of the methods as defined above having superhydrophobic properties.
  • the coated substrate may have a water contact angle (WCA) in the range of about 150° to about
  • WCA water contact angle
  • the coated substrate may be for use in textile processing, packaging materials, paper industry, antifouling clothing, sportswear and boat sails.
  • a polymer nanoadditive composite may comprise a nanoadditive covalently bound to an organopolysiloxane, wherein the nanoadditive comprises a) a nanoadditive substrate and b) a linker covalently bound by a silyloxy moiety to the nanoadditive substrate at one end and said organopolysiloxane at the other end; and wherein the organopolysiloxane comprises one or more non-terminal units of formula (III) in the polymer chains
  • R 1 is independently selected from hydrogen, Ci to Ci 0 -alkyl, Ci to Ci 0 -alkenyl, Ci to Cio-alkyl- C 6 to Ci 0 -aryl or C 6 to Ci 0 -aryl; and R 1 is preferably methyl; and X is the bond to the linker.
  • the organopolysiloxane prior to covalent bonding to the linker, may be a poly(methylhydrosiloxane) of representative formula (II)
  • R 1 represents methyl
  • n is an integer selected to represent an integer so that the poly(methylhydrosiloxane) has a molecular weight range of about 390 to about 10,000.
  • the nanoadditive substrate may be selected from the group consisting of carbon nanotubes, graphene oxides and reduced graphene oxides, clay, silica-dioxide nanoparticles or a polyhedral oligomeric silsesquioxane. Examples
  • Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.
  • Poly(mefhylhydrosiloxane) (average Mn 1,700-3,200, PMHS), Poly(dimefhylsiloxane-co- methylhydrosiloxane), (trimethylsilyl terminated, (PDMS/PMHS), (Mn -13,000, mefhylhydrosiloxane 3-4 mol %) was purchased from Sigma-Aldrich.
  • the clay used is the alkyl quaternary ammonium salt bentonite "CLOISITE 30B".
  • Other chemicals were purchased from Sigma-Aldrich and used as received. Water was purified with a Millipore Milli-Q water system.
  • Example 2 A Preparation of vinylsilane-functionatized silica nanoparticles (SiNPs)
  • tetraethoxysilane (TEOS, 10 mL) and ammonium hydroxide (10 mL) were dissolved into a solution of ethanol/water (428 mL/60 mL, v/v) with gentle stirring at 30 °C for 2 hours.
  • the white product was rinsed 4 times with ethanol and distilled water, respectively.
  • the resulting surfactant -free SiNPs was dried overnight in a vacuum oven at 40 °C to remove the remaining solvent.
  • the SiNPs (1.00 g) was then refluxed for 20 hours in 80.00 mL of anhydrous toluene with 0.25 mL (1.00 mmol) of trimethoxy(vinyl)silane to yield the vinylsilane- functionalized SiNPs.
  • Example 2B Preparation of vinylsilane-functionatized multi-walled carbon nanotubes (MWCNT)
  • MWCNT (0.5 g) was added to 150 mL of H 2 S0 4 (98%) and then sonicated at room temperature for 30 min. 50 mL of concentrated HN0 3 was added to the solution slowly and stirred vigorously at room temperature for 30 minutes. The mixture was heated to 80 °C for 1 hour. After that, the mixture was cooled to room temperature and slowly diluted with Milli-Q water. The mixture was filtered and washed with methanol and distilled water through 0.2 ⁇ filter paper 4 times. After vacuum drying of the filtrate, MWCNTs functionalized (MWCNT-OH) with hydroxyl groups were obtained.
  • Hydroxy functionalized MWCNTs (0.05 g) as prepared above was dispersed in 40 mL toluene by ultrasonication for 10 min. After adding an excess of trimethoxy(vinyl)silane, the suspension was refluxed under N 2 at 100 °C for 6 h. After reaction, the resultant filtrate was washed repeatedly with methanol to remove residual trimethoxy(vinyl)silane. The solid product obtained was dried under vacuum overnight.
  • Example 2C Preparation of vinylsilane-functionalized clay Clay (5.0 g) was mixed with 1, 2.5, or 3.5 M H 2 S0 4 solutions (100 mL). The resulting suspensions were heated at 80 ⁇ 2 °C for 2 hours under continuous stirring. After acid activation, the precipitate was filtered and washed thoroughly with distilled water until the filtrate was free from sulphate ions (tested by BaCl 2 solution). Acid activated clay was then suspended in toluene at the concentration of 10 g/L and a required amount of trimethoxy(vinyl)silane was introduced into the reaction flask and the mixture was refluxed for 6 hrs.
