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WO2025137670A1 - Non-fluorinated polymer additives and related methods - Google Patents

Non-fluorinated polymer additives and related methods Download PDF

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Publication number
WO2025137670A1
WO2025137670A1 PCT/US2024/061638 US2024061638W WO2025137670A1 WO 2025137670 A1 WO2025137670 A1 WO 2025137670A1 US 2024061638 W US2024061638 W US 2024061638W WO 2025137670 A1 WO2025137670 A1 WO 2025137670A1
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poss
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Bong June ZHANG
Miguel Galvez
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • 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
    • C08G77/06—Preparatory processes
    • 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
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—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
    • 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
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • compositions comprising non-fluorinated polyhedral oligomeric silsesquioxane (POSS)-based compounds, and related articles, methods, and kits, are generally described.
  • PES polyhedral oligomeric silsesquioxane
  • compositions comprising non-fluorinated polyhedral oligomeric silsesquioxane (POSS)-based compounds and related articles, methods, and kits.
  • PES non-fluorinated polyhedral oligomeric silsesquioxane
  • a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a multifunctionalized POSS molecule of the structure: wherein: each R 1 is the same or different and is selected from the group consisting of-O-Si(R 2 ) 2 - (R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 )
  • a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a POSS molecule of the structure: wherein: each R 1 is the same or different and is selected from the group consisting of-O-Si(R 2 ) 2 - (R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 ,- O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -, -O-Si(R 2 )
  • a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a POSS molecule of the structure: wherein: each R 1 is the same or different and is selected from the group consisting of -O-Si(R 2 ) 2 - (R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 ,- O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x - -O-Si(R 2 )
  • a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a POSS molecule of the structure: wherein: each R 1 is the same or different and is selected from the group consisting of -O-Si(R 2 ) 2 - (R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 ,-O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -, -O-Si(R
  • FIG. 1 shows, according to one set of embodiments, a schematic diagram of an exemplary article.
  • FIG. 2 shows, according to one set of embodiments, a schematic diagram of an exemplary method of coating a substrate.
  • FIG. 3 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a polyhedral oligomeric silsesquioxane (POSS) molecule functionalized with polydimethylsiloxane.
  • PPS polyhedral oligomeric silsesquioxane
  • FIG. 4 shows, according to one set of embodiments, a thermogravimetric analysis (TGA) plot of a POSS molecule functionalized with poly dimethylsiloxane.
  • TGA thermogravimetric analysis
  • FIG. 5 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with poly dimethylsiloxane and a methacrylate group.
  • FIG. 6 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with a phenyl group.
  • FIG. 7 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with a phenyl group and a primary amine group.
  • FIG. 8 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with a phenyl group and a secondary amine group.
  • FIG. 9 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with a substituted phenyl group.
  • FIG. 10 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with a substituted phenyl group and a secondary amine group.
  • FIG. 11 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with 2,2,4-trimethylhexane.
  • FIG. 12 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with isopentane.
  • FIG. 13 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with isopentane and a primary amine group.
  • FIG. 14 shows, according to one set of embodiments, a gel permeation chromatogram of a POSS-dimer.
  • FIG. 15 shows, according to one set of embodiments, a gel permeation chromatogram of a second POSS-dimer.
  • FIG. 16 shows, according to one set of embodiments, a FT-IR spectrum of the second POSS-dimer.
  • the non-fluorinated POSS-based compound comprises a POSS molecule functionalized with a variety of suitable functional groups, including, for example, polydialkylsiloxane (e.g., polydimethylsiloxane) groups, tris(trialkylsiloxy)silane (e.g., tris(trimethylsiloxy)silane) groups, (meth)acrylate groups, phenyl groups, substituted phenyl groups, amine groups, azide groups, isocyanate groups, -C 1 -C 10 alkyl groups, allyl groups, alcohol groups, epoxy groups, thiol groups, and/or acidic groups.
  • suitable functional groups including, for example, polydialkylsiloxane (e.g., polydimethylsiloxane) groups, tris(trialkylsiloxy)silane (e.g., tris(trimethylsiloxy)silane) groups, (meth)acrylate groups, phenyl
  • the structure of the non-fluorinated POSS -based compound may advantageously be tuned depending on a particular application.
  • the POSS molecule comprises one or more polydialkylsiloxane groups.
  • the POSS molecule comprises one or more (meth)acrylate groups.
  • the non-fluorinated POSS-based compound is configured such that each silicon atom of the POSS molecule is functionalized with the same functional group.
  • the non-fluorinated POSS-based compound is multifunctional such that each silicon atom of the POSS molecule is functionalized with a functional group, wherein at least two functional groups are different (e.g., chemically different).
  • the multifunctionalized POSS-based compound may have multiple functionalities and/or uses.
  • the POSS molecule comprises one or more polydialky I siloxane groups and one or more (meth)acrylate groups.
  • Other combinations of functional groups are possible and a person of ordinary skill in the art would be capable of selecting such functional groups depending on the particular application, based upon the teachings of this specification.
  • the non-fluorinated POSS-based compound is configured such that at least one functional group of the POSS molecule is a bridging moiety to another POSS molecule.
  • the POSS-based compound comprises a first POSS molecule functionalized with one or more (meth)acrylate groups that form a bond to a second POSS molecule.
  • at least one functional group of the POSS molecule is a bridging moiety to another POSS molecule advantageously provides extended structures of POSS-based dimers, oligomers, and/or polymers.
  • each monomer of the POSS-based dimer, oligomer, and/or polymer has the same or different functionalities.
  • the non-fluorinated POSS-based compounds described herein are used as additives in compositions comprising one or more base polymers (e.g., resins such as epoxy-containing resins and/or (meth)acry late-containing resins).
  • the non-fluorinated POSS-based additive is configured to interact (e.g., crosslink) with the one or more base polymers.
  • the use of a non-fluorinated POSS-based additive results in the composition having an advantageously low surface energy, e.g., as compared to a composition that is otherwise equivalent but does not comprise the non-fluorinated POSS-based additive.
  • a composition comprising the non-fluorinated POSS-based compound has a coefficient of friction less than or equal to 0.1.
  • the resulting compositions are used as coatings on a wide variety of substrates, including, for example, glass, ceramics, metals, metal oxides, and/or polymers.
  • POSS-based compounds comprising POSS molecules having 8 Si tetrahedral vertices (T vertices)
  • T vertices Te vertices
  • those of ordinary skill in the art would understand, based upon the teachings of this specification, that other lower-order and/or higher-order POSS molecules are also possible.
  • POSS molecules comprising 4 Si T vertices, 6 Si T vertices, 10 Si T vertices, and/or 12 Si T vertices, or more, are possible.
  • a POSS-based compound (e.g., a POSS-based additive) comprises a plurality of POSS molecules, each POSS molecule having the same or different number of Si tetrahedral vertices.
  • each POSS molecule has 8 Si T vertices as depicted in Formula (I), below.
  • the POSS molecule has a formula as in Si z O 1.5z R 1 z , where each R 1 is the same or different and is selected from the group consisting of-O-Si(R 2 ) 2 -(R 3 ) x - Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x - -O-Si(R 2 ) 2 -(R 3 ) x -O-CH-CH
  • z is greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, greater than or equal to 9, greater than or equal to 10, greater than or equal to 11, or greater than or equal to 12.
  • z is less than or equal to 14, less than or equal to 13, less than or equal to 12, less than or equal to 11, less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, or less than or equal to 5.
  • Combinations of the above-reference ranges are also possible (e.g., z is greater than or equal to 4 and less than or equal to 14). Other ranges are also possible.
  • the POSS-based compound comprises a POSS molecule according to Formula (I): wherein: each R 1 is the same or different and is selected from the group consisting of-O-Si(R 2 ) 2 - (R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -, -O-Si(R 2 ) 2 -(R 3 ) x -O-O-O-O-O-
  • each y is the same or different and is greater than or equal to 1 and less than or equal to 3, and n is greater than or equal to 2 and less than or equal to 100.
  • each R 1 , R 2 , and/or R 3 may, in some embodiments, be optionally substituted.
  • at least one R 1 , R 2 , and/or R 3 is optionally substituted with a poly dialkylsiloxane group (e.g., poly dimethylsiloxane).
  • at least one R 2 is -C 1 -C 10 alkyl substituted with a polydialkylsiloxane (e.g., polydimethylsiloxane) group.
  • each x in the POSS molecule according to Formula (I) may be selected from a variety of suitable values.
  • the value of each x in the POSS molecule according to Formula (I) is independently greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9.
  • the value of each x in the POSS molecule according to Formula (I) is independently less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1.
  • Combinations of the above recited ranges are possible (e.g., the value of each x in the POSS molecule according to Formula (I) is independently greater than or equal to 0 and less than or equal to 10, the value of each x in the POSS molecule according to Formula (I) is independently greater than or equal to 4 and less than or equal to 6).
  • Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for x based upon the teachings of this specification.
  • each y in the POSS molecule according to Formula (I) may be selected from a variety of suitable values. In some embodiments, for example, the value of each y in the POSS molecule according to Formula (I) is independently greater than or equal to 1 or greater than or equal to 2. In some embodiments, the value of each y in the POSS molecule according to Formula (I) is independently less than or equal to 3 or less than or equal to 2. Combinations of the above recited ranges are possible (e.g., the value of each y in the POSS molecule according to Formula (I) is independently greater than or equal to 1 and less than or equal to 3). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for y based upon the teachings of this specification.
  • n in the POSS molecule according to Formula (I) may be selected from a variety of suitable values.
  • the value of n in the POSS molecule according to Formula (I) is greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90.
  • the value of n in the POSS molecule according to Formula (I) is less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 20, less than or equal to 10, less than or equal to 5, or less than or equal to 2.
  • the POSS molecule comprises 8 Si T vertices corresponding to a T 8 cage (e.g., as in Formula (I)). In other embodiments, however, the POSS molecule comprises any of a variety of suitable Si T vertices, as described above. In some embodiments, for example, the POSS molecule comprises 4 Si T vertices (a T 4 cage having 4 R 1 groups), 6 Si T vertices (a T 6 cage having 6 R 1 groups), 10 Si T vertices (a T 10 cage having 10 R 1 groups), or 12 Si T vertices (a T 12 cage having 12 R 1 groups).
  • any of the concepts described herein may also correspond to a POSS molecule comprising a T 4 cage, a T 6 cage, a T 10 cage, or a T 12 cage.
  • the POSS molecule (e.g., such as a POSS molecule according to Formula (I)) is substantially non-fluorinated.
  • the POSS molecule comprises fluorine in an amount less than or equal to 5 wt.%, less than or equal to 4 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, or less than or equal to 0.2 wt.% versus a total weight of the POSS molecule.
  • the POSS molecule comprises fluorine in an amount greater than or equal to 0 wt.%, greater than or equal to 0.2 wt.%, greater than or equal to 0.5 wt.%, greater than or equal to 1 wt.%, greater than or equal to 2 wt.%, greater than or equal to 3 wt.%, or greater than or equal to 4 wt.% versus a total weight of the POSS molecule.
  • the POSS molecule comprises fluorine in an amount less than or equal to 5 wt.% and greater than or equal to 0 wt.% versus a total weight percent of the POSS molecule
  • the POSS molecule comprises fluorine in an amount less than or equal to 2 wt.% and greater than or equal to 1 wt.% versus a total weight of the POSS molecule.
  • Other ranges are also possible.
  • the POSS molecule is non-fluorinated such that the POSS molecule comprises fluorine in an amount of 0 wt.% versus a total weight of the POSS molecule.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with a polydialkylsiloxane group (e.g., polydimethylsiloxane).
  • a POSS molecule functionalized with a polydialkylsiloxane group advantageously provides a hydrophobic and/or low surface energy material.
  • At least one R 1 in the POSS molecule is -O- Si(R 2 ) 2 -(R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 .
  • the at least one R 1 is -O-Si(CH 3 ) 2 -(CH 2 ) x -Si(CH 3 ) 2 -O-[Si(CH 3 ) 2 -O] n -Si(CH 3 ) 3 (e.g., -O- Si(CH 3 ) 2 -(CH 2 ) 2 -Si(CH 3 ) 2 -O-[Si(CH 3 ) 2 -O] n -Si(CH 3 ) 3 ).
  • each R 1 in the POSS molecule is -O-Si(R 2 ) 2 -(R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n - Si(R 2 ) 3 .
  • each R 1 is -O-Si(CH 3 ) 2 -(CH 2 ) x - Si(CH 3 ) 2 -O-[Si(CH 3 ) 2 -O] n -Si(CH 3 ) 3 (e.g., - O-Si(CH 3 ) 2 -(CH 2 ) 2 -Si(CH 3 ) 2 -O-[Si(CH 3 ) 2 -O] n - Si(CH 3 ) 3 ).
  • Other polydialkylsiloxane groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with a tris(trialkylsiloxy)silane group (e.g., tris(trimethylsiloxy)silane).
  • a POSS molecule functionalized with a tris(trialkylsiloxy)silane group advantageously provides a hydrophobic and/or low surface energy material.
  • at least one R 1 in the POSS molecule (e.g., according to Formula (I)) is -O- Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 .
  • the at least one R 1 is -O-Si(CH 3 ) 2 -(CH 2 ) x -Si(OSi(CH 3 ) 3 ) 3 (e.g., -O-Si(CH 3 ) 2 -Si(OSi(CH 3 ) 3 ) 3 ).
  • each R 1 in the POSS molecule e.g., according to Formula (I)
  • each R 1 is -O-Si(CH 3 ) 2 -(CH 2 ) x - Si(OSi(CH 3 ) 3 ) 3 (e.g., -O-Si(CH 3 ) 2 -Si(OSi(CH 3 ) 3 ) 3 ).
  • Other tris(trialkylsiloxy)silane groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with a (meth)acrylate group.
  • a POSS molecule functionalized with a (meth)acrylate group advantageously provides a material capable of crosslinking, e.g., with another POSS molecule and/or with one or more components of a composition comprising the POSS-based compound, as described in greater detail elsewhere herein.
  • At least one R 1 in the POSS molecule is -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) or -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -.
  • the at least one R 1 is -O-Si(CH 3 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ) (e.g., -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )(CH 2 ) 2 -O-C(O)-C(CH 3 )(CH 2 )) or -O- Si(CH 3 ) 2 -(R 3 ) x -C(O)-O(CH 2 ) 2 C(CH 3 )(CH 2 )- (e.g., -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )-C(O)- O(CH 2 ) 2 C(CH 3 )(CH 2 )-).
  • each R 1 in the POSS molecule is -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) or -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -.
  • each R 1 is -O-Si(CH 3 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ) (e.g., -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )(CH 2 ) 2 -O-C(O)-C(CH 3 )(CH 2 )) or -O- Si(CH 3 ) 2 -(R 3 ) x -C(O)-O(CH 2 ) 2 C(CH 3 )(CH 2 )- (e.g., -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )-C(O)- O(CH 2 ) 2 C(CH 3 )(CH 2 )-).
  • Other (meth)acrylate groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with a phenyl group.
  • a POSS molecule functionalized with a phenyl group advantageously provides a hydrophobic material capable of intra- or intermolecular ⁇ - ⁇ stacking interactions.
  • at least one R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -C 6 H 5 .
  • the at least one R 1 is -(CH 2 ) x -C 6 H 5 (e.g., -C 6 H 5 ).
  • each R 1 in the POSS molecule is -(R 3 ) x -C 6 H 5 .
  • each R 1 is -(CH 2 ) x -C 6 H 5 (e.g., -C 6 H 5 ).
  • Other phenyl groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with a substituted phenyl group.
  • a POSS molecule functionalized with a substituted phenyl group advantageously provides a hydrophobic material capable of intra- or intermolecular ⁇ - ⁇ stacking interactions.
  • the substituted phenyl group may be substituted with at least one methyl group, at least one t- butyl group, and/or at least one phenyl group.
  • the substituted phenyl group comprises biphenyl.
  • At least one R 1 in the POSS molecule is -(R 3 ) x -C 6 H 4 -(R 3 ) x -(R 2 ) y .
  • the at least one R 1 is -(CH 2 ) x -C 6 H 4 -CH 3 , -(CH 2 ) x -C 6 H 3 -(CH 3 ) 2 ,-(CH 2 ) x - C 6 H 4 -C(CH 3 ) 3 , -(CH 2 ) x -C 6 H 3 -(C(CH 3 ) 3 ) 2 , or -(CH 2 ) x -C 6 H 4 -C 6 H 5 (e.g., -(CH 2 ) 2 -C 6 H 4 -CH 3 , - (CH 2 ) 2 -C 6 H 3 -(CH 3 ) 2 , -(CH 2 ) 2 -C 6 H 4 -C(CH 3 ) 3 , -(CH 2 ) 2 -C 6 H 3 -(C(CH 3 ) 2 , or -(CH 2 ) 2 -CH 3 , -(CH 2 )
  • each R 1 in the POSS molecule is -(R 3 ) x - C 6 H 4 -(R 3 ) x -(R 2 ) y .
  • each R 1 is -(CH 2 ) x -C 6 H 4 - CH 3 , -(CH 2 ) x -C 6 H 3 -(CH 3 ) 2 , -(CH 2 ) x -C 6 H 4 -C(CH 3 ) 3 , -(CH 2 ) x -C 6 H 3 -(C(CH 3 ) 3 ) 2 , or -(CH 2 ) x - C 6 H 4 -C 6 H 5 (e.g., -(CH 2 ) 2 -C 6 H 4 -CH 3 , -(CH 2 ) 2 -C 6 H 3 -(CH 3 ) 2 ,-(CH
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with an amine group.
  • a POSS molecule functionalized with an amine group advantageously provides a material capable of chemical reactivity (e.g., crosslinking), for example, with one or more components of a composition comprising the POSS-based compound.
  • the amine group is a primary amine group.
  • at least one R 1 in the POSS molecule is -(R 3 ) x -NH 2 .
  • the at least one R 1 is -(CH 2 ) x -NH 2 (e.g., -(CH 2 ) 3 -NH 2 ).
  • each R 1 in the POSS molecule e.g., according to Formula (I)
  • each R 1 is -(CH 2 ) x -NH 2 (e.g., -(CH 2 ) 3 -NH 2 ).
  • Other primary amine groups are also possible.
  • the amine group is a secondary amine group.
  • At least one R 1 in the POSS molecule is -(R 3 ) x -NH-R 2 .
  • the at least one R 1 is -(CH 2 ) x -NH-C 6 H 5 (e.g., -(CH 2 ) 3 -NH-C 6 H 5 ).
  • each R 1 in the POSS molecule is -(R 3 ) x -NH- R 2 .
  • each R 1 is -(CH 2 ) x -NH-C 6 H 5 (e.g., - (CH 2 ) 3 -NH-C 6 H 5 ).
  • the secondary amine group comprises ethylenediamine, trisethylenediamine, and/or tetraethylenediamine.
  • At least one R 1 in the POSS molecule is -(R 3 ) x - NH-(CH 2 ) 2 -NH 2 , -(R 3 ) x -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2 , and/or -(R 3 ) x -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH- (CH 2 ) 2 -NH 2 .
  • each R 1 in the POSS molecule is -(R 3 ) x -NH-(CH 2 ) 2 -NH 2 , -(R 3 ) x -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2 , and/or -(R 3 ) x -NH-(CH 2 ) 2 - NH-(CH 2 ) 2 -NH 2 .
  • Other secondary amine groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with an azide group.
  • a POSS molecule functionalized with an azide group advantageously provides a material capable of chemical reactivity (e.g., click chemistry), for example, with one or more components of a composition comprising the POSS-based compound.
  • at least one R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -N 3 .
  • the at least one R 1 is -(CH 2 ) x -N 3 .
  • each R 1 in the POSS molecule is -(R 3 ) x -N 2 .
  • each R 1 is -(CH 2 ) x -N 3 .
  • Other azide groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with an isocyanate group.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with a -C 1 -C 10 alkyl group.
  • at least one R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -(R 2 ) y .
  • the at least one R 1 is -(CH 2 )-(CH)(CH 3 )-(CH 2 )-C(CH 3 ) 3 or -(CH 2 )- (CH)(CH 3 ) 2 .
  • each R 1 in the POSS molecule is -(R 3 ) x -(R ) y .
  • each R 1 is (CH 2 )- (CH)(CH 3 )-(CH 2 )-C(CH 3 ) 3 or -(CH 2 )-(CH)(CH 3 ) 2 .
  • Other -C 1 -C 10 alkyl groups are also possible.
  • the POSS molecule e.g., according to Formula (I)
  • a POSS molecule functionalized with an allyl group advantageously provides a material capable of crosslinking, e.g., with another POSS molecule and/or with one or more components of a composition comprising the POSS-based compound, as described in greater detail elsewhere herein.
  • at least one R 1 in the POSS molecule e.g., according to Formula (I) is -O- Si(R 2 ) 2 -(R 3 ) x -O-CH 2 CHCH 2 or -O-CH 2 CHCH 2 .
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with an alcohol group.
  • a POSS molecule functionalized with an alcohol group advantageously provides a material capable of chemical reactivity (e.g., crosslinking), for example, with one or more components of a composition comprising the POSS-based compound.
  • at least one R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -OH.
  • at least one R 1 is -(CH 2 ) x -OH.
  • each R 1 in the POSS molecule is -(R 3 ) x -OH.
  • each R 1 is -(CH 2 ) x -OH.
  • Other alcohol groups are possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with an epoxy group.
  • a POSS molecule functionalized with an epoxy group advantageously provides a material capable of chemical reactivity (e.g., covalent bonding), for example, with one or more components of a composition comprising the POSS-based compound.
  • at least one R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -(C 2 H 4 O).
  • the at least one R 1 is -(CH 2 ) x -(C 2 H 4 O).
  • each R 1 in the POSS molecule is -(R 3 ) x -(C 2 H 4 O).
  • each R 1 is -(CH 2 ) x -(C 2 H 4 O).
  • Other epoxy groups are also possible.
  • the POSS molecule e.g., according to Formula (I)
  • a POSS molecule functionalized with a thiol group advantageously provides a material capable of chemical reactivity (e.g., thiol-ene reactions), for example, with one or more components of a composition comprising the POSS-based compound (e.g., a vinyl-containing component).
  • at least one R 1 in the POSS molecule e.g., according to Formula (I)
  • at least one R 1 is -(CH 2 ) x -SH.
  • each R 1 in the POSS molecule is -(R 3 ) x -SH.
  • each R 1 is -(CH 2 ) x -SH.
  • Other thiol groups are also possible.
  • the POSS molecule (e.g., according to Formula (I)) is functionalized with an acidic group.
  • at least one R 1 in the POSS molecule comprises an acidic group.
  • the acidic group is a Bronsted-Lowry acid that is capable of donating a proton.
  • the acid is a Lewis acid that is capable of forming a covalent bond with an electron pair.
  • the acidic group comprises a sulfonic acid group (e.g., -SO 3 H), a phosphoric acid group (e.g., -PO 4 H 2 ), a carboxylic acid group (e.g., -COOH), a thiol group (e.g., -SH), an alcohol group (e.g. , -OH), an amine group (e.g., -NH 2 ), and/or combinations thereof.
  • a sulfonic acid group e.g., -SO 3 H
  • a phosphoric acid group e.g., -PO 4 H 2
  • carboxylic acid group e.g., -COOH
  • a thiol group e.g., -SH
  • an alcohol group e.g. , -OH
  • an amine group e.g., -NH 2
  • the POSS molecule is multifunctionalized.
  • the term “multifunctionalized” refers to a molecule comprising at least two different (e.g., chemically different) functional groups.
  • the POSS molecule e.g., according to Formula (I)
  • the POSS molecule is configured such that at least one R 1 is different from another R 1 .
  • two or more, three or more, four or more, five or more, six or more, or seven or more R 1 groups are different from another R 1 .
  • the following embodiments are meant to be illustrative of some such embodiments but are not intended to be limiting.
  • the multifunctionalized POSS molecule comprises at least two different (e.g., chemically different) functional groups.
  • the POSS molecule e.g., according to Formula (I)
  • a first R 1 in the POSS molecule is different from a second R 1 in the POSS molecule.
  • the ratio of the first R 1 to the second R 1 may be selected from a variety of suitable ratios.
  • the ratio of the first R 1 to the second R 1 is greater than or equal 1 :7 (e.g., n a is 1 and n b is 7), greater than or equal to 2:6 (e.g., n a is 2 and n b is 6), greater than or equal to 3:5 (e.g., n a is 3 and n b is 5), greater than or equal to 4:4 (e.g., n a is 4 and n b is 4), greater than or equal to 5:3 (e.g., n a is 5 and n b is 3), or greater than or equal to 6:2 (e.g., n a is 6 and n b is 2).
  • 1 :7 e.g., n a is 1 and n b is 7
  • 2:6 e.g., n a is 2 and n b is 6
  • 3:5 e.g., n a is 3 and n b is
  • the ratio of the first R 1 to the second R 1 is less than or equal to 7:1 (e.g., n a is 7 and n b is 1), less than or equal to 6:2 (e.g., n a is 6 and n b is 2), less than or equal to 5:3 (e.g., n a is 5 and n b is 3), less than or equal to 4:4 (e.g., n a is 4 and n b is 4), less than or equal to 3:5 (e.g., n a is 3 and n b is 5), or less than or equal to 2:6 (e.g., n a is 2 and n b is 6).
  • 7:1 e.g., n a is 7 and n b is 1
  • 6:2 e.g., n a is 6 and n b is 2
  • 5:3 e.g., n a is 5 and n b is 3
  • the ratio of the first R 1 to the second R 1 is
  • the multifunctionalized POSS molecule comprises at least three different (e.g., chemically different) functional groups.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 in the POSS molecule is different from the second R 1 in the POSS molecule and a third R 1 in the POSS molecule.
  • the second R 1 is different from the third R 1 .
  • the ratio of the first R 1 to the second R 1 and the third R 1 may be selected from a variety of suitable ratios.
  • the multifunctionalized POSS molecule comprises at least four different (e.g., chemically different) functional groups.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is different from the third R 1 and the fourth R 1
  • the third R 1 is different from the fourth R 1 .
  • the ratio of the first R 1 to the second R 1 , the third R 1 , and the fourth R 1 may be selected from a variety of suitable ratios.
  • the multifunctionalized POSS molecule having a T 8 structure comprises n a first R 1 groups, n b second R 1 groups, n c third R 1 groups, and n d fourth R 1 groups, wherein each of n a , n b , n c , and n d are independently greater than or equal to 1 and less than or equal to 5 such that n a + n b + n c + n d 8.
  • the multifunctionalized POSS molecule comprises at least five different (e.g., chemically different) functional groups.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is different from the third R 1 , the fourth R 1 , and the fifth R 1 .
  • the third R 1 is different from the fourth R 1 and the fifth R 1 .
  • the fourth R 1 is different from the fifth R 1 .
  • the ratio of the first R 1 to the second R 1 , the third R 1 , the fourth R 1 , and the fifth R 1 may be selected from a variety of suitable ratios.
  • the multifunctionalized POSS molecule comprises at least six different (e.g., chemically different) functional groups.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 in the POSS molecule is different from the third R 1 in the POSS molecule, the fourth R 1 in the POSS molecule, the fifth R 1 in the POSS molecule, and a sixth R 1 in the POSS molecule.
  • the second R 1 is different from the third R 1 , the fourth R 1 , the fifth R 1 , and the sixth R 1 .
  • the third R 1 is different from the fourth R 1 , the fifth R 1 , and the sixth R 1 .
  • the fourth R 1 is different from the fifth R 1 and the sixth R 1 .
  • the fifth R 1 is different from the sixth R 1 .
  • the ratio of the first R 1 to the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , and the sixth R 1 may be selected from a variety of suitable ratios.
  • the multifunctionalized POSS molecule comprises at least seven different (e.g., chemically different) functional groups.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 in the POSS molecule is different from the second R 1 in the POSS molecule, the third R 1 in the POSS molecule, the fourth R 1 in the POSS molecule, the fifth R 1 in the POSS molecule, the sixth R 1 in the POSS molecule, and a seventh R 1 in the POSS molecule.
  • the second R 1 is different from the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , and the seventh R 1 .
  • the third R 1 is different from the fourth R 1 , the fifth R 1 , the sixth R 1 , and the seventh R 1 .
  • the fourth R 1 is different from the fifth R 1 , the sixth R 1 , and the seventh R 1 .
  • the fifth R 1 is different from the sixth R 1 and the seventh R 1 .
  • the sixth R 1 is different from the seventh R 1 .
  • the ratio of the first R 1 to the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , and the seventh R 1 may be selected from a variety of suitable ratios.
  • the multifunctionalized POSS molecule comprises eight different (e.g., chemically different) functional groups.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 in the POSS molecule is different from the second R 1 in the POSS molecule, the third R 1 in the POSS molecule, the fourth R 1 in the POSS molecule, the fifth R 1 in the POSS molecule, the sixth R 1 in the POSS molecule, the seventh R 1 in the POSS molecule, and an eighth R 1 in the POSS molecule.
  • the second R 1 is different from the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and the eighth R 1 .
  • the third R 1 is different from the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and the eighth R 1 .
  • the fourth R 1 is different from the fifth R 1 , the sixth R 1 , the seventh R 1 , and the eighth R 1 .
  • the fifth R 1 is different from the sixth R 1 , the seventh R 1 , and the eighth R 1 .
  • the sixth R 1 is different from the seventh R 1 and the eighth R 1 .
  • the seventh R 1 is different from the eighth R 1 .
  • a multifunctionalized POSS molecule having a T 4 structure comprises n a first R 1 groups, n b second R 1 groups, n c third R 1 groups, and n d fourth R 1 groups.
  • each first R 1 group, second R 1 group, third R 1 group, and fourth R 1 group may be the same or different provided that at least one R 1 is different from another R 1 .
  • a multifunctionalized POSS molecule having a T 6 structure comprises n a first R 1 groups, n b second R 1 groups, n c third R 1 groups, n d fourth R 1 groups, rie fifth R 1 groups, and n f sixth R 1 groups.
  • each first R 1 group, second R 1 group, third R 1 group, fourth R 1 group, fifth R 1 group, and sixth R 1 group may be the same or different provided that at least one R 1 is different from another R 1 .
  • a multifunctionalized POSS molecule having a T 10 structure comprises n a first R 1 groups, n b second R 1 groups, n c third R 1 groups, n d fourth R 1 groups, n e fifth R 1 groups, n f sixth R 1 groups, n g seventh R 1 groups, n h eighth R 1 groups, n i ninth R 1 groups, and n j tenth R 1 groups.
  • each first R 1 group, second R 1 group, third R 1 group, fourth R 1 group, fifth R 1 group, sixth R 1 group, seventh R 1 group, eighth R 1 group, ninth R 1 group, and tenth R 1 group may be the same or different provided that at least one R 1 is different from another R 1 .
  • a multifunctionalized POSS molecule having a T 12 structure comprises n a first R 1 groups, n b second R 1 groups, n c third R 1 groups, n d fourth R 1 groups, n e fifth R 1 groups, n f sixth R 1 groups, n g seventh R 1 groups, n h eighth R 1 groups, n i ninth R 1 groups, n j tenth R 1 groups, n k eleventh R 1 groups, and n l twelfth R 1 groups.
  • each first R 1 group, second R 1 group, third R 1 group, fourth R 1 group, fifth R 1 group, sixth R 1 group, seventh R 1 group, eighth R 1 group, ninth R 1 group, tenth R 1 group, eleventh R 1 group, and twelfth R 1 group may be the same or different provided that at least one R 1 is different from another R 1 .
  • the multifunctionalized POSS molecule (e.g., according to Formula (I)) is functionalized with a polydialkylsiloxane group (e.g., poly dimethylsiloxane).
  • a polydialkylsiloxane group e.g., poly dimethylsiloxane
  • the first R 1 in the POSS molecule is -O-Si(R 2 ) 2 -(R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 .
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R 2 ) 2 -(R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 - O] n -Si(R 2 ) 3 , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group that is chemically different than the first R 1 , a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group
  • suitable functional groups e.
  • the multifunctionalized POSS is functionalized with a tris(trialkylsiloxy)silane group (e.g., tris(trimethylsiloxy)silane).
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 is -O-Si(CH 3 ) 2 -(CH 2 ) x - Si(OSi(CH 3 ) 3 ) 3 (e.g., -O-Si(CH 3 ) 2 -Si(OSi(CH 3 ) 3 ) 3 ).
  • Other tris(trialkylsiloxy)silane groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group that is chemically different than the first R 1 , a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is functionalized with a (meth)acrylate group.
  • the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) or -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -
  • the first R 1 is -O- Si(CH 3 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) (e.g., -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )(CH 2 ) 2 -O-C(O)- C(CH 3 )(CH 2
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) or -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x - and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group that is chemically different than the first R 1 , a
  • the multifunctionalized POSS molecule is functionalized with a phenyl group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 is -(R 3 ) x -C 6 H 5 .
  • the first R 1 is -(CH 2 ) x -C 6 H 5 (e.g., -C 6 H 5 ).
  • Other phenyl groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is (R 3 ) x -C 6 H 5 , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group that is chemically different than the first R 1 , a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as
  • suitable functional groups e.
  • the multifunctionalized POSS molecule (e.g., according to Formula (I)) is functionalized with a substituted phenyl group.
  • the first R 1 in the POSS molecule (e.g., according to Formula (I)) is - (R 3 ) x -C 6 H 4 -(R 3 ) x -(R 2 ) y .
  • the first R 1 is -(CH 2 ) x -C 6 H 4 -CH 3 , - (CH 2 ) x -C 6 H 3 -(CH 3 ) 2 ,-(CH 2 ) x -C 6 H 4 -C(CH 3 ) 3 , -(CH 2 ) x -C 6 H 3 -(C(CH 3 ) 3 ) 2 , or - (CH 2 ) x -C 6 H 4 -C 6 H 5 (e.g., -(CH 2 ) 2 -C 6 H 4 -CH 3 , -(CH 2 ) 2 -C 6 H 3 -(CH 3 ) 2 ,-(CH 2 ) 2 -C 6 H 4 -C(CH 3 ) 3 , -(CH 2 ) 2 -C 6 H 3 - (C(CH 3 ) 3 , or -(CH 2 ) 2 -C 6 H 4 -CH 3 ,
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is — (R 3 ) x - C 6 H 4 -(R 3 ) x -(R 2 ) y , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group that is chemically different than the first R 1 , an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is functionalized with an amine group.
  • the amine group is a primary amine group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 is -(R 3 ) x -NH 2 .
  • the first R 1 is -(CH 2 ) x -NH 2 (e.g., -(CH 2 ) 3 -NH 2 ).
  • Other primary amine groups are also possible.
  • the amine group is a secondary amine group.
  • the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -NH-R 2 .
  • the first R 1 is -(CH 2 ) x -NH-C 6 H 5 (e.g., -(CH 2 ) 3 -NH-C 6 H 5 ).
  • the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -NH-(CH 2 ) 2 -NH 2 , - (R 3 ) x -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2 , and/or -(R 3 ) x -NH-(CH 2 ) 2 -NH-(CH 2 ) 2 -NH 2 .
  • Other secondary amine groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -NH 2 or -(R 3 ) x -NH-R 2 , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group that is chemically different than the first R 1 , an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group,
  • suitable functional groups e.g
  • the multifunctionalized POSS molecule is functionalized with an azide group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 is -(R 3 ) x -N 3 .
  • the first R 1 is - (CH 2 ) x -N 3 .
  • Other azide groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -N 3 , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group that is chemically different than the first R 1 , an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is a functionalized with an isocyanate group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • suitable functional groups e.g., a polydialkylsiloxane group,
  • the multifunctionalized POSS molecule is functionalized with a -C 1 -C 10 alkyl group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 is -(CH 2 )-(CH)(CH 3 )-(CH 2 )-C(CH 3 ) 3 or -(CH 2 )-(CH)(CH 3 ) 2 .
  • Other - C 1 -C 10 alkyl groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -(R 2 ) y , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group that is chemically different than the first R 1 , an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is functionalized with an allyl group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 in the POSS molecule is -O-Si(R 2 ) 2 -(R 3 ) x -O-CH 2 CHCH 2 or -O-CH 2 CHCH 2 .
  • the first R 1 is -O-Si(CH 3 ) 2 -(R 3 ) x -O-CH 2 CHCH 2 or -O- CH 2 CHCH 2 .
  • Other allyl groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R 2 ) 2 -(R 3 ) x -O-CH 2 CHCH 2 , and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 - C 10 alkyl group, an allyl group that is chemically different than the first R 1 , an alcohol group, an epoxy group,
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is functionalized with an alcohol group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 in the POSS molecule is -(R 3 ) x -OH.
  • the first R 1 is -(CH 2 ) x -OH.
  • Other alcohols are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -OH, and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a-C 1 -C 10 alkyl group, an allyl group, an alcohol group that is chemically different than the first R 1 , an epoxy group, a thiol group, and/or an acidic group), as described in greater
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is functionalized with an epoxy group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 in the POSS molecule is -(R 3 ) x -(C 2 H 4 O).
  • the first R 1 is -(CH 2 ) x -(C 2 H 4 O).
  • Other epoxy groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -(C 2 H 4 O), and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a-C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group that is chemically different than the first R 1 , a thiol group, and/or an acidic group
  • suitable functional groups e.
  • the multifunctionalized POSS molecule is functionalized with a thiol group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 in the POSS molecule is -(R 3 ) x -SH.
  • the first R 1 is - (CH 2 ) x -SH.
  • Other thiols are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -(R 3 ) x -SH, and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group that is chemically different than the first R 1 , and/or an acidic group), as described in
  • the multifunctionalized POSS molecule is functionalized with an acidic group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 in the POSS molecule is a Bronsted-Lowry acid that is capable of donating a proton.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the first R 1 comprises a sulfonic acid group (e.g., -SO3H), a phosphoric acid group (e.g., -PO 4 H 2 ), a carboxylic acid group (e.g., -COOH), a thiol group (e.g., -SH), an alcohol group (e.g. , -OH), an amine group (e.g., -NH 2 ), and/or combinations thereof.
  • a sulfonic acid group e.g., -SO3H
  • a phosphoric acid group e.g., -PO 4 H 2
  • carboxylic acid group e.g., -COOH
  • a thiol group e.g., -SH
  • an alcohol group e.g. , -OH
  • an amine group e.g., -NH 2
  • Other acidic groups are also possible.
  • the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is an acidic group, and at least one of the second R 1 , the third R 1 , the fourth R 1 , the fifth R 1 , the sixth R 1 , the seventh R 1 , and/or the eight R 1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group that is chemically different than the first R 1 ), as described in greater detail elsewhere herein.
  • suitable functional groups e.g.
  • the multifunctionalized POSS molecule is functionalized with a polydialkylsiloxane group (e.g., polydimethylsiloxane) and a (meth)acrylate group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is -O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) or -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) r -.
  • the first R 1 is -O-Si(CH 3 ) 2 -(CH 2 ) 2 -Si(CH 3 ) 2 -O-[Si(CH 3 ) 2 -O] n - Si(CH 3 ) 3 and the second R 1 is -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )(CH 2 ) 2 -O-C(O)-C(CH 3 )(CH 2 ) or- O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )-C(O)-O(CH 2 ) 2 C(CH 3 )(CH 2 )-.
  • the multifunctionalized POSS molecule is functionalized with a phenyl group and a primary amine group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is - (R 3 ) x -NH 2 .
  • the first R 1 is -C 6 H 5 and the second R 1 is - (CH 2 ) 3 -NH 2 .
  • the multifunctionalized POSS molecule is functionalized with a phenyl group and a secondary amine group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is -(R 3 ) x -NH-R 2 .
  • the first R 1 is -C 6 H 5 at the second R 1 is -(CH 2 ) 3 -NH-C 6 H 5 .
  • the multifunctionalized POSS molecule is functionalized with a substituted phenyl group and a primary amine group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is -(R 3 ) x -NH 2 .
  • the first R 1 is -(CH 2 ) 2 -C 6 H 4 -C(CH 3 ) 3 and the second R 1 is -(CH 2 ) 3 -NH 2 .
  • the multifunctionalized POSS molecule is functionalized with a primary amine group and a -C 1 -C 10 alkyl group.
  • the first R 1 in the POSS molecule e.g., according to Formula (I)
  • the second R 1 is — (R 3 ) x -(R 2 ) y .
  • the first R 1 is -(CH 2 ) 3 -NH 2 and the second R 1 is -(CH 2 )-(CH)(CH 3 )-(CH 2 )-C(CH 3 ) 3 or -(CH 2 )-(CH)(CH 3 ) 2 .
  • the POSS molecule (e.g., according to Formula (I)) is a first POSS molecule and at least one R 1 is configured to form a bond to a second POSS molecule.
  • at least one R 1 is a bridging moiety to another silicon (Si) atom of a second POSS molecule.
  • configuring the POSS compound such that at least one R 1 of the first POSS molecule (e.g., according to Formula (I)) is configured to form a bond to a second POSS molecule advantageously provides extended structures of POSS-based dimers, oligomers, and/or polymers.
  • the at least one R 1 configured to form a bond to a second POSS molecule may be selected from a variety of suitable functional groups.
  • the at least one R 1 configured to form a bond to a second POSS molecule comprises a bi-functional moiety that is capable of bridging between two Si atoms.
  • the at least one R 1 configured to form a bond to a second POSS molecule comprises a (meth)acrylate group.
  • the at least one R 1 configured to form a bond to a second POSS molecule is -O- Si(R 2 ) 2 -(R 3 ) x -O-C(O)-C(CH 3 )(CH 2 ) or -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -.
  • the at least one R 1 configured to form a bond to a second POSS molecule is -O- Si(CH 3 ) 2 -(R 3 ) x -C(O)-O(CH 2 ) 2 C(CH 3 )(CH 2 )- (e.g., -O-Si(CH 3 ) 2 -(CH 2 )(CH)(CH 3 )-C(O)- O(CH 2 ) 2 C(CH 3 )(CH 2 )-).
  • Other (meth)acrylate groups are also possible.
  • the at least one R 1 configured to form a bond to a second POSS molecule comprises an allyl group.
  • the second POSS molecule is a POSS molecule according to Formula (I). In some embodiments, the second POSS molecule is multifunctionalized. In some embodiments, the second POSS molecule is the same (e.g., chemically the same) as the first POSS molecule. In other embodiments, the second POSS molecule is different (e.g., chemically different) from the first POSS molecule.
  • the POSS-based compound comprises a POSS molecule according to Formula (II): wherein: each R 1 is the same or different and is selected from the group consisting of-O-Si(R 2 ) 2 - (R 3 ) x -Si(R 2 ) 2 -O-[Si(R 2 ) 2 -O] n -Si(R 2 ) 3 , -O-Si(R 2 ) 2 -(R 3 ) x -Si(OSi(R 2 ) 3 ) 3 ,-O-Si(R 2 ) 2 -(R 3 ) x -O-C(O)- C(CH 3 )(CH 2 ), -O-Si(R 2 ) 2 -(R 3 ) x -C(O)-O-(R 3 ) x -, -O-Si(R 2 ) 2 -(R 3 ) x -O-O-O
  • each y is the same or different and is greater than or equal to 1 and less than or equal to 3
  • n is greater than or equal to 2 and less than or equal to 100
  • m is greater than or equal to 2 and less than or equal to 100.
  • each R 1 , R 1 ’, R 2 , and/or R 3 may, in some embodiments, be optionally substituted.
  • at least one R 1 , R 1 ’, R 2 , and/or R 3 is optionally substituted with a polydialkylsiloxane group (e.g., polydimethylsiloxane).
  • at least one R 2 is -C 1 -C 10 alkyl substituted with a polydialkylsiloxane (e.g., polydimethylsiloxane) group.
  • each x in the POSS molecule according to Formula (II) may be selected from a variety of suitable values.
  • the value of each x in the POSS molecule according to Formula (II) is independently greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9.
  • the value of each x in the POSS molecule according to Formula (II) is independently less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1.
  • Combinations of the above recited ranges are possible (e.g., the value of each x in the POSS molecule according to Formula (II) is independently greater than or equal to 0 and less than or equal to 10, the value of each x in the POSS molecule according to Formula (II) is independently greater than or equal to 4 and less than or equal to 6). Other ranges are also possible.
  • each y in the POSS molecule according to Formula (II) may be selected from a variety of suitable values. In some embodiments, for example, the value of each y in the POSS molecule according to Formula (II) is independently greater than or equal to 1 or greater than or equal to 2. In some embodiments, the value of each y in the POSS molecule according to Formula (II) is independently less than or equal to 3 or less than or equal to 2.
  • n in the POSS molecule according to Formula (II) may be selected from a variety of suitable values.
  • the value of n in the POSS molecule according to Formula (II) is greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90.
  • the value of n in the POSS molecule according to Formula (II) is less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 20, less than or equal to 10, less than or equal to 5, or less than or equal to 2.