  • Fig. 3 refers to images of (a) original clay and (b) vinylsilane-functionalized clay in (A) water and (B) THF, and shows the solubility changes of clay in water and THF before and after vinylsilane treatment.
  • Example 2D Preparation of vinylsilane-functionalized graphene oxide (GO) and reduced graphene oxide (RGO)
  • GO and RGO were prepared according to the literature reported procedures. GO or RGO (0.5 mg mL 1 ) and NaOH (0.25 mL, 2 M) were added into a round bottom flask, which was then topped up with ultrapure water to get the final volume of 100 mL. The solution was stirred vigorously under 80 °C for 30 min. Hot CTAB (10 mL, 0.56 M) was added into the solution, and the mixture was stirred for another half hour. When the temperature was stabilized at 80 °C, TEOS (2 mL) was added dropwise into the solution followed by the addition of trimethoxy( vinyl) silane (0.5 mL) after 15 min. The solution was allowed to incubate at 80 °C for another 4 hours. The final product was collected by centrifugation and washed with HC1 (1 M) and MeOH with equal volumes for 3 times each, and then with pure MeOH for 3 times. The obtained solid product was dried under vacuum overnight.
  • Example 2E Preparation of polymeric coating materials of various nanoadditives crosslinked PMHS PMHS or PDMS/PMHS (6 g) was dissolved in toluene, and the as-prepared vinyloxy- containing nanoadditives 30 mg (POSS, SiNPs, CNT, GO, RGO or clay, respectively) was then added. Platinum(0)-l,3-divinyl-l,l,3,3-tetramethyl-disiloxane complex solution (100 ⁇ ) was dissolved in minimum toluene and added to the above solution slowly under N 2 . Once the addition was complete, the mixture solution was stirred at 80 °C for four hours. The solution was then diluted for further uses.
  • the products obtained were PMHS @POSS, PMHS @SiNP, PMHS @CNT, PMHS @Clay, PMHS@RO, PMHS @RGO, PDMS PMHS @POSS, PDMS PMHS @SiNP, PDMS PMHS @CNT, PDMS PMHS @Clay, PDMS PMHS @RO or PDMS PMHS @RGO, respectably.
  • Fig. 4 to 9 show a set of representative FTIR spectra of pristine nanoadditives, vinylsilane- functionalized nanoadditives, and nanoadditive-modified PMHS.
  • Fig. 4 shows the FTIR spectra of (a) octavinyl POSS and PMHS@POS
  • Fig. 5 shows FTIR spectra of (a) SiNPs, (b) vinylsilane-functionalized SiNPs and (c) PMHS @ SiNPs
  • Fig. 6 shows FTIR spectra of (a) SiNPs, (b) vinylsilane-functionalized SiNPs and (c) PMHS @ SiNPs
  • Fig. 4 shows the FTIR spectra of (a) octavinyl POSS and PMHS@POS
  • Fig. 5 shows FTIR spectra of (a) SiNPs, (b) vinylsilane-functionalized SiNPs and (c) PMHS @ SiNPs
  • Fig. 6 shows
  • FIG. 7 shows FTIR spectra of (a) rough clay, (b) vinylsilane-functionalized clay and (c) PMHS @clay
  • Fig. 8 shows FTIR spectra of (a) GO, (b) vinylsilane-functionalized GO and (c) PMHS @ GO and
  • Fig. 9 shows FTIR spectra of (a) RGO, (b) vinylsilane-functionalized RGO and (c) PMHS @RGO.
  • Figures 10 to 13 show a set of the representative TEM images of vinylsilane functionalized nanoadditives prepared by silylation.
  • Fig. 10 shows a TEM micrograph of vinylsilane- functionalized SiNP
  • Fig. 11 shows TEM micrographs of (a) GO and (b) vinylsilane- functionalized GO
  • Fig. 12 shows a TEM micrograph of vinylsilane-functionalized RGO
  • Fig. 13 shows TEM micrographs of samples of (A) rough clay and (B) vinylsilane- functionalized clay.
  • the characteristic silica shell was found on the surface of nanoadditives, such as CNT, GO, RGO and clay, respectively.
  • Example 4 Superhydrophobic Coating of A Substrate
  • the straightforward "one -pot" synthesis of nanoadditive modified polymeric materials is schematically depicted in Fig. 2.
  • the vinyl-functionalized nanoadditives (202) reacted with polymethylhydrosiloxane (PMHS) (204) in the presence of a catalytic amount of Pt catalyst in toluene to form the nanocomposite material (206).
  • the nanoadditives include POSS (212), SiNP (214), CNT (216), GO or RGO (218) and clay (220).