  • Combinations of the above recited ranges are possible (e.g., the value of n in the POSS molecule according to Formula (II) is greater than or equal to 1 and less than or equal to 100, the value of n in the POSS molecule according to Formula (II) is greater than or equal to 40 and less than or equal to 60).
  • Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for n based upon the teachings of this specification.
  • the value of m in the POSS molecule according to Formula (II) may be selected from a variety of suitable values.
  • the value of m in the POSS molecule according to Formula (II) is greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90.
  • the value of m in the POSS molecule according to Formula (II) is less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 20, less than or equal to 10, less than or equal to 5, or less than or equal to 2.
  • Combinations of the above recited ranges are possible (e.g., the value of m in the POSS molecule according to Formula (II) is greater than or equal to 1 and less than or equal to 100, the value of m in the POSS molecule according to Formula (II) is greater than or equal to 40 and less than or equal to 60).
  • Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for m based upon the teachings of this specification.
  • the value of m in the POSS molecule according to Formula (II) is greater than or equal to 2 and less than or equal to 4. In other nonlimiting embodiments, the value of m in the POSS molecule according to Formula (II) is greater than or equal to 2 and less than or equal to 3. In yet other non-limiting embodiments, the value of m in the POSS molecule according to Formula (II) is 2.
  • the POSS molecule comprises 8 Si T vertices corresponding to a T 8 cage (e.g., as in Formula (II)). In other embodiments, however, the POSS molecule comprises any of a variety of suitable Si T vertices, as described above. In some embodiments, for example, the POSS molecule comprises 4 Si T vertices (a T 4 cage having 4 R 1 groups), 6 Si T vertices (a T 6 cage having 6 R 1 groups), 10 Si T vertices (a T 10 cage having 10 R 1 groups), or 12 Si T vertices (a T 12 cage having 12 R 1 groups).
  • any of the concepts described herein may also correspond to a POSS molecule comprising a T 4 cage, a T 6 cage, a T 10 cage, or a T 12 cage.
  • each R 1 in the POSS molecule may independently comprise a polydialkylsiloxane (e.g., polydimethylsiloxane) group, a tris(trialkylsiloxy)silane (e.g., tris(trimethylsiloxy)silane) group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 -C 10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group, as described herein in greater detail with respect to the POSS molecule according to Formula (I).
  • a polydialkylsiloxane e.g., polydimethylsiloxane
  • a tris(trialkylsiloxy)silane e.g., tris(trimethylsiloxy)silane
  • each R 1 ’ in the POSS molecule comprises a bi-functional moiety that is capable of bridging between two Si atoms.
  • each R 1 ’ comprises a (meth)acrylate group and/or an allyl group.
  • each R 1 ’ in the POSS molecule comprises isoprenyl methacrylate and/or allyl alcohol.
  • the POSS molecule (e.g., according to Formula (II)) is multifunctionalized, as described herein in greater detail with respect to the POSS molecule according to Formula (I).
  • the POSS molecule (e.g., according to Formula (II)) is configured such that at least one R 1 is different from another R 1 .
  • a method of synthesizing a POSS-based compound (e.g., according to Formula (I) and/or Formula (II)) is described.
  • the synthesis of the POSS-based compound is advantageously straightforward and tunable such that a wide variety of POSS-based compounds with various functional groups (e.g., polydialkylsiloxane groups, tris(trialkylsiloxy)silane groups, (meth)acrylate groups, phenyl groups, substituted phenyl groups, amine groups, azide groups, isocyanate groups, -C 1 -C 10 alkyl groups, allyl groups, alcohol groups, epoxy groups, thiol groups, and/or acidic groups) may be obtained.
  • functional groups e.g., polydialkylsiloxane groups, tris(trialkylsiloxy)silane groups, (meth)acrylate groups, phenyl groups, substituted phenyl groups, amine groups, azide groups, isocyanate groups, -C 1 -C 10 alkyl groups, allyl groups, alcohol groups, epoxy groups, thiol groups, and/or acidic groups
  • the one or more precursor compounds comprise a poly dialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C 1 - C 10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group.
  • Other functional groups are also possible.
  • one or more precursor compounds comprising a (meth)acrylate group and/or an allyl group advantageously provides an extended structure of a POSS-based dimer, oligomer, and/or polymer, as described in greater detail elsewhere herein.
  • the one or more precursor compounds comprising the one or more functional groups may be selected from a variety of suitable precursor compounds.
  • the precursor compound comprising the one or more functional groups comprises a mono-vinyl polydialkylsiloxane (e.g., mono-vinyl polydimethylsiloxane) and/or isoprenyl methacrylate (IPEMA).
  • IPEMA isoprenyl methacrylate
  • reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups comprises reacting the precursor POSS molecule with one precursor compound comprising one or more functional groups.
  • reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups comprises reacting the precursor POSS molecule with more than one precursor compound (e.g., two precursor compounds, three precursor compounds, four precursor compounds, five precursor compounds, six precursor compounds, seven precursor compounds, or eight precursor compounds) comprising one or more functional groups.
  • reacting the precursor POSS molecule with more than one precursor compound comprising the one or more functional groups advantageously provides a multifunctionalized POSS molecule.
  • reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed in the presence of a catalyst.
  • the catalyst may be selected from a variety of suitable catalysts.
  • the catalyst comprises a metal such as palladium (Pd) (e.g., palladium metal or Pd(0)), a hydroxide (OH-) (e.g., potassium hydroxide or KOH), and/or water (H 2 O).
  • Pd palladium
  • OH- hydroxide
  • H 2 O water
  • the composition of the catalyst depends on the composition of the starting materials (e.g., the precursor POSS molecule and/or the one or more precursor compounds comprising one or more functional groups) and/or the reaction solvent.
  • Reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups may be performed at any of a variety of suitable temperatures. In some embodiments, for example, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 20 °C, greater than or equal to 40 °C, greater than or equal to 60 °C, greater than or equal to 80 °C, greater than or equal to 100 °C, greater than or equal to 120 °C, greater than or equal to 140 °C, greater than or equal to 160 °C, or greater than or equal to 180 °C.
  • reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature less than or equal to 200 °C, less than or equal to 180 °C, less than or equal to 160 °C, less than or equal to 140 °C, less than or equal to 120 °C, less than or equal to 100 °C, less than or equal to 80 °C, less than or equal to 60 °C, or less than or equal to 40 °C.
  • reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 20 °C and less than or equal to 200 °C
  • reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 100 °C and less than or equal to 120 °C.
  • the temperature of the reaction between the precursor POSS molecule and the one or more precursor compounds comprising the one or more functional groups depends on the composition of the starting materials (e.g., the precursor POSS molecule and/or the one or more precursor compounds comprising one or more functional groups) and/or the reaction solvent.
  • the precursor compound comprises trimethoxyphenylsilane, (3-aminopropyl)trimethoxysilane, N-(3- (trimethoxysilyl)propyl)aniline, p-(t-butyl)phenethyltrichlorosilane, trimethoxy(2,4,4- trimethylpentyl)silane, and/or isobutyltrimethoxysilane.
  • Other silicon-containing precursor compounds comprising one or more functional groups are also possible.
  • the composition comprises the POSS-based compound in an amount less than or equal to 10 wt.%, less than or equal to 9 wt.%, less than or equal to 8 wt.%, less than or equal to 7 wt.%, less than or equal to 6 wt.%, less than or equal to 5 wt.%, less than or equal to 4 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, or less than or equal to 0.2 wt.% versus a total weight of the composition.
  • the composition may comprise the one or more components (e.g., one or more base polymers) in any of a variety of suitable amounts.
  • the composition comprises the one or more components in an amount greater than or equal to 90 wt.%, greater than or equal to 91 wt.%, greater than or equal to 92 wt.%, greater than or equal to 93 wt.%, greater than or equal to 94 wt.%, greater than or equal to 95 wt.%, greater than or equal to 96 wt.%, greater than or equal to 97 wt.%, greater than or equal to 98 wt.%, greater than or equal to 99 wt.%, greater than or equal to 99.5 wt.%, or greater than or equal to 99.8 wt.% versus a total weight of the composition.
  • the composition comprises the one or more components in an amount less than or equal to 99.9 wt.%, less than or equal to 99.8 wt.%, less than or equal to 99.5 wt.%, less than or equal to 99 wt.%, less than or equal to 98 wt.%, less than or equal to 97 wt.%, less than or equal to 96 wt.%, less than or equal to 95 wt.%, less than or equal to 94 wt.%, less than or equal to 93 wt.%, less than or equal to 92 wt.%, or less than or equal to 91 wt.% versus a total weight of the composition.
  • the composition has a coefficient of friction greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.03, greater than or equal 0.04, greater than or equal 0.05, greater than or equal to 0.06, greater than or equal 0.07, greater than or equal 0.08, or greater than or equal to 0.09.
  • the composition has a coefficient of friction less than or equal to 0.1 and greater than or equal to 0.01, the composition has a coefficient of friction less than or equal to 0.06 and greater than or equal to 0.04).
  • Other ranges are also possible.
  • the coefficient of friction of the composition is determined using a portable friction meter muse.
  • the composition (e.g., the low surface energy material) is hydrophobic.
  • the composition may have any of a variety of suitable water contact angles.
  • the composition has a water contact angle greater than or equal to 90°, greater than or equal to 95°, greater than or equal to 100°, greater than or equal to 105°, greater than or equal to 110°, greater than or equal to 115°, greater than or equal to 120°, greater than or equal to 125°, greater than or equal to 130°, greater than or equal to 135°, greater than or equal to 140°, greater than or equal to 145°, greater than or equal to 150°, greater than or equal to 155°, greater than or equal to 160°, greater than or equal to 165°, greater than or equal to 170°, or greater than or equal to 175°.
  • the composition has a water contact angle less than or equal to 180°, less than or equal to 175°, less than or equal to 170°, less than or equal to 165°, less than or equal to 160°, less than or equal to 155°, less than or equal to 150°, less than or equal to 145°, less than or equal to 140°, less than or equal to 135°, less than or equal to 130°, less than or equal to 125°, less than or equal to 120°, less than or equal to 115°, less than or equal to 110°, less than or equal to 105°, less than or equal to 100°, or less than or equal to 95°.
  • the composition has a water contact angle greater than or equal to 90° and less than or equal to 180°, the composition has a water contact angle greater than or equal to 130° and less than or equal to 140°). Other ranges are also possible.
  • the water contact angle of the composition is determined using a goniometer.
  • FIG. 1 shows, according to some embodiments, a schematic diagram of an exemplary article.
  • article 100 comprises substrate 110 comprising at least one surface 120. Suitable substrate materials are described in greater detail elsewhere herein.
  • composition 130 is disposed on at least a portion of at least one surface 120 of substrate 110 such that composition 130 coats at least the portion of at least one surface 120 of substrate 110.
  • composition 130 comprises a low surface energy material comprising a POSS-based compound, as described in greater detail elsewhere herein.
  • composition coating the surface of the substrate may have any of a variety of suitable thicknesses. Referring to FIG. 1, for example, composition 130 coating at least the portion of at least one surface 120 of substrate 110 has thickness 132. In some embodiments, the composition coating the surface has an average thickness of greater than or equal to 5 nm, greater than or equal to 10 nm, greater than or equal to 20 nm, greater than or equal to 30 nm, greater than or equal to 40 nm, greater than or equal to 50 nm, greater than or equal to 60 nm, greater than or equal to 70 nm, greater than or equal to 80 nm, or greater than or equal to 90 nm.
  • the composition coating the surface has an average thickness of less than or equal to 100 nm, less than or equal to 90 nm, less than or equal to 80 nm, less than or equal to 70 nm, less than or equal to 60 nm, less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 30 nm, less than or equal to 20 nm, or less than or equal to 10 nm.
  • the composition coating the surface has an average thickness of greater than or equal to 5 nm and less than or equal to 100 nm, the composition coating the surface has an average thickness of greater than or equal to 40 nm and less than or equal to 60 nm).
  • the average thickness of the composition coating the surface is determined by ellipsometry.
  • composition 130 coating surface 120 of substrate 110 is depicted in FIG. 1 as a smooth layer of uniform thickness, those of ordinary skill in the art would understand that this is for illustration purposes only and the thickness of the composition coating the surface of the substrate may have a particular roughness and/or may vary in thickness, in accordance with some embodiments.
  • the composition coating the surface of the substrate is of relatively uniform thickness (e.g., within less than or equal to 10% of the total thickness) over at least a substantial portion of the surface of the substrate (e.g., greater than or equal to 75% of the surface area of the surface of the substrate on which the composition is disposed).
  • the composition coating the surface of the substrate may comprise a plurality of features.
  • the composition coating the surface of the substrate comprises a plurality of microscale and/or nanoscale features.
  • the plurality of features may advantageously render the composition more hydrophobic as compared to a composition that does not comprise the plurality of microscale and/or nanoscale features but is otherwise equivalent.
  • a composition comprising a plurality of features may have a water contact angle greater than or equal to 120°.
  • the plurality of features comprise at least one member selected from the group consisting of particles, amorphous particles, substantially spherical particles, posts, nanoneedles, microneedles, nanograss, micrograss, pores, grooves, ridges, and/or combinations thereof. According to some embodiments, the plurality of features may be formed as the composition is deposited on the surface of the substrate.
  • At least a portion of the composition comprising the low surface energy material is immobilized on at least the portion of the at least one surface of the substrate.
  • at least a portion of composition 130 is immobilized on at least the portion of at least one surface 120 of substrate 110.
  • at least a portion of composition 130 is chemically bound (e.g., covalently bound, non-covalently bound) to at least the portion of at least one surface 120 of substrate 110.
  • suitable bonding interactions include, in some embodiments, covalent bonding, non-co valent bonding, ionic bonding, hydrogen bonding, van der Waals forces, electrostatic forces, dipole interactions, coordination, chelation, and the like.
  • at least the portion of the composition is immobilized on at least the portion of the at least one surface of the substrate via at least one -Si-O- linkage.
  • alkyl refers to a radical of a straight-chain or branched saturated hydrocarbon group.
  • an alkali group has 1 to 10 carbon atoms (“C 1 -C 10 alkyl”).
  • an alkyl group has 1 to 9 carbon atoms (“C 1 -C 9 alkyl”).
  • an alkyl group has 1 to 8 carbon atoms (“C 1 -C 8 alkyl”).
  • an alkyl group has 1 to 7 carbon atoms (“C 1 - C 7 alkyl”).
  • an alkyl group has 1 to 6 carbon atoms (“C 1 -C 6 alkyl”).
  • an alkyl group has 1 to 5 carbon atoms (“C 1 -C 5 alkyl”). In some embodiments, an alkyl group has 1 to 4 carbon atoms (“C 1 -C 4 alkyl”). In some embodiments, an alkyl group has 1 to 3 carbon atoms (“C 1 -C 3 alkyl”). In some embodiments, an alkyl group has 1 to 2 carbon atoms (“C 1 -C 2 alkyl”). In some embodiments, an alkyl group has 1 carbon atom (“C 1 alkyl”).
  • an alkyl group has greater than or equal to 1 carbon atom.
  • an alkyl group has greater than or equal to 1 carbon atom, greater than or equal to 2 carbon atoms, greater than or equal to 3 carbon atoms, greater than or equal to 4 carbon atoms, greater than or equal to 5 carbon atoms, greater than or equal to 6 carbon atoms, greater than or equal to 7 carbon atoms, greater than or equal to 8 carbon atoms, greater than or equal to 9 carbon atoms, or greater than or equal to 10 carbon atoms.
  • an alkyl group has less than or equal to 20 carbon atoms, less than or equal to 10 carbon atoms, less than or equal to 9 carbon atoms, less than or equal to 8 carbon atoms, less than or equal to 7 carbon atoms, less than or equal to 6 carbon atoms, less than or equal to 5 carbon atoms, less than or equal to 4 carbon atoms, less than or equal to 3 carbon atoms, or less than or equal to 2 carbon atoms.
  • an alkyl group has greater than or equal to 1 carbon atom and less than or equal to 20 carbon atoms, an alkyl group has greater than or equal to 4 carbon atoms and less than or equal to 6 carbon atoms). Other ranges are also possible.
  • an alkyl group has 1 to 6 carbon atoms (“C 1 -C 6 alkyl”).
  • C 1 -C 6 alkyl groups include methyl (C 1 ), ethyl (C 2 ), n-propyl (C 3 ), isopropyl (C 3 ), n- butyl (C 4 ), tert-butyl (C 4 ), sec-butyl (C 4 ), iso-butyl (C 4 ), n-pentyl (C 5 ), 3-pentanyl (C 5 ), amyl (C 5 ), neopentyl (C 5 ), 3-methyl-2-butanyl (C 5 ), tertiary amyl (C 5 ), and n-hexyl (C 6 ).
  • alkyl groups include n-heptyl (C 7 ), n-octyl (C 8 ), and the like. Unless otherwise specified, each instance of an alkyl group is independently unsubstituted (an “unsubstituted alkyl”) or substituted (a “substituted alkyl”) with one or more substituents. In some embodiments, the alkyl group is an unsubstituted C 1 -C 10 alkyl (e.g., -CH 3 ). In some embodiments, the alkyl group is a substituted C 1 -C 10 alkyl.
  • alkenyl includes a radical of a straight-chain or branched saturated hydrocarbon group having from 2 to 10 carbon atoms, and also includes at least one carbon-carbon double bond. It will be understood that in some embodiments, alkenyl may be advantageously of limited length, including C 2 -C 10 , C 2 -C 9 , C 2 -C 8 , C 2 - C 7 , C 2 -C 6 , C 2 -C 5 , C 2 -C 4 , and C 2 -C 3 .
  • alkynyl includes a radical of a straight-chain or branched saturated hydrocarbon group having from 3 to 10 carbon atoms, and also includes at least one carbon-carbon triple bond. It will be understood that in some embodiments, alkenyl may be advantageously of limited length, including C 3 -C 10 , C 3 -C 9 , C 3 -C 8 , C 3 -C 7 , C 3 -C 6 , C 3 -C 5 , and C 3 -C 4 .
  • alkylene is the divalent moiety of alkyl (e.g., an acyclic carbon or a saturated acyclic carbon chain represented by the formula -C n H 2n -)
  • alkenylene is the divalent moiety of alkenyl (e.g., an acyclic carbon chain which contains a carbon-to-carbon double bond represented by the formula -C n H 2n-2 -)
  • alkynylene is the divalent moiety of alkynyl (e.g., an acyclic carbon chain which contains a carbon-to-carbon triple bond represented by the formula -C n H 2n-4 -).
  • alkylyne is the trivalent moiety of alkyl
  • alkenylyne is the trivalent moiety of alkenyl
  • alkynylyne is the trivalent moiety of alkynyl
  • halogen refers to fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), or iodine (iodo, -I).
  • alkoxy refers to an -O-(alkyl) or an -O-(cycloalkyl) group.
  • Representative alkoxy group examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and the like.
  • alkyl, alkylene, and alkylyne groups are, in some embodiments, optionally substituted.
  • Optionally substituted refers to a group which may be substituted or unsubstituted (e.g., “substituted” or “unsubstituted” alkyl).
  • the product was characterized by 1 H-NMR: -Si(CH 3 ) 2 -/-Si(CH 3 ) 3 (m, 0.25 ppm); Si-CH 2 -CH 2 -Si (t, 0.7 ppm).
  • the product was also characterized by FT-IR: -Si(CH 3 ) 2 -/-Si(CH 3 ) 3 (2965 cm -1 and 790 cm -1 ); -O-Si-O- (1070 cm -1 ).
  • the product was also characterized by 29 Si-NMR: T 8 /T 10 /T 12 (-80.3 ppm).
  • the product was also characterized by FT-IR: -Si-C 6 H 6 (2965 cm -1 ); -C 6 H 6 (1595 cm -1 and 1429 cm -1 ); -O-Si-O- (1070 cm -1 ).
  • the product was characterized by FT-IR: -NH 2 (br, 3500 cm -1 ); -Si-C 6 H 6 (3072 cm -1 and 3049 cm -1 ); -C 6 H 6 (1595 cm -1 and 1429 cm -1 ); -O-Si-O- (1070 cm -1 ).
  • the product was characterized by FT-IR: -NH 2 (br, 3500 cm -1 ); -Si C 6 H 6 (3072 cm -1 and 3049 cm -1 ); -C 6 H 6 (1595 cm -1 , 1506 cm -1 , and 1429 cm -1 ); -O-Si-O- (1070 cm -1 ).
  • the product was also characterized by 29 Si-NMR: T 8 (-64.91 ppm).
  • the product was characterized by GPC, and the peak molecular weight was determined to be 17,005 Da (see FIG. 14). It was determined that the structure of the product was a POSS-dimer multifunctionalized with 10 polydimethylsiloxane groups and 4 methacrylate groups, with one bridging methacrylate group between the two POSS cages.
  • the product was characterized by gel permeation chromatography (GPC), and the peak molecular weight was determined to be 14,520 Da (see FIG. 15). It was determined that the structure of the product was a POSS-dimer multifunctionalized with 6 polydimethylsiloxane groups and 8 methacrylate groups, with one bridging methacrylate group between the two POSS cages.
  • GPC gel permeation chromatography
  • a reference to “A and/or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified.
  • “at least one of A and B” can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

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Abstract

Compositions comprising non-fluorinated polyhedral oligomeric silsesquioxane (POSS)-based compounds, and related articles, methods, and kits, are generally described. In an exemplary set of embodiments, the non-fluorinated POSS-based compound comprises a POSS molecule functionalized with a variety of suitable functional groups, including, for example, polydialkylsiloxane (e.g., polydimethylsiloxane) groups, tris(trialkylsiloxy)silane (e.g., tris(trimethylsiloxy)silane) groups, (meth)acrylate groups, phenyl groups, substituted phenyl groups, amine groups, azide groups, isocyanate groups, –C1-C10 alkyl groups, allyl groups, alcohol groups, epoxy groups, thiol groups, and/or acidic groups.

Description

NON-FLUORINATED POLYMER ADDITIVES AND RELATED METHODS
TECHNICAL FIELD
[00001] Compositions comprising non-fluorinated polyhedral oligomeric silsesquioxane (POSS)-based compounds, and related articles, methods, and kits, are generally described.
BACKGROUND
[00002] Conventional POSS-based compounds comprise fluorinated components that lower the surface energy of the material, but present toxicity and bioaccumulation issues that limit large-scale applications. In view of the toxicity and bioaccumulation issues presented by per- and polyfluoroalkyl substances (PF AS), global regulations have banned certain fluorinated molecules in products such as food packaging, firefighting foam, and personal care products.
[00003] Accordingly, improved compositions, and related articles, methods, and kits, are necessary.
SUMMARY
[00004] Described herein are compositions comprising non-fluorinated polyhedral oligomeric silsesquioxane (POSS)-based compounds and related articles, methods, and kits. The subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
[00005] According to some embodiments, a polyhedral oligomeric silsesquioxane (POSS)-based compound is described. In some embodiments, the compound comprises a multifunctionalized POSS molecule of the structure:
Figure imgf000004_0001
wherein: each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3, -O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-, -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)y, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, optionally substituted, with the proviso that a first R1 is different from a second R1; each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted; each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted; each x is the same or different and is greater than or equal to 0 and less than or equal to 10; each y is the same or different and is greater than or equal to 1 and less than or equal to 3; n is greater than or equal to 2 and less than or equal to 100; and the multifunctionalized POSS molecule is substantially non-fluorinated.
[00006] According to some embodiments, a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a POSS molecule of the structure:
Figure imgf000005_0001
wherein: each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,- O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-, -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=0, -(R3)x-(R2)y, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, optionally substituted, with the proviso that at least one R1 is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3; each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3- C10 alkynyl, and aryl, optionally substituted; each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted; each x is the same or different and is greater than or equal to 0 and less than or equal to 10; each y is the same or different and is greater than or equal to 1 and less than or equal to 3; n is greater than or equal to 2 and less than or equal to 100; and the POSS molecule is substantially non-fluorinated.
[00007] In some embodiments, a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a POSS molecule of the structure:
Figure imgf000006_0001
wherein: each R1 is the same or different and is selected from the group consisting of -O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,- O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)y, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, optionally substituted, with the proviso that at least one R1 is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- or -O-Si(R2)2-(R3): O-CH2CHCH2; each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted; each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted; each x is the same or different and is greater than or equal to 0 and less than or equal to 10; each y is the same or different and is greater than or equal to 1 and less than or equal to 3; n is greater than or equal to 2 and less than or equal to 100; and the POSS molecule is substantially non-fluorinated.
[00008] According to some embodiments, a polyhedral oligomeric silsesquioxane (POSS)-based compound comprises a POSS molecule of the structure:
Figure imgf000007_0001
wherein: each R1 is the same or different and is selected from the group consisting of -O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,-O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-, -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)3,-(R3)x-NH2, -(R3)x-NH-R2, - (R3)x-N3, -(N)=C=O, -(R3)x-(R2)3, -(R3)x- OH, -(R3)x-(C2H4O), and (R3)x-SH, optionally substituted; each R1’ is the same or different and is a bridging moiety to another silicon atom of the POSS molecule, wherein each R1’ is selected from the group consisting of-O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O- (R3)x— , and -O-Si(R2)2-(R3)x-O-CH2CHCH2, optionally substituted; each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2- C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted; each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted; each x is the same or different and is greater than or equal to 0 and less than or equal to 10; each y is the same or different and is greater than or equal to 1 and less than or equal to 3; n is greater than or equal to 2 and less than or equal to 100; m is greater than or equal to 2 and less than or equal to 100; and the POSS molecule is substantially non-fluorinated.
[00009] Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention when considered in conjunction with the accompanying figures. In cases where the present specification and a document incorporated by reference include conflicting and/or inconsistent disclosure, the present specification shall control.
BRIEF DESCRIPTION OF THE DRAWINGS
[00010] Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In the figures:
[00011] FIG. 1 shows, according to one set of embodiments, a schematic diagram of an exemplary article.
[00012] FIG. 2 shows, according to one set of embodiments, a schematic diagram of an exemplary method of coating a substrate.
[00013] FIG. 3 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a polyhedral oligomeric silsesquioxane (POSS) molecule functionalized with polydimethylsiloxane.
[00014] FIG. 4 shows, according to one set of embodiments, a thermogravimetric analysis (TGA) plot of a POSS molecule functionalized with poly dimethylsiloxane.
[00015] FIG. 5 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with poly dimethylsiloxane and a methacrylate group.
[00016] FIG. 6 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with a phenyl group.
[00017] FIG. 7 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with a phenyl group and a primary amine group. [00018] FIG. 8 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with a phenyl group and a secondary amine group.
[00019] FIG. 9 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with a substituted phenyl group.
[00020] FIG. 10 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with a substituted phenyl group and a secondary amine group.
[00021] FIG. 11 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with 2,2,4-trimethylhexane.
[00022] FIG. 12 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule functionalized with isopentane.
[00023] FIG. 13 shows, according to one set of embodiments, a schematic representation of an exemplary synthesis of a POSS molecule multifunctionalized with isopentane and a primary amine group.
[00024] FIG. 14 shows, according to one set of embodiments, a gel permeation chromatogram of a POSS-dimer.
[00025] FIG. 15 shows, according to one set of embodiments, a gel permeation chromatogram of a second POSS-dimer.
[00026] FIG. 16 shows, according to one set of embodiments, a FT-IR spectrum of the second POSS-dimer.
DETAILED DESCRIPTION
[00027] Compositions comprising non-fluorinated polyhedral oligomeric silsesquioxane (POSS)-based compounds, and related articles, methods, and kits, are generally described. In an exemplary set of embodiments, the non-fluorinated POSS-based compound comprises a POSS molecule functionalized with a variety of suitable functional groups, including, for example, polydialkylsiloxane (e.g., polydimethylsiloxane) groups, tris(trialkylsiloxy)silane (e.g., tris(trimethylsiloxy)silane) groups, (meth)acrylate groups, phenyl groups, substituted phenyl groups, amine groups, azide groups, isocyanate groups, -C1-C10 alkyl groups, allyl groups, alcohol groups, epoxy groups, thiol groups, and/or acidic groups. In some cases, the structure of the non-fluorinated POSS -based compound may advantageously be tuned depending on a particular application. For example, in some embodiments (e.g., wherein a hydrophobic and/or low surface energy material is desirable), the POSS molecule comprises one or more polydialkylsiloxane groups. In some embodiments (e.g., wherein a material capable of crosslinking is desirable), the POSS molecule comprises one or more (meth)acrylate groups. [00028] In some embodiments, the non-fluorinated POSS-based compound is configured such that each silicon atom of the POSS molecule is functionalized with the same functional group. In other embodiments, the non-fluorinated POSS-based compound is multifunctional such that each silicon atom of the POSS molecule is functionalized with a functional group, wherein at least two functional groups are different (e.g., chemically different). Advantageously, the multifunctionalized POSS-based compound may have multiple functionalities and/or uses. For example, in some embodiments (e.g., wherein both a hydrophobic and/or low surface energy material and a material capable of crosslinking is desirable), the POSS molecule comprises one or more polydialky I siloxane groups and one or more (meth)acrylate groups. Other combinations of functional groups are possible and a person of ordinary skill in the art would be capable of selecting such functional groups depending on the particular application, based upon the teachings of this specification.
[00029] According to some embodiments, the non-fluorinated POSS-based compound is configured such that at least one functional group of the POSS molecule is a bridging moiety to another POSS molecule. For example, in some embodiments, the POSS-based compound comprises a first POSS molecule functionalized with one or more (meth)acrylate groups that form a bond to a second POSS molecule. In some cases, embodiments in which at least one functional group of the POSS molecule is a bridging moiety to another POSS molecule advantageously provides extended structures of POSS-based dimers, oligomers, and/or polymers. In some embodiments, each monomer of the POSS-based dimer, oligomer, and/or polymer has the same or different functionalities. [00030] In some embodiments, the non-fluorinated POSS-based compounds described herein are used as additives in compositions comprising one or more base polymers (e.g., resins such as epoxy-containing resins and/or (meth)acry late-containing resins). In some embodiments, the non-fluorinated POSS-based additive is configured to interact (e.g., crosslink) with the one or more base polymers. In some embodiments, the use of a non-fluorinated POSS-based additive results in the composition having an advantageously low surface energy, e.g., as compared to a composition that is otherwise equivalent but does not comprise the non-fluorinated POSS-based additive. For example, in some embodiments, a composition comprising the non-fluorinated POSS-based compound has a coefficient of friction less than or equal to 0.1. In some embodiments, the resulting compositions are used as coatings on a wide variety of substrates, including, for example, glass, ceramics, metals, metal oxides, and/or polymers.
[00031] While much of the description herein and below generally relates to POSS-based compounds comprising POSS molecules having 8 Si tetrahedral vertices (T vertices), those of ordinary skill in the art would understand, based upon the teachings of this specification, that other lower-order and/or higher-order POSS molecules are also possible. For example, in some embodiments, POSS molecules comprising 4 Si T vertices, 6 Si T vertices, 10 Si T vertices, and/or 12 Si T vertices, or more, are possible. As such, the concepts described herein are, in some embodiments, applicable to POSS molecules comprising 4 Si T vertices, 6 Si T vertices, 8 Si T vertices, 10 Si T vertices, and/or 12 Si T vertices. In some embodiments, a POSS-based compound (e.g., a POSS-based additive) comprises a plurality of POSS molecules, each POSS molecule having the same or different number of Si tetrahedral vertices. In an exemplary set of embodiments, each POSS molecule has 8 Si T vertices as depicted in Formula (I), below.
[00032] In some embodiments, the POSS molecule has a formula as in SizO1.5zR1 z, where each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2-(R3)x- Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3, -O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)y, -(R3)x- OH, -(R3) X-(C2H4O), and — (R3)x-SH, any of which may be optionally substituted, wherein each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, - C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, any of which may be optionally substituted, and wherein each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene- and aryl, any of which may be optionally substituted.
[00033] In some embodiments z is greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, greater than or equal to 9, greater than or equal to 10, greater than or equal to 11, or greater than or equal to 12. In some embodiments, z is less than or equal to 14, less than or equal to 13, less than or equal to 12, less than or equal to 11, less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, or less than or equal to 5. Combinations of the above-reference ranges are also possible (e.g., z is greater than or equal to 4 and less than or equal to 14). Other ranges are also possible.
[00034] In some embodiments, the POSS-based compound comprises a POSS molecule according to Formula (I):
Figure imgf000012_0001
wherein: each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3, -O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-, -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)X-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)y, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, any of which may be optionally substituted; each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, any of which may be optionally substituted, each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, any of which may be optionally substituted, each x is the same or different and is greater than or equal to 0 and less than or equal to
10, each y is the same or different and is greater than or equal to 1 and less than or equal to 3, and n is greater than or equal to 2 and less than or equal to 100.
[00035] As described above, each R1, R2, and/or R3 may, in some embodiments, be optionally substituted. For example, in some embodiments, at least one R1, R2, and/or R3 is optionally substituted with a poly dialkylsiloxane group (e.g., poly dimethylsiloxane). In some non-limiting embodiments, for example, at least one R2 is -C1-C10 alkyl substituted with a polydialkylsiloxane (e.g., polydimethylsiloxane) group.
[00036] The value of each x in the POSS molecule according to Formula (I) may be selected from a variety of suitable values. For example, in some embodiments, the value of each x in the POSS molecule according to Formula (I) is independently greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9. In some embodiments, the value of each x in the POSS molecule according to Formula (I) is independently less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1. Combinations of the above recited ranges are possible (e.g., the value of each x in the POSS molecule according to Formula (I) is independently greater than or equal to 0 and less than or equal to 10, the value of each x in the POSS molecule according to Formula (I) is independently greater than or equal to 4 and less than or equal to 6). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for x based upon the teachings of this specification.
[00037] The value of each y in the POSS molecule according to Formula (I) may be selected from a variety of suitable values. In some embodiments, for example, the value of each y in the POSS molecule according to Formula (I) is independently greater than or equal to 1 or greater than or equal to 2. In some embodiments, the value of each y in the POSS molecule according to Formula (I) is independently less than or equal to 3 or less than or equal to 2. Combinations of the above recited ranges are possible (e.g., the value of each y in the POSS molecule according to Formula (I) is independently greater than or equal to 1 and less than or equal to 3). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for y based upon the teachings of this specification.
[00038] The value of n in the POSS molecule according to Formula (I) may be selected from a variety of suitable values. In some embodiments, for example, the value of n in the POSS molecule according to Formula (I) is greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90. In some embodiments, the value of n in the POSS molecule according to Formula (I) is less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 20, less than or equal to 10, less than or equal to 5, or less than or equal to 2.
Combinations of the above recited ranges are possible (e.g., the value of n in the POSS molecule according to Formula (I) is greater than or equal to 1 and less than or equal to 100, the value of n in the POSS molecule according to Formula (I) is greater than or equal to 40 and less than or equal to 60). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for n based upon the teachings of this specification.
[00039] According to some embodiments, the POSS molecule comprises 8 Si T vertices corresponding to a T8 cage (e.g., as in Formula (I)). In other embodiments, however, the POSS molecule comprises any of a variety of suitable Si T vertices, as described above. In some embodiments, for example, the POSS molecule comprises 4 Si T vertices (a T4 cage having 4 R1 groups), 6 Si T vertices (a T6 cage having 6 R1 groups), 10 Si T vertices (a T10 cage having 10 R1 groups), or 12 Si T vertices (a T12 cage having 12 R1 groups). Those of ordinary skill in the art would understand, based upon the teachings of this specification, that any of the concepts described herein (e.g., such as those described with respect to the POSS molecule according to Formula (I)) may also correspond to a POSS molecule comprising a T4 cage, a T6 cage, a T10 cage, or a T12 cage.
[00040] In some embodiments, the POSS molecule (e.g., such as a POSS molecule according to Formula (I)) is substantially non-fluorinated. For example, in some embodiments, the POSS molecule comprises fluorine in an amount less than or equal to 5 wt.%, less than or equal to 4 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, or less than or equal to 0.2 wt.% versus a total weight of the POSS molecule. In some embodiments, the POSS molecule comprises fluorine in an amount greater than or equal to 0 wt.%, greater than or equal to 0.2 wt.%, greater than or equal to 0.5 wt.%, greater than or equal to 1 wt.%, greater than or equal to 2 wt.%, greater than or equal to 3 wt.%, or greater than or equal to 4 wt.% versus a total weight of the POSS molecule.
Combinations of the above recited ranges are possible (e.g., the POSS molecule comprises fluorine in an amount less than or equal to 5 wt.% and greater than or equal to 0 wt.% versus a total weight percent of the POSS molecule, the POSS molecule comprises fluorine in an amount less than or equal to 2 wt.% and greater than or equal to 1 wt.% versus a total weight of the POSS molecule). Other ranges are also possible.
[00041] In some non-limiting embodiments, the POSS molecule is non-fluorinated such that the POSS molecule comprises fluorine in an amount of 0 wt.% versus a total weight of the POSS molecule.
[00042] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a polydialkylsiloxane group (e.g., polydimethylsiloxane). In some embodiments, a POSS molecule functionalized with a polydialkylsiloxane group, advantageously provides a hydrophobic and/or low surface energy material. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -O- Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3. For example, in some non-limiting embodiments, the at least one R1 is -O-Si(CH3)2-(CH2)x-Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3 (e.g., -O- Si(CH3)2-(CH2)2-Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3). In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2-O]n- Si(R2)3. For example, in some non-limiting embodiments, each R1 is -O-Si(CH3)2-(CH2)x- Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3 (e.g., - O-Si(CH3)2-(CH2)2-Si(CH3)2-O-[Si(CH3)2-O]n- Si(CH3)3). Other polydialkylsiloxane groups are also possible.
[00043] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a tris(trialkylsiloxy)silane group (e.g., tris(trimethylsiloxy)silane). In some embodiments, a POSS molecule functionalized with a tris(trialkylsiloxy)silane group advantageously provides a hydrophobic and/or low surface energy material. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -O- Si(R2)2-(R3)x-Si(OSi(R2)3)3. For example, in some non-limiting embodiments, the at least one R1 is -O-Si(CH3)2-(CH2)x-Si(OSi(CH3)3)3 (e.g., -O-Si(CH3)2-Si(OSi(CH3)3)3). In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x- Si(OSi(R2)3)3. For example, in some non-limiting embodiments, each R1 is -O-Si(CH3)2-(CH2)x- Si(OSi(CH3)3)3 (e.g., -O-Si(CH3)2-Si(OSi(CH3)3)3). Other tris(trialkylsiloxy)silane groups are also possible.
[00044] In accordance with some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a (meth)acrylate group. In some embodiments, a POSS molecule functionalized with a (meth)acrylate group advantageously provides a material capable of crosslinking, e.g., with another POSS molecule and/or with one or more components of a composition comprising the POSS-based compound, as described in greater detail elsewhere herein. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-. For example, in some non-limiting embodiments, the at least one R1 is -O-Si(CH3)2-(R3)x-O-C(O)- C(CH3)(CH2) (e.g., -O-Si(CH3)2-(CH2)(CH)(CH3)(CH2)2-O-C(O)-C(CH3)(CH2)) or -O- Si(CH3)2-(R3)x-C(O)-O(CH2)2C(CH3)(CH2)- (e.g., -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)- O(CH2)2C(CH3)(CH2)-). In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-. For example, in some non-limiting embodiments, each R1 is -O-Si(CH3)2-(R3)x-O-C(O)- C(CH3)(CH2) (e.g., -O-Si(CH3)2-(CH2)(CH)(CH3)(CH2)2-O-C(O)-C(CH3)(CH2)) or -O- Si(CH3)2-(R3)x-C(O)-O(CH2)2C(CH3)(CH2)- (e.g., -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)- O(CH2)2C(CH3)(CH2)-). Other (meth)acrylate groups are also possible.
[00045] In some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a phenyl group. In some embodiments, a POSS molecule functionalized with a phenyl group advantageously provides a hydrophobic material capable of intra- or intermolecular π-π stacking interactions. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-C6H5. For example, in some non-limiting embodiments, the at least one R1 is -(CH2)x-C6H5 (e.g., -C6H5). According to some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-C6H5. For example, in some non-limiting embodiments, each R1 is -(CH2)x-C6H5 (e.g., -C6H5). Other phenyl groups are also possible.
[00046] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a substituted phenyl group. In some embodiments, a POSS molecule functionalized with a substituted phenyl group advantageously provides a hydrophobic material capable of intra- or intermolecular π-π stacking interactions. According to some embodiments, the substituted phenyl group may be substituted with at least one methyl group, at least one t- butyl group, and/or at least one phenyl group. For example, in some embodiments, the substituted phenyl group comprises biphenyl. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-C6H4-(R3)x-(R2)y. For example, in some nonlimiting embodiments, the at least one R1 is -(CH2)x-C6H4-CH3, -(CH2)x-C6H3-(CH3)2,-(CH2)x- C6H4-C(CH3)3, -(CH2)x-C6H3-(C(CH3)3)2, or -(CH2)x-C6H4-C6H5 (e.g., -(CH2)2-C6H4-CH3, - (CH2)2-C6H3-(CH3)2, -(CH2)2-C6H4-C(CH3)3, -(CH2)2-C6H3-(C(CH3)3)2, or -(CH2)2-C6H4-C6H5). In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x- C6H4-(R3)x-(R2)y. For example, in some non-limiting embodiments, each R1 is -(CH2)x-C6H4- CH3, -(CH2)x-C6H3-(CH3)2, -(CH2)x-C6H4-C(CH3)3, -(CH2)x-C6H3-(C(CH3)3)2, or -(CH2)x- C6H4-C6H5 (e.g., -(CH2)2-C6H4-CH3, -(CH2)2-C6H3-(CH3)2,-(CH2)2-C6H4-C(CH3)3, -(CH2)2- C6H3-(C(CH3)3)2, or -(CH2)2-C6H4-C6H5). Other substituted phenyl groups are also possible. [00047] In some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an amine group. According to some embodiments, a POSS molecule functionalized with an amine group advantageously provides a material capable of chemical reactivity (e.g., crosslinking), for example, with one or more components of a composition comprising the POSS-based compound. In some embodiments, the amine group is a primary amine group. For example, in some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH2. In some non-limiting embodiments, the at least one R1 is -(CH2)x-NH2 (e.g., -(CH2)3-NH2). In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH2. For example, in some non-limiting embodiments, each R1 is -(CH2)x-NH2 (e.g., -(CH2)3-NH2). Other primary amine groups are also possible. In some embodiments, the amine group is a secondary amine group. In some embodiments, for example, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH-R2. In some non-limiting embodiments, the at least one R1 is -(CH2)x-NH-C6H5 (e.g., -(CH2)3-NH-C6H5). In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH- R2. For example, in some non-limiting embodiments, each R1 is -(CH2)x-NH-C6H5 (e.g., - (CH2)3-NH-C6H5). In some embodiments, the secondary amine group comprises ethylenediamine, trisethylenediamine, and/or tetraethylenediamine. For example, in some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x- NH-(CH2)2-NH2, -(R3)x-NH-(CH2)2-NH-(CH2)2-NH2, and/or -(R3)x-NH-(CH2)2-NH-(CH2)2-NH- (CH2)2-NH2. In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH-(CH2)2-NH2, -(R3)x-NH-(CH2)2-NH-(CH2)2-NH2, and/or -(R3)x-NH-(CH2)2- NH-(CH2)2-NH-(CH2)2-NH2. Other secondary amine groups are also possible.
[00048] In some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an azide group. According to some embodiments, a POSS molecule functionalized with an azide group advantageously provides a material capable of chemical reactivity (e.g., click chemistry), for example, with one or more components of a composition comprising the POSS-based compound. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-N3. For example, in some non-limiting embodiments, the at least one R1 is -(CH2)x-N3. According to some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-N2. For example, in some non-limiting embodiments, each R1 is -(CH2)x-N3. Other azide groups are also possible.
[00049] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an isocyanate group. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(N)=C=O. According to some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(N)=C=O.
[00050] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a -C1-C10 alkyl group. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(R2)y. For example, in some nonlimiting embodiments, the at least one R1 is -(CH2)-(CH)(CH3)-(CH2)-C(CH3)3 or -(CH2)- (CH)(CH3)2. In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (l)) is -(R3) x-(R )y. For example, in some non-hmitmg embodiments, each R1 is (CH2)- (CH)(CH3)-(CH2)-C(CH3)3 or -(CH2)-(CH)(CH3)2. Other -C1-C10 alkyl groups are also possible. [00051] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an allyl group. In some embodiments, a POSS molecule functionalized with an allyl group advantageously provides a material capable of crosslinking, e.g., with another POSS molecule and/or with one or more components of a composition comprising the POSS-based compound, as described in greater detail elsewhere herein. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -O- Si(R2)2-(R3)x-O-CH2CHCH2 or -O-CH2CHCH2. For example, in some non-limiting embodiments, the at least one R1 is -O-Si(CH3)2-(R3)x-O-CH2CHCH2 or -O-CH2CHCH2. In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2- (R3)x-O-CH2CHCH2 or -O-CH2CHCH2. For example, in some non-limiting embodiments, each R1 is -O-Si(CH3)2-(R3)x-O-CH2CHCH2 or -O-CH2CHCH2. Other allyl groups are also possible. [00052] In some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an alcohol group. According to some embodiments, a POSS molecule functionalized with an alcohol group advantageously provides a material capable of chemical reactivity (e.g., crosslinking), for example, with one or more components of a composition comprising the POSS-based compound. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-OH. For example, in some non-limiting embodiments, at least one R1 is -(CH2)x-OH. In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-OH. For example, in some non-limiting embodiments, each R1 is -(CH2)x-OH. Other alcohol groups are possible.