  • PMHS was used as polymer matrix, which has 25 to 50 methylhydrosiloxane units in its polymer structure.
  • the multiple reaction sites offer strong covalent bonding between nanoadditives and polymer matrix, preventing phase separation in the final hybrid materials.
  • the nanoadditive modified PMHS materials were dispersed into toluene to form a coating solution.
  • the coating solution can be directly applied onto the textile substrate using dip- coating.
  • the coated textile substrates were dried for a few hours in a fume hood and subsequently placed in an oven for drying at 60 °C overnight.
  • the water contact angle measurement revealed that cotton fabrics coated with nanoadditive - PMHS hybrids showed a nearly sphere -like water droplet, as shown in Fig. 14.
  • the images show 5 uL drops of water on (A) PMHS @POSS, (B) PMHS @SiNPs, (C) PMHS @CNT, (D) PMHS @Clay, (E) PMHS @ GO and (F) PMHS @RGO.
  • the nanoadditives were found to significantly affect the superhydrophobicity of coated textiles.
  • the average contact angles on the cotton surfaces coated with PMHS@SiNP, PMHS@POSS, PMHS@CNT, PMHS@RGO, PMHS@Clay, and PMHS@GO were about 130°, about 150°, about 160°, about 160°, about 170° and about 170°, respectively.
  • the contact angle increased as the nanoadditives were changed from zero-dimensional to two-dimensional structure.
  • Fig. 15 shows a set of representative SEM images showing the morphology change in cotton fibre before and after coating with various coating materials of the present disclosure, where (A) uncoated, (B) coated with PMHS @SiNPs, (C) coated with PMHS @POSS, and (D) coated with PMHS @Clay.
  • Pristine un-coated textile substrates possess a rather rough surface as shown in Fig. 15(A). Consistent with contact angle analysis, a set of distinct smooth silica shells contour of the original shape of the textile weave as observed by SEM images, which correspond to the coating layer of polymeric hybrid materials.
  • the coating solutions were applied to various natural or man-made fibers, e.g. polyester, cotton, asbestos cloth et al, using the same dip-coating method. As shown in Fig. 16, the superhydrophobicity was also observed on three different knitting type of textiles, (1) knit, (2) nonwoven and (3) woven.
  • the images show drops on textiles (A) uncoated, (B) coated with PMHS @POSS, (C) coated with PMHS @ Silica, (D) coated with PMHS @CNT, (E) coated with PMHS @GO, (F) coated with PMHS@RGO, and (G) coated with PMHS @Clay.
  • the knitting pattern of a textile has significant impact on the water contact angles.
  • Polymers modified with one -dimensional and two-dimensional nanoadditives demonstrated consistent water contact angles on various type of textiles.
  • the water contact angles of polymers modified with zero-dimensional nanoadditives (POSS and SiNPs) were significantly correlated to the morphology of the textile.
  • the water contact angle decreased to 90-130° for textile substrates that were sparsely knitted.
  • the coating materials of the present disclosure take advantage of the inherent morphological anisotropy of textile substrates which have a hierarchical roughness in the micro scale, to further enhance the surface hydrophobicity. Based on such superhydrophobic features, a mechanism of how the coatings of the present disclosure works is proposed, as depicted in Fig. 17. Without being bound to theory, it is proposed that the coatings of the present disclosure enhances the surface roughness and surface chemistry of the textile substrate to mimic lotus leaves.
  • Superhydrophobic textile coatings that confer properties such as stain resistance and self- cleaning capabilities to the substrate to be coated have led to various applications in the textile industry.
  • the coating solutions were applied to fibers, e.g. polyester, cotton, asbestos cloth et al, using the same dip-coating method.
  • the coated textile substrates were also stained with pigmented water to test stain resistance.
  • the cotton glove coated with PMHS@Clay was easily cleaned after immersion into a stained solution by rinsing with water.
  • Fig. 18(B) shows that unlike conventional coatings of this kind, the coating material PMHS@Clay as disclosed in the present application does not change the white colour of the textile substrate.
  • the self-cleaning test of the PMHS@Clay coated cotton is shown in Fig. 18(D) that the water dropped on the uncoated cotton surface were difficult to carry away the dust when tilting 10°. However, when the PMHS@Clay coated cotton titling 10°, the water droplets could easily roll off, leaving an clean surface as shown in Fig. 18(D). Due to the contact area of dirty particles to the PMHS@Clay coated cotton decreasing, the adherence strength between dirty particles and PMHS@Clay coated cotton surface decreases, too, so the dirt on nanostructure materials is easier taken away by water. This self-cleaning test validates that the developed method has successfully mimicked the self-cleaning mechanism of lotus leaf.