[00053] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an epoxy group. According to some embodiments, a POSS molecule functionalized with an epoxy group advantageously provides a material capable of chemical reactivity (e.g., covalent bonding), for example, with one or more components of a composition comprising the POSS-based compound. In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(C2H4O). For example, in some non-limiting embodiments, the at least one R1 is -(CH2)x-(C2H4O). According to some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(C2H4O). For example, in some non-limiting embodiments, each R1 is -(CH2)x-(C2H4O). Other epoxy groups are also possible. [00054] In some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with a thiol group. According to some embodiments, a POSS molecule functionalized with a thiol group advantageously provides a material capable of chemical reactivity (e.g., thiol-ene reactions), for example, with one or more components of a composition comprising the POSS-based compound (e.g., a vinyl-containing component). In some embodiments, at least one R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-SH. For example, in some non-limiting embodiments, at least one R1 is -(CH2)x-SH. In some embodiments, each R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-SH. For example, in some non-limiting embodiments, each R1 is -(CH2)x-SH. Other thiol groups are also possible.
[00055] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is functionalized with an acidic group. For example, in some embodiments, at least one R1 in the POSS molecule comprises an acidic group. In some embodiments, for example, the acidic group is a Bronsted-Lowry acid that is capable of donating a proton. In some embodiments, the acid is a Lewis acid that is capable of forming a covalent bond with an electron pair. In certain embodiments, the acidic group comprises a sulfonic acid group (e.g., -SO3H), a phosphoric acid group (e.g., -PO4H2), a carboxylic acid group (e.g., -COOH), a thiol group (e.g., -SH), an alcohol group (e.g. , -OH), an amine group (e.g., -NH2), and/or combinations thereof.
[00056] In some embodiments, the POSS molecule is multifunctionalized. As used herein, the term “multifunctionalized” refers to a molecule comprising at least two different (e.g., chemically different) functional groups. For example, in some embodiments, the POSS molecule (e.g., according to Formula (I)) is configured such that at least one R1 is different from another R1. In some embodiments, two or more, three or more, four or more, five or more, six or more, or seven or more R1 groups are different from another R1. The following embodiments are meant to be illustrative of some such embodiments but are not intended to be limiting.
[00057] In some embodiments, the multifunctionalized POSS molecule comprises at least two different (e.g., chemically different) functional groups. For example, according to some embodiments wherein the POSS molecule (e.g., according to Formula (I)) is multifunctionalized, a first R1 in the POSS molecule is different from a second R1 in the POSS molecule.
[00058] The ratio of the first R1 to the second R1 may be selected from a variety of suitable ratios. According to some embodiments, for example, the multifunctionalized POSS molecule having a T8 structure comprises na first R1 groups and nb second R1 groups, wherein each of na and nb are independently greater than or equal to 1 and less than or equal to 7 such that na + nb = 8.
[00059] In some embodiments, the ratio of the first R1 to the second R1 is greater than or equal 1 :7 (e.g., na is 1 and nb is 7), greater than or equal to 2:6 (e.g., na is 2 and nb is 6), greater than or equal to 3:5 (e.g., na is 3 and nb is 5), greater than or equal to 4:4 (e.g., na is 4 and nb is 4), greater than or equal to 5:3 (e.g., na is 5 and nb is 3), or greater than or equal to 6:2 (e.g., na is 6 and nb is 2). In some embodiments, the ratio of the first R1 to the second R1 is less than or equal to 7:1 (e.g., na is 7 and nb is 1), less than or equal to 6:2 (e.g., na is 6 and nb is 2), less than or equal to 5:3 (e.g., na is 5 and nb is 3), less than or equal to 4:4 (e.g., na is 4 and nb is 4), less than or equal to 3:5 (e.g., na is 3 and nb is 5), or less than or equal to 2:6 (e.g., na is 2 and nb is 6). Combinations of the above recited ranges are possible (e.g., the ratio of the first R1 to the second R1 is greater than or equal 1 :7 and less than or equal to 7: 1, the ratio of the first R1 to the second R1 is greater than or equal 3:5 and less than or equal to 5:3). Other ranges are also possible.
[00060] In some non-limiting embodiments, the ratio of the first R1 to the second R1 is
4:4.
[00061] In some embodiments, the multifunctionalized POSS molecule comprises at least three different (e.g., chemically different) functional groups. For example, according to some embodiments wherein the POSS molecule is multifunctionalized, the first R1 in the POSS molecule (e.g., according to Formula (I)) is different from the second R1 in the POSS molecule and a third R1 in the POSS molecule. In some embodiments, the second R1 is different from the third R1.
[00062] The ratio of the first R1 to the second R1 and the third R1 may be selected from a variety of suitable ratios. In some embodiments, for example, the multifunctionalized POSS molecule having a T8 structure comprises na first R1 groups, nb second R1 groups, and nc third R1 groups, wherein each of na, nb, and nc are independently greater than or equal to 1 and less than or equal to 6 such that na + nb + nc = 8.
[00063] In some embodiments, the multifunctionalized POSS molecule comprises at least four different (e.g., chemically different) functional groups. For example, in some embodiments wherein the POSS molecule is multifunctionalized, the first R1 in the POSS molecule (e.g., according to Formula (I)) is different from the second R1 in the POSS molecule, the third R1 in the POSS molecule, and a fourth R1 in the POSS molecule. In some embodiments, the second R1 is different from the third R1 and the fourth R1. In some embodiments, the third R1 is different from the fourth R1.
[00064] The ratio of the first R1 to the second R1, the third R1, and the fourth R1 may be selected from a variety of suitable ratios. In some embodiments, for example, the multifunctionalized POSS molecule having a T8 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, and nd fourth R1 groups, wherein each of na, nb, nc, and nd are independently greater than or equal to 1 and less than or equal to 5 such that na + nb + nc + nd 8.
[00065] In some embodiments, the multifunctionalized POSS molecule comprises at least five different (e.g., chemically different) functional groups. For example, according to some embodiments wherein the POSS molecule is multifunctionalized, the first R1 in the POSS molecule (e.g., according to Formula (I)) is different from the second R1 in the POSS molecule, the third R1 in the POSS molecule, the fourth R1 in the POSS molecule, and a fifth R1 in the POSS molecule. In some embodiments, the second R1 is different from the third R1, the fourth R1, and the fifth R1. In some embodiments, the third R1 is different from the fourth R1 and the fifth R1. In some embodiments, the fourth R1 is different from the fifth R1.
[00066] The ratio of the first R1 to the second R1, the third R1, the fourth R1, and the fifth R1 may be selected from a variety of suitable ratios. In some embodiments, for example, the multifunctionalized POSS molecule having a T8 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, nd fourth R1 groups, and ne fifth R1 groups, wherein each of na, nb, nc, nd and ne are independently greater than or equal to 1 and less than or equal to 4 such that na + nb + nc + nd + ne = 8.
[00067] In some embodiments, the multifunctionalized POSS molecule comprises at least six different (e.g., chemically different) functional groups. For example, according to some embodiments wherein the POSS molecule is multifunctionalized, the first R1 in the POSS molecule (e.g., according to Formula (I)) is different from the second R1 in the POSS molecule, the third R1 in the POSS molecule, the fourth R1 in the POSS molecule, the fifth R1 in the POSS molecule, and a sixth R1 in the POSS molecule. In some embodiments, the second R1 is different from the third R1, the fourth R1, the fifth R1, and the sixth R1. In some embodiments, the third R1 is different from the fourth R1, the fifth R1, and the sixth R1. In some embodiments, the fourth R1 is different from the fifth R1 and the sixth R1. In some embodiments, the fifth R1 is different from the sixth R1.
[00068] The ratio of the first R1 to the second R1, the third R1, the fourth R1, the fifth R1, and the sixth R1 may be selected from a variety of suitable ratios. In some embodiments, for example, the multifunctionalized POSS molecule having a T8 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, nd fourth R1 groups, ne fifth R1 groups, and nf sixth R1 groups, wherein each of na, nb, nc, nd, ne, and nf are independently greater than or equal to 1 and less than or equal to 3 such that na + nb + nc + nd + ne + nf = 8. [00069] In some embodiments, the multifunctionalized POSS molecule comprises at least seven different (e.g., chemically different) functional groups. For example, according to some embodiments wherein the POSS molecule is multifunctionalized, the first R1 in the POSS molecule (e.g., according to Formula (I)) is different from the second R1 in the POSS molecule, the third R1 in the POSS molecule, the fourth R1 in the POSS molecule, the fifth R1 in the POSS molecule, the sixth R1 in the POSS molecule, and a seventh R1 in the POSS molecule. In some embodiments, the second R1 is different from the third R1, the fourth R1, the fifth R1, the sixth R1, and the seventh R1. In some embodiments, the third R1 is different from the fourth R1, the fifth R1, the sixth R1, and the seventh R1. In some embodiments, the fourth R1 is different from the fifth R1, the sixth R1, and the seventh R1. In some embodiments, the fifth R1 is different from the sixth R1 and the seventh R1. In some embodiments, the sixth R1 is different from the seventh R1.
[00070] The ratio of the first R1 to the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, and the seventh R1 may be selected from a variety of suitable ratios. In some embodiments, for example, the multifunctionalized POSS molecule having a Tg structure comprises na first R1 groups, second R1 groups, nc third R1 groups, nd fourth R1 groups, ne fifth R1 groups, nf sixth R1 groups, and ng seventh R1 groups, wherein each of na, nb, nc, nd, ne, nf and ng are independently greater than or equal to 1 and less than or equal to 2 such that na + nb + nc + nd + ne + nf + ng = 8.
[00071] In some embodiments, the multifunctionalized POSS molecule comprises eight different (e.g., chemically different) functional groups. For example, according to some embodiments wherein the POSS molecule is multifunctionalized, the first R1 in the POSS molecule (e.g., according to Formula (I)) is different from the second R1 in the POSS molecule, the third R1 in the POSS molecule, the fourth R1 in the POSS molecule, the fifth R1 in the POSS molecule, the sixth R1 in the POSS molecule, the seventh R1 in the POSS molecule, and an eighth R1 in the POSS molecule. In some embodiments, the second R1 is different from the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and the eighth R1. In some embodiments, the third R1 is different from the fourth R1, the fifth R1, the sixth R1, the seventh R1, and the eighth R1. In some embodiments, the fourth R1 is different from the fifth R1, the sixth R1, the seventh R1, and the eighth R1. In some embodiments, the fifth R1 is different from the sixth R1, the seventh R1, and the eighth R1. In some embodiments, the sixth R1 is different from the seventh R1 and the eighth R1. In some embodiments, the seventh R1 is different from the eighth R1.
[00072] While much of the description above refers to multifunctionalized POSS molecules having a T8 structure, those of ordinary skill in the art would readily envision, based upon the teachings of this specification, combinations of R1 groups for multifunctionalized POSS molecules having any number of Si tetrahedral vertices.
[00073] For example, according to some embodiments, a multifunctionalized POSS molecule having a T4 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, and nd fourth R1 groups. In some embodiments, each first R1 group, second R1 group, third R1 group, and fourth R1 group may be the same or different provided that at least one R1 is different from another R1. In some embodiments, na, nb, nc, nd and are independently greater than or equal to 1 and less than or equal to 3 such that na + nb + nc + nd = 4.
[00074] According to some embodiments, a multifunctionalized POSS molecule having a T6 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, nd fourth R1 groups, rie fifth R1 groups, and nf sixth R1 groups. In some embodiments, each first R1 group, second R1 group, third R1 group, fourth R1 group, fifth R1 group, and sixth R1 group may be the same or different provided that at least one R1 is different from another R1. In some embodiments, each of na, nb, nc, nd, ne, and nf are independently greater than or equal to 1 and less than or equal to 5 such that na + nb + nc + nd + ne + nf = 6.
[00075] According to some embodiments, a multifunctionalized POSS molecule having a T10 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, nd fourth R1 groups, ne fifth R1 groups, nf sixth R1 groups, ng seventh R1 groups, nh eighth R1 groups, ni ninth R1 groups, and nj tenth R1 groups. In some embodiments, each first R1 group, second R1 group, third R1 group, fourth R1 group, fifth R1 group, sixth R1 group, seventh R1 group, eighth R1 group, ninth R1 group, and tenth R1 group may be the same or different provided that at least one R1 is different from another R1. In some embodiments, each of na, nb, nc, nd, ne, nf, ng, nh, ni, and nj are independently greater than or equal to 1 and less than or equal to 9 such that na + nb + nc + nd + ne + nf + ng + nh + ni + nj = 10.
[00076] According to some embodiments, a multifunctionalized POSS molecule having a T12 structure comprises na first R1 groups, nb second R1 groups, nc third R1 groups, nd fourth R1 groups, ne fifth R1 groups, nf sixth R1 groups, ng seventh R1 groups, nh eighth R1 groups, ni ninth R1 groups, nj tenth R1 groups, nk eleventh R1 groups, and nl twelfth R1 groups. In some embodiments, each first R1 group, second R1 group, third R1 group, fourth R1 group, fifth R1 group, sixth R1 group, seventh R1 group, eighth R1 group, ninth R1 group, tenth R1 group, eleventh R1 group, and twelfth R1 group may be the same or different provided that at least one R1 is different from another R1. In some embodiments, each of na, nb, nc, nd, ne, nf, ng, nh, ni, nj, nk, and nl are independently greater than or equal to 1 and less than or equal to 11 such that na + nb + nc + nd + ne + nf + ng + nh + ni + nj + nk + nl = 12.
[00077] In some embodiments, the multifunctionalized POSS molecule (e.g., according to Formula (I)) is functionalized with a polydialkylsiloxane group (e.g., poly dimethylsiloxane). In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3. In some non-limiting embodiments, the first R1 is -O-Si(CH3)2-(CH2)x-Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3 (e.g., -O-Si(CH3)2-(CH2)2- Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3). Other polydialkylsiloxane groups are also possible.
[00078] In some embodiments, the POSS molecule is multifunctionalized and the first R 1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2- O]n-Si(R2)3, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group that is chemically different than the first R1, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a-C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00079] According to some embodiments, the multifunctionalized POSS is functionalized with a tris(trialkylsiloxy)silane group (e.g., tris(trimethylsiloxy)silane). In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2- (R3)x-Si(OSi(R2)3)3. In some non-limiting embodiments, the first R1 is -O-Si(CH3)2-(CH2)x- Si(OSi(CH3)3)3 (e.g., -O-Si(CH3)2-Si(OSi(CH3)3)3). Other tris(trialkylsiloxy)silane groups are also possible.
[00080] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group that is chemically different than the first R1, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00081] According to some embodiments, the multifunctionalized POSS molecule is functionalized with a (meth)acrylate group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- In some non-limiting embodiments, the first R1 is -O- Si(CH3)2-(R3)x-O-C(O)-C(CH3)(CH2) (e.g., -O-Si(CH3)2-(CH2)(CH)(CH3)(CH2)2-O-C(O)- C(CH3)(CH2)) or -O-Si(CH3)2-(R3)x-C(O)-O(CH2)2C(CH3)(CH2)- (e.g., -O-Si(CH3)2- (CH2)(CH)(CH3)-C(O)-O(CH2)2C(CH3)(CH2)-). Other (meth)acrylate groups are also possible. [00082] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group that is chemically different than the first R1, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a-C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein. [00083] In some embodiments, the multifunctionalized POSS molecule is functionalized with a phenyl group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-C6H5. In some non-limiting embodiments, the first R1 is -(CH2)x-C6H5 (e.g., -C6H5). Other phenyl groups are also possible.
[00084] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is (R3)x-C6H5, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group that is chemically different than the first R1, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00085] According to some embodiments, the multifunctionalized POSS molecule (e.g., according to Formula (I)) is functionalized with a substituted phenyl group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is - (R3)x-C6H4-(R3)x-(R2)y. In some non-limiting embodiments, the first R1 is -(CH2)x-C6H4-CH3, - (CH2)x-C6H3-(CH3)2,-(CH2)x-C6H4-C(CH3)3, -(CH2)x-C6H3-(C(CH3)3)2, or - (CH2)x-C6H4-C6H5 (e.g., -(CH2)2-C6H4-CH3, -(CH2)2-C6H3-(CH3)2,-(CH2)2-C6H4-C(CH3)3, -(CH2)2-C6H3- (C(CH3)3)2, or -(CH2)2-C6H4-C6H5). Other substituted phenyl groups are also possible.
[00086] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is — (R3)x- C6H4-(R3) x-(R2)y, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group that is chemically different than the first R1, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00087] According to some embodiments, the multifunctionalized POSS molecule is functionalized with an amine group. In some embodiments, the amine group is a primary amine group. For example, in some embodiments, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH2. In some non-limiting embodiments, the first R1 is -(CH2)x-NH2 (e.g., -(CH2)3-NH2). Other primary amine groups are also possible. In some embodiments, the amine group is a secondary amine group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH-R2. In some non-limiting embodiments, the first R1 is -(CH2)x-NH-C6H5 (e.g., -(CH2)3-NH-C6H5). In some embodiments, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH-(CH2)2-NH2, - (R3)x-NH-(CH2)2-NH-(CH2)2-NH2, and/or -(R3)x-NH-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH2. Other secondary amine groups are also possible.
[00088] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH2 or -(R3)x-NH-R2, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group that is chemically different than the first R1, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00089] In some embodiments, the multifunctionalized POSS molecule is functionalized with an azide group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-N3. In some non-limiting embodiments, the first R1 is - (CH2)x-N3. Other azide groups are also possible.
[00090] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-N3, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group that is chemically different than the first R1, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00091] In some embodiments, the multifunctionalized POSS molecule is a functionalized with an isocyanate group. For example, in some embodiments, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(N)=C=O.
[00092] According to some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(N)=C=O, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, a-C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00093] According to some embodiments, the multifunctionalized POSS molecule is functionalized with a -C1-C10 alkyl group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(R2)y. In some non-limiting embodiments, the first R1 is -(CH2)-(CH)(CH3)-(CH2)-C(CH3)3 or -(CH2)-(CH)(CH3)2. Other - C1-C10 alkyl groups are also possible.
[00094] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(R2)y, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group that is chemically different than the first R1, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00095] According to some embodiments, the multifunctionalized POSS molecule is functionalized with an allyl group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-O-CH2CHCH2 or -O-CH2CHCH2. In some non-limiting embodiments, the first R1 is -O-Si(CH3)2-(R3)x-O-CH2CHCH2 or -O- CH2CHCH2. Other allyl groups are also possible.
[00096] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-O-CH2CHCH2, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1- C10 alkyl group, an allyl group that is chemically different than the first R1, an alcohol group, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00097] In some embodiments, the multifunctionalized POSS molecule is functionalized with an alcohol group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-OH. In some non-limiting embodiments, the first R1 is -(CH2)x-OH. Other alcohols are also possible.
[00098] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-OH, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a-C1-C10 alkyl group, an allyl group, an alcohol group that is chemically different than the first R1, an epoxy group, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00099] According to some embodiments, the multifunctionalized POSS molecule is functionalized with an epoxy group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(C2H4O). In some non-limiting embodiments, the first R1 is -(CH2)x-(C2H4O). Other epoxy groups are also possible.
[00100] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-(C2H4O), and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a-C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group that is chemically different than the first R1, a thiol group, and/or an acidic group), as described in greater detail elsewhere herein.
[00101] In some embodiments, the multifunctionalized POSS molecule is functionalized with a thiol group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-SH. In some non-limiting embodiments, the first R1 is - (CH2)x-SH. Other thiols are also possible.
[00102] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-SH, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group that is chemically different than the first R1, and/or an acidic group), as described in greater detail elsewhere herein.
[00103] According to some embodiments, the multifunctionalized POSS molecule is functionalized with an acidic group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is a Bronsted-Lowry acid that is capable of donating a proton. In some embodiments, the first R1 in the POSS molecule (e.g., according to Formula (I)) is a Lewis acid that is capable of forming a covalent bond with an electron pair. In some non-limiting embodiments, the first R1 comprises a sulfonic acid group (e.g., -SO3H), a phosphoric acid group (e.g., -PO4H2), a carboxylic acid group (e.g., -COOH), a thiol group (e.g., -SH), an alcohol group (e.g. , -OH), an amine group (e.g., -NH2), and/or combinations thereof. Other acidic groups are also possible.
[00104] In some embodiments, the POSS molecule is multifunctionalized and the first R1 in the POSS molecule (e.g., according to Formula (I)) is an acidic group, and at least one of the second R1, the third R1, the fourth R1, the fifth R1, the sixth R1, the seventh R1, and/or the eight R1 are selected from a variety of suitable functional groups (e.g., a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group that is chemically different than the first R1), as described in greater detail elsewhere herein.
[00105] According to some embodiments, the multifunctionalized POSS molecule is functionalized with a polydialkylsiloxane group (e.g., polydimethylsiloxane) and a (meth)acrylate group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3 and the second R1 is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)r-. In some non-limiting embodiments, the first R1 is -O-Si(CH3)2-(CH2)2-Si(CH3)2-O-[Si(CH3)2-O]n- Si(CH3)3 and the second R1 is -O-Si(CH3)2-(CH2)(CH)(CH3)(CH2)2-O-C(O)-C(CH3)(CH2) or- O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)-O(CH2)2C(CH3)(CH2)-.
[00106] In some embodiments, the multifunctionalized POSS molecule is functionalized with a phenyl group and a primary amine group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-C6H5 and the second R1 is - (R3)x-NH2. In some non-limiting embodiments, the first R1 is -C6H5 and the second R1 is - (CH2)3-NH2.
[00107] In accordance with some embodiments, the multifunctionalized POSS molecule is functionalized with a phenyl group and a secondary amine group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-C6H5 and the second R1 is -(R3)x-NH-R2. In some non-limiting embodiments, the first R1 is -C6H5 at the second R1 is -(CH2)3-NH-C6H5.