  • the superhydrophobic coating also showed good resistance to boiling water.
  • Experimental results showed that the coated textile substrate had no change in superamphiphobicity after boiling the coated textile substrate in water for 2 hours. Therefore, the coating not only granted the textile substrate super water-repellent properties, but also showed excellent chemical resistance.
  • Fig. 22 shows representative set of SEM images of the morphology changes of cotton fibre coated with PMHS @Clay after washing for different lengths of times. Although the silica shell became cracked, especially at the fibre connections, the silica shell on individual fibres was maintained. The surface morphology was qualitatively consistent with the water contact angles as measured in Fig. 21. Industrial Applicability
  • the coating material of the present disclosure and the substrate coated with the coating material have a wide range of applications in surgical tools, medical devices, textiles (such as swimwear and military clothing), maritime industry and in environmental applications.
  • applications in agriculture may include seed/crop covers, bags, shade materials, irrigation systems, pond liners and hoses
  • applications in clothing may include shoe upper and linings, artificial leather/bags/belts, rainwear, garment linings, backing/stiffeners, gloves and hats
  • applications in geotextiles may include settling pond liners, irrigation liners, landfill liners and covers, soil stabilizers and erosion barriers
  • applications in construction may include safety fencing, wind covers, safety vests, conveyer belting and truck covers
  • applications in home furnishings may include upholstery, trim, carpet backing, drapery backing, bedding and artificial leather
  • applications in industry may include conveyer belts, filtration, barrier materials, field covers, abrasive backing and mechanical rubber goods, as well as applications in medical equipment, tents, transportation, sport, leisure, packaging and protective equipment.

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Abstract

L'invention concerne un matériau de revêtement polymère comprenant un nanoadditif fonctionnalisé en surface, tel que fonctionnalisé par vinyle, lié de manière covalente à un organopolysiloxane, tel qu'un poly(méthylhydrosiloxane) (PMHS), le nanoadditif comprenant (a) un substrat de nanoadditif substrat et (b) un lieur lié de manière covalente par un fragment silyloxy au substrat de nanoadditif en une extrémité et audit organopolysiloxane à l'autre extrémité. L'invention concerne également un procédé de fabrication d'un tel matériau de revêtement, l'utilisation d'un tel matériau de revêtement, un procédé de revêtement d'un substrat par un tel matériau de revêtement et un substrat revêtu pouvant être obtenu par un tel procédé.
PCT/SG2016/050615 2015-12-23 2016-12-23 Revêtement superhydrophobe durable Ceased WO2017111702A1 (fr)

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CA3092019A1 (fr) * 2018-02-22 2019-08-29 Azra Shs Tech Inc. Revetement superhydrophobe durable
CN109440525A (zh) * 2018-10-31 2019-03-08 华南理工大学 一种耐磨超疏水纸及其制备方法
PE20220390A1 (es) * 2018-12-31 2022-03-18 Zydex Inc Composiciones estabilizadoras del suelo
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CN110183158A (zh) * 2019-06-05 2019-08-30 广西大学 一种超疏水涂层的制备方法
CN111286976B (zh) * 2020-03-04 2022-03-08 盐城工学院 一种基于化学镀镍超疏水油水分离涤纶织物的制备方法和产品
CN112144286B (zh) * 2020-09-29 2022-10-21 上海承一化学科技有限公司 一种有耐磨自清洁功能的纺织品及其应用
CN113265180B (zh) * 2021-04-16 2022-05-27 清远慧谷新材料技术有限公司 一种硅改性石墨烯水性涂料及其制备方法
CN116750759B (zh) * 2023-06-08 2025-11-28 湖南科技学院 一种聚硅氧烷改性单层氧化石墨烯及其制备方法
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8575045B1 (en) * 2004-06-10 2013-11-05 The United States Of America As Represented By The Secretary Of The Army Fiber modified with particulate through a coupling agent
CN104262639B (zh) * 2014-09-05 2016-11-23 陕西科技大学 超疏水型交联聚硅氧烷-聚倍半硅氧烷纳米球杂化材料的制备方法
WO2016076801A1 (fr) * 2014-11-14 2016-05-19 Agency For Science, Technology And Research Revêtements hydrophobes comprenant de l'oxyde de graphène réduit modifié avec un polymère siloxane
CN104805680A (zh) * 2015-04-28 2015-07-29 武汉纺织大学 一种功能性织物的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111472176A (zh) * 2020-04-15 2020-07-31 江南大学 一种石墨烯/聚二甲基硅氧烷改性棉织物方法

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