[00108] According to some embodiments, the multifunctionalized POSS molecule is functionalized with a substituted phenyl group and a primary amine group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is - (R3)x-C6Il4-(R3)x-(R2)y and the second R1 is -(R3)x-NH2. In some non-limiting embodiments, the first R1 is -(CH2)2-C6H4-C(CH3)3 and the second R1 is -(CH2)3-NH2. [00109] In some embodiments, the multifunctionalized POSS molecule is functionalized with a primary amine group and a -C1-C10 alkyl group. In some embodiments, for example, the first R1 in the POSS molecule (e.g., according to Formula (I)) is -(R3)x-NH2 and the second R1 is — (R3)x-(R2)y. In some non-limiting embodiments, the first R1 is -(CH2)3-NH2 and the second R1 is -(CH2)-(CH)(CH3)-(CH2)-C(CH3)3 or -(CH2)-(CH)(CH3)2.
[00110] According to some embodiments, the POSS molecule (e.g., according to Formula (I)) is a first POSS molecule and at least one R1 is configured to form a bond to a second POSS molecule. In some embodiments, for example, at least one R1 is a bridging moiety to another silicon (Si) atom of a second POSS molecule. According to some embodiments, configuring the POSS compound such that at least one R1 of the first POSS molecule (e.g., according to Formula (I)) is configured to form a bond to a second POSS molecule advantageously provides extended structures of POSS-based dimers, oligomers, and/or polymers.
[00111] The at least one R1 configured to form a bond to a second POSS molecule may be selected from a variety of suitable functional groups. In some embodiments, the at least one R1 configured to form a bond to a second POSS molecule comprises a bi-functional moiety that is capable of bridging between two Si atoms. In some embodiments, the at least one R1 configured to form a bond to a second POSS molecule comprises a (meth)acrylate group. In some embodiments, the at least one R1 configured to form a bond to a second POSS molecule is -O- Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-. In some non-limiting embodiments, the at least one R1 configured to form a bond to a second POSS molecule is -O- Si(CH3)2-(R3)x-C(O)-O(CH2)2C(CH3)(CH2)- (e.g., -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)- O(CH2)2C(CH3)(CH2)-). Other (meth)acrylate groups are also possible. In some embodiments, the at least one R1 configured to form a bond to a second POSS molecule comprises an allyl group. In some embodiments, the at least one R1 configured to form a bond to a second POSS molecule is -O-Si(R2)2-(R3)x-O-CH2CHCH2. Other allyl groups are also possible.
[00112] In some embodiments, the second POSS molecule is a POSS molecule according to Formula (I). In some embodiments, the second POSS molecule is multifunctionalized. In some embodiments, the second POSS molecule is the same (e.g., chemically the same) as the first POSS molecule. In other embodiments, the second POSS molecule is different (e.g., chemically different) from the first POSS molecule.
[00113] According to some embodiments, the POSS-based compound comprises a POSS molecule according to Formula (II):
Figure imgf000035_0001
wherein: each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,-O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-, -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)3, -(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)3, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, any of which may be optionally substituted, each R1’ is the same or different and is a bridging moiety to another Si atom of the POSS molecule, wherein each R1’ is selected from the group consisting of -O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- and -O-Si(R2)2-(R3)x-O-CH2CHCH2, any of which may be optionally substituted, each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, any of which may be optionally substituted, each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, any of which may be optionally substituted, each x is the same or different and is greater than or equal to 0 and less than or equal to
10, each y is the same or different and is greater than or equal to 1 and less than or equal to 3, n is greater than or equal to 2 and less than or equal to 100, and m is greater than or equal to 2 and less than or equal to 100.
[00114] As described above, each R1, R1’, R2, and/or R3 may, in some embodiments, be optionally substituted. For example, in some embodiments, at least one R1, R1’, R2, and/or R3 is optionally substituted with a polydialkylsiloxane group (e.g., polydimethylsiloxane). In some non-limiting embodiments, for example, at least one R2 is -C1-C10 alkyl substituted with a polydialkylsiloxane (e.g., polydimethylsiloxane) group.
[00115] The value of each x in the POSS molecule according to Formula (II) may be selected from a variety of suitable values. In some embodiments, for example, the value of each x in the POSS molecule according to Formula (II) is independently greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9. In some embodiments, the value of each x in the POSS molecule according to Formula (II) is independently less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1. Combinations of the above recited ranges are possible (e.g., the value of each x in the POSS molecule according to Formula (II) is independently greater than or equal to 0 and less than or equal to 10, the value of each x in the POSS molecule according to Formula (II) is independently greater than or equal to 4 and less than or equal to 6). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for x based upon the teachings of this specification. [00116] The value of each y in the POSS molecule according to Formula (II) may be selected from a variety of suitable values. In some embodiments, for example, the value of each y in the POSS molecule according to Formula (II) is independently greater than or equal to 1 or greater than or equal to 2. In some embodiments, the value of each y in the POSS molecule according to Formula (II) is independently less than or equal to 3 or less than or equal to 2. Combinations of the above recited ranges are possible (e.g., the value of each y in the POSS molecule according to Formula (II) is independently greater than or equal to 1 and less than or equal to 3). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for y based upon the teachings of this specification.
[00117] The value of n in the POSS molecule according to Formula (II) may be selected from a variety of suitable values. In some embodiments, for example, the value of n in the POSS molecule according to Formula (II) is greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90. In some embodiments, the value of n in the POSS molecule according to Formula (II) is less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 20, less than or equal to 10, less than or equal to 5, or less than or equal to 2. Combinations of the above recited ranges are possible (e.g., the value of n in the POSS molecule according to Formula (II) is greater than or equal to 1 and less than or equal to 100, the value of n in the POSS molecule according to Formula (II) is greater than or equal to 40 and less than or equal to 60). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for n based upon the teachings of this specification.
[00118] The value of m in the POSS molecule according to Formula (II) may be selected from a variety of suitable values. In some embodiments, for example, the value of m in the POSS molecule according to Formula (II) is greater than or equal to 1, greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 40, greater than or equal to 50, greater than or equal to 60, greater than or equal to 70, greater than or equal to 80, or greater than or equal to 90. In some embodiments, the value of m in the POSS molecule according to Formula (II) is less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, less than or equal to 60, less than or equal to 50, less than or equal to 40, less than or equal to 30, less than or equal to 20, less than or equal to 10, less than or equal to 5, or less than or equal to 2. Combinations of the above recited ranges are possible (e.g., the value of m in the POSS molecule according to Formula (II) is greater than or equal to 1 and less than or equal to 100, the value of m in the POSS molecule according to Formula (II) is greater than or equal to 40 and less than or equal to 60). Other ranges are also possible. Those of ordinary skill in the art would be capable of selecting other values for m based upon the teachings of this specification.
[00119] In some non-limiting embodiments, the value of m in the POSS molecule according to Formula (II) is greater than or equal to 2 and less than or equal to 4. In other nonlimiting embodiments, the value of m in the POSS molecule according to Formula (II) is greater than or equal to 2 and less than or equal to 3. In yet other non-limiting embodiments, the value of m in the POSS molecule according to Formula (II) is 2.
[00120] According to some embodiments, the POSS molecule comprises 8 Si T vertices corresponding to a T8 cage (e.g., as in Formula (II)). In other embodiments, however, the POSS molecule comprises any of a variety of suitable Si T vertices, as described above. In some embodiments, for example, the POSS molecule comprises 4 Si T vertices (a T4 cage having 4 R1 groups), 6 Si T vertices (a T6 cage having 6 R1 groups), 10 Si T vertices (a T10 cage having 10 R1 groups), or 12 Si T vertices (a T12 cage having 12 R1 groups). Those of ordinary skill in the art would understand, based upon the teachings of this specification, that any of the concepts described herein (e.g., such as those described with respect to the POSS molecule according to Formula (II)) may also correspond to a POSS molecule comprising a T4 cage, a T6 cage, a T10 cage, or a T12 cage.
[00121] According to some embodiments, each R1 in the POSS molecule (e.g., according to Formula (II)) may independently comprise a polydialkylsiloxane (e.g., polydimethylsiloxane) group, a tris(trialkylsiloxy)silane (e.g., tris(trimethylsiloxy)silane) group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1-C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group, as described herein in greater detail with respect to the POSS molecule according to Formula (I).
[00122] According to some embodiments, each R1’ in the POSS molecule (e.g., according to Formula (II)) comprises a bi-functional moiety that is capable of bridging between two Si atoms. In some embodiments, for example, each R1’ comprises a (meth)acrylate group and/or an allyl group. In certain embodiments, each R1’ in the POSS molecule (e.g., according to Formula (II)) comprises isoprenyl methacrylate and/or allyl alcohol.
[00123] In some embodiments, the POSS molecule (e.g., according to Formula (II)) is multifunctionalized, as described herein in greater detail with respect to the POSS molecule according to Formula (I). For example, in some embodiments, the POSS molecule (e.g., according to Formula (II)) is configured such that at least one R1 is different from another R1. [00124] According to some embodiments, a method of synthesizing a POSS-based compound (e.g., according to Formula (I) and/or Formula (II)) is described. In some embodiments, the synthesis of the POSS-based compound is advantageously straightforward and tunable such that a wide variety of POSS-based compounds with various functional groups (e.g., polydialkylsiloxane groups, tris(trialkylsiloxy)silane groups, (meth)acrylate groups, phenyl groups, substituted phenyl groups, amine groups, azide groups, isocyanate groups, -C1-C10 alkyl groups, allyl groups, alcohol groups, epoxy groups, thiol groups, and/or acidic groups) may be obtained.
[00125] According to some embodiments, the stoichiometry of the starting materials can be tuned to provide a POSS-based compound with desirable properties depending on the application in which the POSS-based compound will be used. In some embodiments, for example, the stoichiometry of one or more precursors can be tuned to provide a functionalized POSS-based compound comprising eight of the same functional groups. In other embodiments, the stoichiometry of one or more precursors can be tuned to provide a multifunctionalized POSS- based compound comprising at least two and less than or equal to eight different (e.g., chemically different) functional groups. In yet other embodiments, the stoichiometry of one or more precursors can be tuned to provide a POSS-based compound comprising an extended structure of a POSS-based dimer, oligomer, and/or polymer. In some such embodiments, the POSS-based dimer, oligomer, and/or polymer comprises the same or different (e.g., chemically different) functional groups.
[00126] In some embodiments, a method of synthesizing the POSS-based compound comprises reacting a precursor POSS molecule with one or more precursor compounds comprising one or more functional groups, thereby providing the POSS-based compound. [00127] The precursor POSS molecule may be selected from a variety of suitable precursor POSS molecules. In some embodiments, for example, the precursor POSS molecule is octasilane POSS, octavinyl POSS, glycidyl POSS, methacrylic POSS, and the like. In some embodiments, the precursor POSS molecule is commercially available. Other precursor POSS molecules are also possible.
[00128] The one or more functional groups of the one or more precursor compounds may be selected from a variety of suitable functional groups. In some embodiments, the one or more precursor compounds comprise a vinyl group. In some embodiments, the vinyl group is configured to react with one or more groups (e.g., one or more silane groups) of the precursor POSS molecule. In some embodiments, the one or more precursor compounds comprise a poly dialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1- C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group. Other functional groups are also possible.
[00129] According to some embodiments, one or more precursor compounds comprising a (meth)acrylate group and/or an allyl group advantageously provides an extended structure of a POSS-based dimer, oligomer, and/or polymer, as described in greater detail elsewhere herein.
[00130] The one or more precursor compounds comprising the one or more functional groups may be selected from a variety of suitable precursor compounds. In some non-limiting embodiments, for example, the precursor compound comprising the one or more functional groups comprises a mono-vinyl polydialkylsiloxane (e.g., mono-vinyl polydimethylsiloxane) and/or isoprenyl methacrylate (IPEMA). [00131] In some embodiments, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups comprises reacting the precursor POSS molecule with one precursor compound comprising one or more functional groups. In some embodiments, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups comprises reacting the precursor POSS molecule with more than one precursor compound (e.g., two precursor compounds, three precursor compounds, four precursor compounds, five precursor compounds, six precursor compounds, seven precursor compounds, or eight precursor compounds) comprising one or more functional groups. In some embodiments, reacting the precursor POSS molecule with more than one precursor compound comprising the one or more functional groups advantageously provides a multifunctionalized POSS molecule.
[00132] According to some embodiments, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed in the presence of a catalyst. The catalyst may be selected from a variety of suitable catalysts. In some embodiments, for example, the catalyst comprises a metal such as palladium (Pd) (e.g., palladium metal or Pd(0)), a hydroxide (OH-) (e.g., potassium hydroxide or KOH), and/or water (H2O). Other catalysts are also possible. In some embodiments, the composition of the catalyst depends on the composition of the starting materials (e.g., the precursor POSS molecule and/or the one or more precursor compounds comprising one or more functional groups) and/or the reaction solvent.
[00133] Reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups may be performed at any of a variety of suitable temperatures. In some embodiments, for example, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 20 °C, greater than or equal to 40 °C, greater than or equal to 60 °C, greater than or equal to 80 °C, greater than or equal to 100 °C, greater than or equal to 120 °C, greater than or equal to 140 °C, greater than or equal to 160 °C, or greater than or equal to 180 °C. In some embodiments, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature less than or equal to 200 °C, less than or equal to 180 °C, less than or equal to 160 °C, less than or equal to 140 °C, less than or equal to 120 °C, less than or equal to 100 °C, less than or equal to 80 °C, less than or equal to 60 °C, or less than or equal to 40 °C. Combinations of the above recited ranges are possible (e.g., reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 20 °C and less than or equal to 200 °C, reacting the precursor POSS molecule with the one or more precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 100 °C and less than or equal to 120 °C). In some embodiments, the temperature of the reaction between the precursor POSS molecule and the one or more precursor compounds comprising the one or more functional groups depends on the composition of the starting materials (e.g., the precursor POSS molecule and/or the one or more precursor compounds comprising one or more functional groups) and/or the reaction solvent. In some embodiments, for example, the temperature of the reaction between the precursor POSS molecule and the one or more precursor compounds comprising the one more functional groups is a reflux temperature of the reaction solvent. [00134] According to some embodiments, a method of synthesizing the POSS-based compound comprises reacting one or more silicon-containing precursor compounds comprising one or more functional groups, thereby providing the POSS-based compound.
[00135] The one or more functional groups of the one or more silicon-containing precursor compounds may be selected from a variety of suitable functional groups. In some embodiments, the one or more silicon-containing precursor compounds comprise a polydialkylsiloxane group, a tris(trialkylsiloxy)silane group, a (meth)acrylate group, a phenyl group, a substituted phenyl group, an amine group, an azide group, an isocyanate group, a -C1- C10 alkyl group, an allyl group, an alcohol group, an epoxy group, a thiol group, and/or an acidic group. Other functional groups are also possible.
[00136] According to some embodiments, one or more silicon-containing precursor compounds comprising a (meth)acrylate group and/or an ally group advantageously provides an extended structure of a POSS-based dimer, oligomer, and/or polymer, as described in greater- detail elsewhere herein. [00137] The one or more silicon-containing precursor compounds comprising the one or more functional groups may be selected from a variety of suitable silicon-containing precursor compounds. In some non-limiting embodiments, for example, the precursor compound comprises trimethoxyphenylsilane, (3-aminopropyl)trimethoxysilane, N-(3- (trimethoxysilyl)propyl)aniline, p-(t-butyl)phenethyltrichlorosilane, trimethoxy(2,4,4- trimethylpentyl)silane, and/or isobutyltrimethoxysilane. Other silicon-containing precursor compounds comprising one or more functional groups are also possible.
[00138] In some embodiments, reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups comprises reacting one silicon- containing precursor compound comprising one or more functional groups. In some embodiments, reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups comprises reacting more than one silicon-containing precursor compounds (e.g., two silicon-containing precursor compounds, three silicon-containing precursor compounds, four silicon-containing precursor compounds, five silicon-containing precursor compounds, six silicon-containing precursor compounds, seven silicon-containing precursor compounds, or eight silicon-containing precursor compounds) comprising one or more functional groups. In some embodiments, reacting more than one silicon-containing precursor compound comprising the one or more functional groups advantageously provides a multifunctionalized POSS molecule.
[00139] According to some embodiments, reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups is performed in the presence of a catalyst. The catalyst may be selected from a variety of suitable catalysts. In some embodiments, for example, the catalyst comprises a metal such as palladium (Pd) (e.g., palladium metal or Pd(0)), a hydroxide (OH-) (e.g., potassium hydroxide or KOH), and/or water (H2O). Other catalysts are also possible. In some embodiments, the composition of the catalyst depends on the composition of the starting materials (e.g., the one or more silicon-containing precursor compounds comprising one or more functional groups) and/or the reaction solvent. [00140] Reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups may be performed at any of a variety of suitable temperatures. In some embodiments, for example, reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 20 °C, greater than or equal to 40 °C, greater than or equal to 60 °C, greater than or equal to 80 °C, greater than or equal to 100 °C, greater than or equal to 120 °C, greater than or equal to 140 °C, greater than or equal to 160 °C, or greater than or equal to 180 °C. In some embodiments, reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups is performed at a temperature less than or equal to 200 °C, less than or equal to 180 °C, less than or equal to 160 °C, less than or equal to 140 °C, less than or equal to 120 °C, less than or equal to 100 °C, less than or equal to 80 °C, less than or equal to 60 °C, or less than or equal to 40 °C. Combinations of the above recited ranges are possible (e.g., reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 20 °C and less than or equal to 200 °C, reacting the one or more silicon-containing precursor compounds comprising the one or more functional groups is performed at a temperature greater than or equal to 100 °C and less than or equal to 120 °C). In some embodiments, the temperature of the reaction between the one or more silicon-containing precursor compounds comprising the one more functional groups depends on the composition of the starting materials (e.g., the one or more silicon- containing precursor compounds comprising one or more functional groups) and/or the reaction solvent. In some embodiments, for example, the temperature of the reaction between the one or more silicon-containing precursor compounds comprising the one more functional groups is a reflux temperature of the reaction solvent.
[00141] According to some embodiments, the structure of the POSS-based compound is determined by spectroscopic techniques, including, but not limited to, proton nuclear magnetic resonance (1H-NMR), silicon nuclear magnetic resonance (29Si-NMR), and/or infrared (IR) spectroscopy (e.g., Fourier transform IR or FT-IR).
[00142] The POSS-based compound may have any of a variety of suitable weight average molecular weights (Mw). In some embodiments, for example, the POSS-based compound has a Mw greater than or equal to 2,000 Da, greater than or equal to 5,000 Da, greater than or equal to 10,000 Da, greater than or equal to 15,000 Da, greater than or equal to 20,000 Da, greater than or equal to 50,000 Da, greater than or equal to 100,000 Da, greater than or equal to 200,000 Da, or greater than or equal to 500,000 Da. In some embodiments, the POSS-based compound has a Mw less than or equal to 1,000,000 Da, less than or equal to 500,000 Da, less than or equal to 200,000 Da, less than or equal to 100,000 Da, less than or equal to 50,000 Da, less than or equal to 20,000 Da, less than or equal to 15,000 Da, less than or equal to 10,000 Da, or less than or equal to 5,000 Da. Combinations of the above recited ranges are possible (e.g., the POSS-based compound has a Mw greater than or equal to 2,000 Da and less than or equal to 1,000,000 Da, the POSS-based compound has a Mw greater than or equal to 10,000 Da and less than or equal to 15,000 Da). Other ranges are also possible. In some embodiments, the Mw of the POSS-based compound is determined by gel permeation chromatography (GPC).
[00143] The POSS-based compound may have any of a variety of suitable number average molecular weights (Mn). In some embodiments, for example, the POSS-based compound has a Mn greater than or equal to 2,000 Da, greater than or equal to 5,000 Da, greater than or equal to 10,000 Da, greater than or equal to 15,000 Da, greater than or equal to 20,000 Da, greater than or equal to 50,000 Da, greater than or equal to 100,000 Da, greater than or equal to 200,000 Da, or greater than or equal to 500,000 Da. In some embodiments, the POSS-based compound has a Mn less than or equal to 1,000,000 Da, less than or equal to 500,000 Da, less than or equal to 200,000 Da, less than or equal to 100,000 Da, less than or equal to 50,000 Da, less than or equal to 20,000 Da, less than or equal to 15,000 Da, less than or equal to 10,000 Da, or less than or equal to 5,000 Da. Combinations of the above recited ranges are possible (e.g., the POSS-based compound has a Mn greater than or equal to 2,000 Da and less than or equal to 1,000,000 Da, the POSS-based compound has a Mn greater than or equal to 10,000 Da and less than or equal to 15,000 Da). Other ranges are also possible. In some embodiments, the Mn of the POSS-based compound is determined by gel permeation chromatography (GPC).
[00144] The POSS-based compound may have any of a variety of suitable polydispersity indices. In some embodiments, for example, the POSS-based compound has a polydispersity index greater than or equal to 1, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.4, greater than or equal to 1.5, greater than or equal to 1.6, greater than or equal to 1.7, greater than or equal to 1.8, or greater than or equal to 1.9. In some embodiments, the POSS-based compound has a polydispersity index less than or equal to 2, less than or equal to 1.9, less than or equal to 1.8, less than or equal to 1.7, less than or equal to 1.6, less than or equal to 1.5, less than or equal to 1.4, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above recited ranges are possible (e.g., the POSS-based compound has a polydispersity index greater than or equal to 1 and less than or equal to 2, the POSS-based compound has a polydispersity index greater than or equal to 1.4 and less than or equal to 1.6). Other ranges are also possible. The polydispersity index of the POSS-based compound is calculated by dividing the Mw of the POSS-based compound by the Mn of the POSS-based compound.
[00145] The POSS-based compound may have any of a variety of suitable peak molecular weights (Mp) as determined by GPC. In some embodiments, for example, the POSS-based compound has a Mp greater than or equal to 2,000 Da, greater than or equal to 5,000 Da, greater than or equal to 10,000 Da, greater than or equal to 15,000 Da, greater than or equal to 20,000 Da, greater than or equal to 50,000 Da, greater than or equal to 100,000 Da, greater than or equal to 200,000 Da, or greater than or equal to 500,000 Da. In some embodiments, the POSS-based compound has a Mp less than or equal to 1,000,000 Da, less than or equal to 500,000 Da, less than or equal to 200,000 Da, less than or equal to 100,000 Da, less than or equal to 50,000 Da, less than or equal to 20,000 Da, less than or equal to 15,000 Da, less than or equal to 10,000 Da, or less than or equal to 5,000 Da. Combinations of the above recited ranges are possible (e.g., the POSS-based compound has a Mp greater than or equal to 2,000 Da and less than or equal to 1,000,000 Da, the POSS-based compound has a Mp greater than or equal to 10,000 Da and less than or equal to 15,000 Da). Other ranges are also possible.
[00146] According to some embodiments, a composition is described. In some embodiments, the composition comprises a low surface energy material. In some embodiments, the low surface energy material comprises a POSS-based compound (e.g., according to Formula (I) and/or Formula (II)) as described in greater detail elsewhere herein.
[00147] In some embodiments, the composition is substantially non-fluorinated. For example, in some embodiments, the composition comprises fluorine in an amount less than or equal to 5 wt.%, less than or equal to 4 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, or less than or equal to 0.2 wt.% versus a total weight of the composition. In some embodiments, the composition comprises fluorine in an amount greater than or equal to 0 wt.%, greater than or equal to 0.2 wt.%, greater than or equal to 0.5 wt.%, greater than or equal to 1 wt.%, greater than or equal to 2 wt.%, greater than or equal to 3 wt.%, or greater than or equal to 4 wt.% versus a total weight of the composition. Combinations of the above recited ranges are possible (e.g., the composition comprises fluorine in an amount less than or equal to 5 wt.% and greater than or equal to 0 wt.% versus a total weight percent of the composition, the composition comprises fluorine in an amount less than or equal to 2 wt.% and greater than or equal to 1 wt.% versus a total weight of the composition). Other ranges are also possible.
[00148] In some non-limiting embodiments, the composition is non-fluorinated such that the composition comprises fluorine in an amount of 0 wt.% versus a total weight of the composition.
[00149] The composition (e.g., low surface material) may comprise the POSS-based compound in any of a variety of suitable amounts. In some embodiments, the composition comprises an advantageously low amount (e.g., an additive amount) of the POSS-based compound. In some embodiments, the composition comprises the POSS-based compound in an amount greater than or equal to 0.1 wt.%, greater than or equal to 0.2 wt.%, greater than or equal to 0.5 wt.%, greater than or equal to 1 wt.%, greater than or equal to 2 wt.%, greater than or equal to 3 wt.%, greater than or equal to 4 wt.%, greater than or equal to 5 wt.%, greater than or equal to 6 wt.%, greater than or equal to 7 wt.%, greater than or equal to 8 wt.%, or greater than or equal to 9 wt.% versus a total weight of the composition. In some embodiments, the composition comprises the POSS-based compound in an amount less than or equal to 10 wt.%, less than or equal to 9 wt.%, less than or equal to 8 wt.%, less than or equal to 7 wt.%, less than or equal to 6 wt.%, less than or equal to 5 wt.%, less than or equal to 4 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, or less than or equal to 0.2 wt.% versus a total weight of the composition. Combinations of the above recited ranges are possible (e.g., the composition comprises the POSS-based compound in an amount greater than or equal to 0.1 wt.% and less than or equal to 10 wt.% versus a total weight of the composition, the composition comprises the POSS-based compound in an amount greater than or equal to 4 wt.% and less than or equal to 6 wt.% versus a total weight of the composition). Other ranges are also possible.
[00150] In some embodiments, the POSS-based compound is configured to interact with one or more components of the composition. In some embodiments, for example, the POSS- based compound is functionalized with one or more functional groups that are configured to interact with one or more components of the composition. In some embodiments, the interaction between the POSS-based compound and the one or more components of the composition is a bonding interaction or a non-bonding interaction. Suitable interactions include, for example, covalent bonding, non-covalent bonding, ionic bonding, hydrogen-bonding, van der Waals forces, electrostatic forces, dipole interactions, coordination, chelation, and the like. In some embodiments, the POSS-based compound is configured to crosslink with one or more components of the composition.
[00151] The one or more components of the composition may be selected from a variety of suitable components. In some embodiments, for example, the one or more components of the composition comprise one or more base polymers. In some embodiments, the base polymer comprises an epoxy and/or a (meth)acrylate.
[00152] The composition (e.g., low surface material) may comprise the one or more components (e.g., one or more base polymers) in any of a variety of suitable amounts. In some embodiments, the composition comprises the one or more components in an amount greater than or equal to 90 wt.%, greater than or equal to 91 wt.%, greater than or equal to 92 wt.%, greater than or equal to 93 wt.%, greater than or equal to 94 wt.%, greater than or equal to 95 wt.%, greater than or equal to 96 wt.%, greater than or equal to 97 wt.%, greater than or equal to 98 wt.%, greater than or equal to 99 wt.%, greater than or equal to 99.5 wt.%, or greater than or equal to 99.8 wt.% versus a total weight of the composition. In some embodiments, the composition comprises the one or more components in an amount less than or equal to 99.9 wt.%, less than or equal to 99.8 wt.%, less than or equal to 99.5 wt.%, less than or equal to 99 wt.%, less than or equal to 98 wt.%, less than or equal to 97 wt.%, less than or equal to 96 wt.%, less than or equal to 95 wt.%, less than or equal to 94 wt.%, less than or equal to 93 wt.%, less than or equal to 92 wt.%, or less than or equal to 91 wt.% versus a total weight of the composition. Combinations of the above recited ranges are possible (e.g., the composition comprises the one or more components in an amount greater than or equal to 90 wt.% and less than or equal to 99.9 wt.% versus a total weight of the composition, the composition comprises the one or more components in an amount greater than or equal to 94 wt.% and less than or equal to 96 wt.% versus a total weight of the composition). Other ranges are also possible.
[00153] The composition (e.g., low surface energy material) may have any of a variety of suitable coefficient of friction values. In some embodiments, the coefficient of friction of the composition is advantageously low. In some embodiments, the composition has a coefficient of friction less than or equal to 0.1, less than or equal to 0.09, less than or equal to 0.08, less than or equal to 0.07, less than or equal to 0.06, less than or equal to 0,05, less than or equal to 0.04, less than or equal to 0.03, or less than or equal to 0.02. In some embodiments, the composition has a coefficient of friction greater than or equal to 0.01, greater than or equal to 0.02, greater than or equal to 0.03, greater than or equal 0.04, greater than or equal 0.05, greater than or equal to 0.06, greater than or equal 0.07, greater than or equal 0.08, or greater than or equal to 0.09.
Combinations of the above recited ranges are possible (e.g., the composition has a coefficient of friction less than or equal to 0.1 and greater than or equal to 0.01, the composition has a coefficient of friction less than or equal to 0.06 and greater than or equal to 0.04). Other ranges are also possible. According to some embodiments, the coefficient of friction of the composition is determined using a portable friction meter muse.
[00154] According to some embodiments, the composition (e.g., the low surface energy material) is hydrophobic. The composition may have any of a variety of suitable water contact angles. In some embodiments, for example, the composition has a water contact angle greater than or equal to 90°, greater than or equal to 95°, greater than or equal to 100°, greater than or equal to 105°, greater than or equal to 110°, greater than or equal to 115°, greater than or equal to 120°, greater than or equal to 125°, greater than or equal to 130°, greater than or equal to 135°, greater than or equal to 140°, greater than or equal to 145°, greater than or equal to 150°, greater than or equal to 155°, greater than or equal to 160°, greater than or equal to 165°, greater than or equal to 170°, or greater than or equal to 175°. In some embodiments, the composition has a water contact angle less than or equal to 180°, less than or equal to 175°, less than or equal to 170°, less than or equal to 165°, less than or equal to 160°, less than or equal to 155°, less than or equal to 150°, less than or equal to 145°, less than or equal to 140°, less than or equal to 135°, less than or equal to 130°, less than or equal to 125°, less than or equal to 120°, less than or equal to 115°, less than or equal to 110°, less than or equal to 105°, less than or equal to 100°, or less than or equal to 95°. Combinations of the above recited ranges are possible (e.g., the composition has a water contact angle greater than or equal to 90° and less than or equal to 180°, the composition has a water contact angle greater than or equal to 130° and less than or equal to 140°). Other ranges are also possible. In some embodiments, the water contact angle of the composition is determined using a goniometer.
[00155] Turning to the figures, specific non-limiting embodiments are described in further detail. It should be understood that the various systems, components, features, and methods described relative to these embodiments may be used either individually and/or in any desired combination as the disclosure is not limited to only the specific embodiments described herein.
[00156] FIG. 1 shows, according to some embodiments, a schematic diagram of an exemplary article. In some embodiments, article 100 comprises substrate 110 comprising at least one surface 120. Suitable substrate materials are described in greater detail elsewhere herein.
[00157] In accordance with some embodiments, composition 130 is disposed on at least a portion of at least one surface 120 of substrate 110 such that composition 130 coats at least the portion of at least one surface 120 of substrate 110. In some embodiments, composition 130 comprises a low surface energy material comprising a POSS-based compound, as described in greater detail elsewhere herein.
[00158] The composition coating the surface of the substrate may have any of a variety of suitable thicknesses. Referring to FIG. 1, for example, composition 130 coating at least the portion of at least one surface 120 of substrate 110 has thickness 132. In some embodiments, the composition coating the surface has an average thickness of greater than or equal to 5 nm, greater than or equal to 10 nm, greater than or equal to 20 nm, greater than or equal to 30 nm, greater than or equal to 40 nm, greater than or equal to 50 nm, greater than or equal to 60 nm, greater than or equal to 70 nm, greater than or equal to 80 nm, or greater than or equal to 90 nm. In some embodiments, the composition coating the surface has an average thickness of less than or equal to 100 nm, less than or equal to 90 nm, less than or equal to 80 nm, less than or equal to 70 nm, less than or equal to 60 nm, less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 30 nm, less than or equal to 20 nm, or less than or equal to 10 nm.
Combinations of the above recited ranges are possible (e.g., the composition coating the surface has an average thickness of greater than or equal to 5 nm and less than or equal to 100 nm, the composition coating the surface has an average thickness of greater than or equal to 40 nm and less than or equal to 60 nm). Other ranges are also possible. In some embodiments, the average thickness of the composition coating the surface is determined by ellipsometry.
[00159] While composition 130 coating surface 120 of substrate 110 is depicted in FIG. 1 as a smooth layer of uniform thickness, those of ordinary skill in the art would understand that this is for illustration purposes only and the thickness of the composition coating the surface of the substrate may have a particular roughness and/or may vary in thickness, in accordance with some embodiments. In some embodiments, the composition coating the surface of the substrate is of relatively uniform thickness (e.g., within less than or equal to 10% of the total thickness) over at least a substantial portion of the surface of the substrate (e.g., greater than or equal to 75% of the surface area of the surface of the substrate on which the composition is disposed). [00160] According to certain embodiments, the composition coating the surface of the substrate may comprise a plurality of features. In some embodiments, for example, the composition coating the surface of the substrate comprises a plurality of microscale and/or nanoscale features. In some embodiments, the plurality of features may advantageously render the composition more hydrophobic as compared to a composition that does not comprise the plurality of microscale and/or nanoscale features but is otherwise equivalent. For example, in some embodiments, a composition comprising a plurality of features may have a water contact angle greater than or equal to 120°.
[00161] In some embodiments, the plurality of features comprise at least one member selected from the group consisting of particles, amorphous particles, substantially spherical particles, posts, nanoneedles, microneedles, nanograss, micrograss, pores, grooves, ridges, and/or combinations thereof. According to some embodiments, the plurality of features may be formed as the composition is deposited on the surface of the substrate.
[00162] According to some embodiments, at least a portion of the composition comprising the low surface energy material is immobilized on at least the portion of the at least one surface of the substrate. Referring to FIG. 1, for example, at least a portion of composition 130 is immobilized on at least the portion of at least one surface 120 of substrate 110. In some embodiments, for example, at least a portion of composition 130 is chemically bound (e.g., covalently bound, non-covalently bound) to at least the portion of at least one surface 120 of substrate 110. Examples of suitable bonding interactions include, in some embodiments, covalent bonding, non-co valent bonding, ionic bonding, hydrogen bonding, van der Waals forces, electrostatic forces, dipole interactions, coordination, chelation, and the like. In some embodiments, at least the portion of the composition is immobilized on at least the portion of the at least one surface of the substrate via at least one -Si-O- linkage.
[00163] In some embodiments, an article comprising the composition comprising the POSS-based compound is substantially non-fluorinated. For example, in some embodiments, the article comprises fluorine in an amount less than or equal to 5 wt.%, less than or equal to 4 wt.%, less than or equal to 3 wt.%, less than or equal to 2 wt.%, less than or equal to 1 wt.%, less than or equal to 0.5 wt.%, or less than or equal to 0.2 wt.% versus a total weight of the article. In some embodiments, the article comprises fluorine in an amount greater than or equal to 0 wt.%, greater than or equal to 0.2 wt.%, greater than or equal to 0.5 wt.%, greater than or equal to 1 wt.%, greater than or equal to 2 wt.%, greater than or equal to 3 wt.%, or greater than or equal to 4 wt.% versus a total weight of the article. Combinations of the above recited ranges are possible (e.g., the article comprises fluorine in an amount less than or equal to 5 wt.% and greater than or equal to 0 wt.% versus a total weight percent of the article, the article comprises fluorine in an amount less than or equal to 2 wt.% and greater than or equal to 1 wt.% versus a total weight of the article). Other ranges are also possible.
[00164] In some non-limiting embodiments, the article comprising the composition comprising the POSS-based compound is non-fluorinated such that the article comprises fluorine in an amount of 0 wt.% versus a total weight of the article. [00165] According to some embodiments, the substrate is optically transparent. The substrate may have any of a variety of suitable percent optical transmittances. In some embodiments, for example, the percent optical transmittance of the substrate is greater than or equal to 90%, greater than or equal to 92%, greater than or equal to 94%, greater than or equal to 96%, greater than or equal to 98%, or greater than or equal to 99%. In some embodiments, the percent optical transmittance of the substrate is less than or equal to 100%, less than or equal to 99%, less than or equal to 98%, less than or equal to 96%, less than or equal to 94%, or less than or equal to 92%. Combinations of the above recited ranges are possible (e.g., the percent optical transmittance of the substrate is greater than or equal to 90% and less than or equal to 100%, the percent optical transmittance of the substrate is greater than or equal to 98% and less than or equal to 99%). Other ranges are also possible. According to some embodiments, the percent optical transmittance of the substrate is determined using a spectrophotometer.
[00166] The substrate may comprise any of a variety of suitable materials. In some embodiments, for example, the substrate comprises glass, a ceramic, a metal, a metal oxide, a polymer (e.g., an acrylic polymer, a plastic), an electronic component (e.g., a silicon wafer), and/or combinations thereof. Other materials are also possible.
[00167] According to some embodiments, a method of coating a substrate is described. FIG. 2 shows, according to some embodiments, a schematic diagram of an exemplary method of coating a substrate.
[00168] In some embodiments, step 202 of method 200 comprises providing substrate 110 comprising at least one surface 120. According to some embodiments, the method comprises activating at least a portion the substrate. In some embodiments, for example, the substrate is activated by exposing the substrate to a plasma of inert gas, such as, but not limited to, argon (Ar), neon (Ne), helium (He), nitrogen (N2), oxygen (O2), water (H2O), and/or mixtures thereof. In some embodiments, the substrate is activated by corona treatment. In some embodiments, the substrate is activated by mechanically treating the surface (e.g., with a metal oxide). In some embodiments, the substrate is activated by acid etching (e.g., with piranha solution (a mixture of sulfuric acid and hydrogen peroxide), hydrofluoric acid, and/or hydrochloric acid). Without wishing to be bound by any particular theory, as a result of activating the substrate, the density of hydroxyl (-OH) moieties on the surface of the substrate is increased, thereby facilitating immobilization (e.g., bonding) of at least a portion of the composition on the surface of the substrate, as described in greater detail elsewhere herein.
[00169] Step 204 of method 200 comprises, in accordance with some embodiments, disposing (e.g., depositing) composition 130 on at least a portion of at least one surface 120 of substrate 110 such that composition 130 coats at least the portion of at least one surface 120 of substrate 110. In some embodiments, as described in greater detail elsewhere herein, as a result of disposing the composition on at least a portion of the at least one surface of the substrate, at least a portion of the composition is immobilized on (e.g., bound to) the surface of the substrate, as described in greater detail elsewhere herein.
[00170] According to some embodiments, although not shown in the figures, the composition is disposed (e.g., deposited) on at least a portion of more than one surface of the substrate (e.g., two surfaces of the substrate, three surfaces of the substrate, four surfaces of the substrate, etc.).
[00171] Depositing the composition on at least the portion of the at least one surface of the substrate may comprise any of a variety of suitable deposition methods. According to some embodiments, for example, depositing the composition comprises spraying (e.g., spray coating), spinning (e.g., spin coating), dipping (e.g., dip coating), wiping, chemical vapor deposition (CVD), physical vapor deposition (PVD), and/or combinations thereof.
[00172] Step 206 of method 200 comprises, in some embodiments, applying heat 132 to composition 130 after depositing composition 130 on at least the portion of at least one surface 120 of substrate 110. In some embodiments, for example, applying heat to the composition comprises curing and/or annealing the composition. Other methods of applying heat to the composition are also possible.
[00173] The composition may be heated (e.g., cured) to any of a variety of suitable temperatures. In some embodiments, for example, the composition is heated to a temperature of greater than or equal to 25 °C, greater than or equal to 50 °C, greater than or equal to 75 °C, greater than or equal to 100 °C, greater than or equal to 110 °C, greater than or equal to 120 °C, greater than or equal to 130 °C, or greater than or equal to 140 °C. In some embodiments, the composition is heated to a temperature of less than or equal to 150 °C, less than or equal to 140 °C, less than or equal to 130 °C, less than or equal to 120 °C, less than or equal to 110 °C, less than or equal to 100 °C, less than or equal to 75 °C, or less than or equal to 50 °C. Combinations of the above recited ranges are possible (e.g., the composition is heated to a temperature of greater than or equal to 25 °C and less than or equal to 150 °C, the composition is heated to a temperature of greater than or equal to 120 °C and less than or equal to 140 °C). Other ranges are also possible.
[00174] The composition may be heated (e.g., cured) to any of the aforementioned temperatures for any of a variety of suitable times. In some embodiments, for example, the composition is heated for greater than or equal to 1 minute, greater than or equal to 30 minutes, greater than or equal to 1 hour, greater than or equal to 5 hours, greater than or equal to 10 hours, greater than or equal to 24 hours, greater than or equal to 48 hours, or greater than or equal to 72 hours. In some embodiments, the composition is heated for less than or equal to 96 hours, less than or equal to 72 hours, less than or equal to 48 hours, less than or equal to 24 hours, less than or equal to 10 horns, less than or equal to 5 hours, less than or equal to 1 hour, or less than or equal to 30 minutes. Combinations of the above recited ranges are possible (e.g., the composition is heated for greater than or equal to 1 minute and less than or equal to 96 hours, the composition is heated for greater than or equal to 10 horns and less than or equal to 24 hours). Other ranges are also possible.
[00175] In some embodiments, the amount of time that the composition is heated (e.g., cured) depends on the temperature at which the composition is heated. In some embodiments, for example, higher heating temperatures (e.g., greater than or equal to 100 °C) are associated with shorter heating times (e.g., less than or equal to 1 hour). In some embodiments, lower heating temperatures (e.g., less than or equal to 75 °C) are associated with longer heating times (e.g., greater than or equal to 5 hours).
[00176] In some embodiments, the amount of time that the composition is heated (e.g., cured) and/or the temperature at which the composition is heated depends on the substrate on which the composition is disposed (e.g., deposited). In some embodiments, for example, higher- heating temperatures (e.g., greater than or equal to 100 °C) and shorter heating times (e.g., less than or equal to 1 hour) are associated with compositions disposed on glass substrates. In some embodiments, lower heating temperatures (e.g., less than or equal to 75 °C) and longer heating times (e.g., greater than or equal to 5 hours) are associated with compositions disposed on polymer (e.g., plastic) substrates.
[00177] According to some embodiments, applying heat 132 to composition 130 disposed on at least the portion of at least one surface 120 of substrate 110 results in article 100, as shown in step 208 of method 200.
[00178] According to some embodiments, a kit is described. In some embodiments, the kit comprises a low surface energy material comprising a POSS-based compound, as described herein in greater detail. According to some embodiments, the low surface energy material is provided as a solid, and the kit comprises one or more solvents configured to dissolve the low surface energy material. In other embodiments, the low surface energy material is provided in solution. For example, in some embodiments, the kit comprises the low surface energy material pre-dissolved in one or more solvents and ready for application onto a surface of a substrate.
[00179] In some embodiments, the kit comprises one or more precursors configured to form a POSS-based compound. For example, in some embodiments, the kit comprises a precursor POSS molecule, one or more precursor compounds comprising one or more functional groups, and one or more catalysts. In other embodiments, the kit comprises one or more silicon- containing precursor compounds comprising one or more functional groups and one or more catalysts.
[00180] In some embodiments, the one or more precursors configured to form the POSS- based compound and/or the one or more catalysts is provided as a solid, and the kit comprises one or more solvents configured to dissolve the one or more precursors. In other embodiments, the one or more precursors configured to form the POSS-based compound and/or the one or more catalysts are provided in solution.
[00181] According to some embodiments wherein the kit comprises one or more precursors configured to form the POSS-based compound, the kit comprises one or more components configured to form a composition comprising the POSS-based compound. In some embodiments, for example, the kit comprises one or more base polymers. In some embodiments, the one or more base polymers comprise an epoxy and/or a (meth)acrylate such that the one or more base polymers are configured to interact with the POSS-based compound.
[00182] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed., inside cover, and specific functional groups are generally defined as described therein and are incorporated herein by reference in their entirety. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito: 1999, the entire contents of which are incorporated herein by reference.
[00183] It will be appreciated that the compounds, as described herein, may be substituted with any number of substituents or functional moieties. In general, the term “substituted” whether preceded by the term “optionally” or not, and substituents contained in formulas of this invention, refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent (e.g., a substituent which upon substitution results in a stable compound, such as a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction). When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
[00184] As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds, “permissible” being in the context of the chemical rules of valence known to those of ordinary skill in the art, and includes any of the substituents described herein that results in the formation of a stable compound. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. For purposes of this invention, heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valencies of the heteroatoms and results in the formation of a stable moiety. Furthermore, this invention is not intended to be limited in any manner by the permissible substituents of organic compounds. Combinations of substituents and variables envisioned by this invention are preferably those that result in the formation of stable compounds useful in POSS-based compounds and/or coating applications. The term “stable”, as used herein, preferably refers to compounds which possess stability sufficient to allow manufacture and which maintain the integrity of the compound for a sufficient period of time to be detected and preferably for a sufficient period of time to be useful for the purposes detailed herein.
[00185] As used herein, “alkyl” refers to a radical of a straight-chain or branched saturated hydrocarbon group. In some embodiments, an alkali group has 1 to 10 carbon atoms (“C1-C10 alkyl”). In some embodiments, an alkyl group has 1 to 9 carbon atoms (“C1-C9 alkyl”). In some embodiments, an alkyl group has 1 to 8 carbon atoms (“C1-C8 alkyl”). In some embodiments, an alkyl group has 1 to 7 carbon atoms (“C1- C7 alkyl”). In some embodiments, an alkyl group has 1 to 6 carbon atoms (“C1-C6 alkyl”). In some embodiments, an alkyl group has 1 to 5 carbon atoms (“C1-C5 alkyl”). In some embodiments, an alkyl group has 1 to 4 carbon atoms (“C1-C4 alkyl”). In some embodiments, an alkyl group has 1 to 3 carbon atoms (“C1-C3 alkyl”). In some embodiments, an alkyl group has 1 to 2 carbon atoms (“C1-C2 alkyl”). In some embodiments, an alkyl group has 1 carbon atom (“C1 alkyl”).
[00186] In some embodiments, an alkyl group has greater than or equal to 1 carbon atom. For example, in some embodiments, an alkyl group has greater than or equal to 1 carbon atom, greater than or equal to 2 carbon atoms, greater than or equal to 3 carbon atoms, greater than or equal to 4 carbon atoms, greater than or equal to 5 carbon atoms, greater than or equal to 6 carbon atoms, greater than or equal to 7 carbon atoms, greater than or equal to 8 carbon atoms, greater than or equal to 9 carbon atoms, or greater than or equal to 10 carbon atoms. In some embodiments, an alkyl group has less than or equal to 20 carbon atoms, less than or equal to 10 carbon atoms, less than or equal to 9 carbon atoms, less than or equal to 8 carbon atoms, less than or equal to 7 carbon atoms, less than or equal to 6 carbon atoms, less than or equal to 5 carbon atoms, less than or equal to 4 carbon atoms, less than or equal to 3 carbon atoms, or less than or equal to 2 carbon atoms. Combinations of the above recited ranges are possible (e.g., an alkyl group has greater than or equal to 1 carbon atom and less than or equal to 20 carbon atoms, an alkyl group has greater than or equal to 4 carbon atoms and less than or equal to 6 carbon atoms). Other ranges are also possible.
[00187] In some embodiments, an alkyl group has 1 to 6 carbon atoms (“C1-C6 alkyl”). Examples of C1-C6 alkyl groups include methyl (C1), ethyl (C2), n-propyl (C3), isopropyl (C3), n- butyl (C4), tert-butyl (C4), sec-butyl (C4), iso-butyl (C4), n-pentyl (C5), 3-pentanyl (C5), amyl (C5), neopentyl (C5), 3-methyl-2-butanyl (C5), tertiary amyl (C5), and n-hexyl (C6). Additional examples of alkyl groups include n-heptyl (C7), n-octyl (C8), and the like. Unless otherwise specified, each instance of an alkyl group is independently unsubstituted (an “unsubstituted alkyl”) or substituted (a “substituted alkyl”) with one or more substituents. In some embodiments, the alkyl group is an unsubstituted C1-C10 alkyl (e.g., -CH3). In some embodiments, the alkyl group is a substituted C1-C10 alkyl.
[00188] As used herein, the term “alkenyl” includes a radical of a straight-chain or branched saturated hydrocarbon group having from 2 to 10 carbon atoms, and also includes at least one carbon-carbon double bond. It will be understood that in some embodiments, alkenyl may be advantageously of limited length, including C2-C10, C2-C9, C2-C8, C2- C7, C2-C6, C2-C5, C2-C4, and C2-C3.
[00189] As used herein, the term “alkynyl” includes a radical of a straight-chain or branched saturated hydrocarbon group having from 3 to 10 carbon atoms, and also includes at least one carbon-carbon triple bond. It will be understood that in some embodiments, alkenyl may be advantageously of limited length, including C3-C10, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, and C3-C4.
[00190] It should be understood that affixing the suffix “-ene” to a group indicates the group is a divalent moiety. For example, alkylene is the divalent moiety of alkyl (e.g., an acyclic carbon or a saturated acyclic carbon chain represented by the formula -CnH2n-), alkenylene is the divalent moiety of alkenyl (e.g., an acyclic carbon chain which contains a carbon-to-carbon double bond represented by the formula -CnH2n-2-), and alkynylene is the divalent moiety of alkynyl (e.g., an acyclic carbon chain which contains a carbon-to-carbon triple bond represented by the formula -CnH2n-4-). Affixing the suffice “-yne” to a group indicates the group is trivalent moiety (e.g., alkylyne is the trivalent moiety of alkyl, alkenylyne is the trivalent moiety of alkenyl, and alkynylyne is the trivalent moiety of alkynyl).
[00191] As used herein, the term “halogen” refers to fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), or iodine (iodo, -I).
[00192] As used herein, the term “hydroxy” or “hydroxyl” refers to an -OH group.
[00193] As used herein, the term “alkoxy” refers to an -O-(alkyl) or an -O-(cycloalkyl) group. Representative alkoxy group examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and the like.
[00194] As understood from the above, alkyl, alkylene, and alkylyne groups, as defined herein, are, in some embodiments, optionally substituted. Optionally substituted refers to a group which may be substituted or unsubstituted (e.g., “substituted” or “unsubstituted” alkyl).
[00195] The following examples are intended to illustrate some embodiments of the present invention, but do not exemplify the full scope of the invention.
EXAMPLE 1
[00196] The following example describes the synthesis and characterization of a POSS molecule functionalized with polydimethylsiloxane.
[00197] Octasilane POSS (1 molar equivalent) and mono-vinyl polydimethylsiloxane (8 molar equivalents) were added to toluene in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of platinum metal. The product was isolated and dried under vacuum. A schematic representation of the synthesis is shown in FIG. 3.
[00198] The product was characterized by 1H-NMR: -Si(CH3)2-/-Si(CH3)3 (m, 0.25 ppm); Si-CH2-CH2-Si (t, 0.7 ppm).
[00199] The product was also characterized by FT-IR: -Si(CH3)2-/-Si(CH3)3 (2965 cm-1 and 790 cm-1); -O-Si-O- (1070 cm-1).
[00200] The product was also characterized by TGA (see FIG. 4). No thermal degradation and/or decomposition, represented by a weight loss of less than 0.3%, was observed up to 175 °C. EXAMPLE 2
[00201] The following example describes the synthesis and characterization of a POSS molecule multifunctionalized with poly dimethylsiloxane and a methacrylate.
[00202] Octasilane POSS (1 molar equivalent), mono-vinyl poly dimethylsiloxane (m molar equivalents), and isoprenyl methacrylate (IPEMA) (n molar equivalents) were added to toluene in a round-bottom flask, with m + n = 8. The mixture was refluxed in the presence of a catalytic amount of platinum metal. The product was isolated and dried under vacuum. A schematic representation of the synthesis with m = 4 and n = 4 is shown in FIG. 5.
[00203] The product was characterized by 1H-NMR: -Si(CH3)2-/-Si(CH3)3 (m, 0.25 ppm); Si-CH2-CH2-Si (t, 0.7 ppm, 4H); -(C=O)O-CH2- (t, 4.3 ppm, 2H); -CH=CH2 (dd, 5.6- 6.25 ppm, 3H).
[00204] The product was also characterized by FT-IR: -Si(CH3)2-/-Si(CH3)3 (2965 cm-1 and 790 cm-1); -(C=O)- (1720 cm-1); -CH2=CH2 (1420 cm-1); -O-Si-O- (1070 cm-1).
EXAMPLE 3
[00205] The following example describes the synthesis and characterization of a POSS molecule functionalized with a phenyl group.
[00206] Trimethoxyphenylsilane was added to toluene in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of potassium hydroxide. The product was isolated and dried under vacuum. A schematic representation of the synthesis is shown in FIG. 6.
[00207] The product was characterized by 1H-NMR: C6H5 (phenyl) (br, 7 ppm, 40H).
[00208] The product was also characterized by 29Si-NMR: T8/T10/T12 (-80.3 ppm).
[00209] The product was also characterized by FT-IR: -Si-C6H6 (2965 cm-1); -C6H6 (1595 cm-1 and 1429 cm-1); -O-Si-O- (1070 cm-1).
EXAMPLE 4
[00210] The following example describes the synthesis and characterization of a POSS molecule multifunctionalized with a phenyl group and a primary amine. [00211] Trimethoxyphenylsilane (m molar equivalents) and (3- aminopropyl)trimethoxysilane (n molar equivalents) were added to toluene in a round-bottom flask, with m + n = 8. The mixture was refluxed in the presence of a catalytic amount of potassium hydroxide. The product was isolated and dried under vacuum. A schematic representation of the synthesis with m = 7 and n = 1 is shown in FIG. 7.
[00212] The product was characterized by FT-IR: -NH2 (br, 3500 cm-1); -Si-C6H6 (3072 cm-1 and 3049 cm-1); -C6H6 (1595 cm-1 and 1429 cm-1); -O-Si-O- (1070 cm-1).
EXAMPLE 5
[00213] The following example describes the synthesis and characterization of a POSS molecule multifunctionalized with a phenyl group and a secondary amine.
[00214] Trimethoxyphenylsilane (m molar equivalents) and N-(3- (trimethoxysilyl)propyl)aniline (n molar equivalents) were added to toluene in a round-bottom flask, with m + n = 8. The mixture was refluxed in the presence of a catalytic amount of potassium hydroxide. The product was isolated and dried under vacuum. A schematic representation of the synthesis with m = 7 and n = 1 is shown in FIG. 8.
[00215] The product was characterized by FT-IR: -NH2 (br, 3500 cm-1); -Si C6H6 (3072 cm-1 and 3049 cm-1); -C6H6 (1595 cm-1, 1506 cm-1, and 1429 cm-1); -O-Si-O- (1070 cm-1).
EXAMPLE 6
[00216] The following example describes the synthesis and characterization of a POSS molecule functionalized with a substituted phenyl group.
[00217] P-(t-butyl)phenethyltrichlorosilane was added to methanol in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of water. The product was isolated and dried under vacuum. A schematic representation of the synthesis is shown in FIG.
9.
[00218] The product was characterized by 1H-NMR: Si-CH2- (t, 0.9 ppm, 2H); -C(CH3)3 (s, 1.15 ppm, 9H); CH2CH2 (t, 2.8 ppm, 2H); Si-CH2 (t, 0.9 ppm, 2H); CH- (d, 7.3 ppm, 2H); -CH= (d, 7.0 ppm, 2H). [00219] The product was also characterized by 29Si-NMR: T8 (-64.91 ppm).
[00220] The product was also characterized by FT-IR: -Si-CH (2960 cm-1 and 2870 cm-
1); -C6H6 (1516 cm-1, 1460 cm-1, and 1363 cm-1); -O-Si-O- (1049 cm-1).
EXAMPLE 7
[00221] The following example describes the synthesis and characterization of a POSS molecule functionalized with a substituted phenyl group and a secondary amine.
[00222] P-(t-butyl)phenethyltrichlorosilane (m molar equivalents) and N-(3- (trimethoxysilyl)propyl)aniline (n molar equivalents) were added to methanol in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of water. The product was isolated and dried under vacuum. A schematic representation of the synthesis with m = 7 and n = 1 is shown in FIG. 10.
[00223] The product was also characterized by FT-IR: -NH? (br, 3300 cm-1); -Si-CH (2960 cm-1 and 2868 cm-1); -C6H6 (1516 cm-1, 1460 cm-1, and 1363 cm-1); -O-Si-O- (1070 cm- ')•
EXAMPLE 8
[00224] The following example describes the synthesis and characterization of a POSS molecule functionalized with 2,2,4-trimethylhexane.
[00225] Trimethoxy(2,4,4-trimethylpentyl)silane was added to methanol in a roundbottom flask. The mixture was refluxed in the presence of a catalytic amount of potassium hydroxide. The product was isolated and dried under vacuum. A schematic representation of the synthesis with m = 7 and n = 1 is shown in FIG. 11.
[00226] The product was characterized by 1H-NMR: -Si-CH2- (d, 0.5 ppm, 2H); - CH(CH3)2 (s, 0.95 ppm, 6H); -CH(CH3)2 (m, 1.85 ppm, 1H).
[00227] The product was also characterized by 29Si-NMR: T8 -67.9 ppm.
[00228] The product was also characterized by FT-IR: -Si-CH (2961 cm-1 and 2870 cm-
1); 1467 cm-1, 1363 cm-1, 1226 cm-1, and 1363 cm-1; -O-Si-O- (1093 cm-1). EXAMPLE 9
[00229] The following example describes the synthesis and characterization of a POSS molecule functionalized with isopentane.
[00230] Isobutyltrimethoxysilane was added to methanol in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of potassium hydroxide. The product was isolated and dried under vacuum. A schematic representation of the synthesis is shown in FIG. 12.
[00231] The product was characterized by 1H-NMR: -Si-CH2- (d, 0.5 ppm, 2H);
CH(CH3)2 (S, 0.95 ppm, 6H); -CH(CH3)2 (m, 1.85 ppm, 1H).
[00232] The product was also characterized by 29Si-NMR: T8 -67.9 ppm.
EXAMPLE 10
[00233] The following example describes the synthesis and characterization of a POSS molecule multifunctionalized with isopentane and a primary amine.
[00234] Isobutyltrimethoxy silane (m molar equivalents) and (3- aminopropyl)trimethoxysilane (n molar equivalents) were added to methanol in a round-bottom flask, with m + n = 8. The mixture was refluxed in the presence of a catalytic amount of potassium hydroxide. The product was isolated and dried under vacuum. A schematic representation of the synthesis with m = 7 and n = 1 is shown in FIG. 13.
EXAMPLE 11
[00235] The following example describes the synthesis and characterization of a POSS dimer.
[00236] Octasilane POSS (1 molar equivalent), mono-vinyl polydimethylsiloxane (5 molar equivalents), and isoprenyl methacrylate (IPEMA) (3 molar equivalents) were added to toluene in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of platinum metal. The product was isolated and dried under vacuum.
[00237] The product was characterized by GPC, and the peak molecular weight was determined to be 17,005 Da (see FIG. 14). It was determined that the structure of the product was a POSS-dimer multifunctionalized with 10 polydimethylsiloxane groups and 4 methacrylate groups, with one bridging methacrylate group between the two POSS cages.
EXAMPLE 12
[00238] The following example describes the synthesis and characterization of a second POSS dimer.
[00239] Octasilane POSS (1 molar equivalent), mono-vinyl poly dimethylsiloxane (3 molar equivalents), and isoprenyl methacrylate (IPEMA) (5 molar equivalents) were added to toluene in a round-bottom flask. The mixture was refluxed in the presence of a catalytic amount of platinum metal. The product was isolated and dried under vacuum.
[00240] The product was characterized by gel permeation chromatography (GPC), and the peak molecular weight was determined to be 14,520 Da (see FIG. 15). It was determined that the structure of the product was a POSS-dimer multifunctionalized with 6 polydimethylsiloxane groups and 8 methacrylate groups, with one bridging methacrylate group between the two POSS cages.
[00241] The product was also characterized by FT-IR (see FIG. 16): -Si(CH3)2-/~ Si(CH3)3 and CH3-/-(CH2)2- (2965 cm-1); -(C=O)- (1737 cm-1); -CH2=CH2 (1411 cm-1); -O-Si- O- (1090 cm-1); Si(CH3)3-/-Si(CH3)2- (790 cm-1).
[00242] While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the ail will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, and/or methods, if such features, systems, articles, materials, and/or methods are not mutually inconsistent, is included within the scope of the present invention. [00243] In cases where the present specification and a document incorporated by reference include conflicting and/or inconsistent disclosure, the present specification shall control. If two or more documents incorporated by reference include conflicting and/or inconsistent disclosure with respect to each other, then the document having the later effective date shall control.
[00244] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
[00245] The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.” [00246] The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified unless clearly indicated to the contrary. Thus, as a non-limiting example, a reference to “A and/or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
[00247] As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or" as used herein shall only be interpreted as indicating exclusive alternatives (i.e., “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
[00248] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
[00249] In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

Claims

CLAIMS What is claimed is:
1. A polyhedral oligomeric silsesquioxane (POSS)-based compound, the compound comprising: a multifunctionalized POSS molecule of the structure:
Figure imgf000068_0001
wherein: each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3, -O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y, -(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)y, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, optionally substituted, with the proviso that a first R1 is different from a second R1, each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted, each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted, each x is the same or different and is greater than or equal to 0 and less than or equal to
10, each y is the same or different and is greater than or equal to 1 and less than or equal to 3, n is greater than or equal to 2 and less than or equal to 100, and the multifunctionalized POSS molecule is substantially non-fluorinated.
2. The compound of claim 1, wherein a ratio of the first R1 to the second R1 is greater than or equal 1 :7 and less than or equal to 7: 1.
3. The compound of any one of claims 1-2, wherein the ratio of the first R1 to the second R1 is greater than or equal to 2:6 and less than or equal to 6:2.
4. The compound of any one of claims 1-3, wherein the ratio of the first R1 to the second R1 is greater than or equal to 3:5 and less than or equal to 5:3.
5. The compound of any one of claims 1-4, wherein the ratio of the first R1 to the second R1 is 4:4.
6. The compound of claim 1, wherein: the first R1 is different from the second R1 and a third R1, and the second R1 is different from the third R1.
7. The compound of claim 1, wherein: the first R1 is different from the second R1, the third R1, and a fourth R1, the second R1 is different from the third R1 and the fourth R1, and the third R1 is different from the fourth R1.
8. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with poly dimethylsiloxane.
9. The compound of any one of claims 1-8, wherein the first R1 is -O-Si(R2)2-(R3)x-Si(R2)2- O-[Si(R2)2-O]n-Si(R2)3.
10. The compound of any one of claims 8-9, wherein the first R1 is -O-Si(CH3)2-(CH2)2- Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3.
11. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with tris(trimethylsiloxy)silane.
12. The compound of claim 11, wherein the first R1 is -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3.
13. The compound of any one of claims 11-12, wherein the first R1 is -O-Si(CH3)2- Si(OSi(CH3)3)3.
14. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with an acrylate group and/or a methacrylate group.
15. The compound of claim 14, wherein the first R1 is -O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2) or -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-.
16. The compound of any one of claims 14-15, wherein the first R1 is -O-Si(CH3)2- (CH2)(CH)(CH3)(CH2)2-O-C(O)-C(CH3)(CH2) or -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)- O(CH2)2C(CH3)(CH2)-.
17. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with: (i) poly dimethylsiloxane; and (ii) an acrylate group and/or a methacrylate group.
18. The compound of claim 17, wherein the first R1 is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2- O]n-Si(R2)3 and the second R1 is -O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2) or -O-Si(R2)2-(R3)x- C(O)-O-(R3)x-.
19. The compound of any one of claims 17-18, wherein the first R1 is -O-Si(CH3)2-(CH2)2- Si(CH3)2-O-[Si(CH3)2-O]n-Si(CH3)3 and the second R1 is -O-Si(CH3)2-(CH2)(CH)(CH3)(CH2)2- O-C(O)-C(CH3)(CH2) or -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)-O(CH2)2C(CH3)(CH2)-.
20. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with a phenyl group.
21. The compound of claim 20, wherein the first R1 is -(R3)x-C6H5.
22. The compound of any one of claims 20-21, wherein the first R1 is -C6H5.
23. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with an amine group.
24. The compound of claim 23, wherein the amine group is a primary amine group.
25. The compound of any one of claims 23-24, wherein the first R1 is -(R3)x-NH2.
26. The compound of any one of claims 23-25, wherein the first R1 is -(CH2)3-NH2.
27. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with: (i) a phenyl group; and (ii) a primary amine group.
28. The compound of claim 27, wherein the first R1 is -(R3)x-C6H5 and the second R1 is - (R3)x-NH2.
29. The compound of any one of claims 27-28, wherein the first R1 is -C6H5 and the second R1 is -(CH2)3-NH2.
30. The compound of claim 23, wherein the amine group is a secondary amine group.
31. The compound of claim 30, wherein the first R1 is -(R3)x-NH-R2.
32. The compound of any one of claims 30-31, wherein the first R1 is -(CH2)3-NH-C6H5.
33. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with: (i) a phenyl group; and (ii) a secondary amine group.
34. The compound of claim 33, wherein the first R1 is -(R3)x-C6H5 and the second R1 is - (R3)x-NH-R2.
35. The compound of any one of claims 33-34, wherein the first R1 is C6H5 at the second R1 is -(CH2)3-NH-C6H5.
36. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with a substituted phenyl group.
37. The compound of claim 36, wherein the first R1 is -(R3)x-C6H4-(R3)x-(R2)y.
38. The compound of any one of claims 36-37, wherein the first R1 is -(CH2)2-C6H4- C(CH3)3.
39. The compound of any one of claims 1-7, wherein the functionalized POSS molecule is functionalized with: (i) a substituted phenyl group; and (ii) a primary amine group.
40. The compound of claim 39, wherein the first R1 is -(R3)x-C6H4-(R3)x-(R2)y and the second R1 is -(R3)x-NH2.
41. The compound of any one of claims 39-40, wherein the first R1 is -(CH2)2-C6H4-C(CH3)3 and the second R1 is -(CH2)3-NH2.
42. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with a -C1-C10 alkyl group.
43. The compound of claim 42, wherein the first R1 is -(R3)x-(R2)y.
44. The compound of any one of claims 42-43, wherein the first R1 is -(CH2)-(CH)(CH3)- (CH2)-C(CH3)3 or -(CH2)-(CH)(CH3)2.
45. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with: (i) a primary amine group; and (ii) a -C1-C10 alkyl group.
46. The compound of claim 45, wherein the first R1 is -(R3)x-NH2 and the second R1 is (R3)x-(R2)y.
47. The compound of any one of claims 45-46, wherein the first R1 is -(CH2)3-NH2 and the second R1 is -(CH2)-(CH)(CH3)-(CH2)-C(CH3)3 or -(CH2)-(CH)(CH3)2.
48. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with an alcohol group.
49. The compound of claim 48, wherein the first R1 is -(R3)x-OH.
50. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with a thiol group.
51. The compounds of claim 50, wherein the first R1 is -(R3)x-SH.
52. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with an azide group.
53. The compound of claim 52, wherein the first R1 is -(R3)x-N3.
54. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with an isocyanate group.
55. The compound of claim 54, wherein the first R1 is -(N)=C=O.
56. The compound of any one of claims 1-7, wherein the multifunctionalized POSS molecule is functionalized with an epoxy group.
57. The compound of claim 56, wherein the first R1 is -(R3)x-(C2H4O).
58. The compound of any one of claims 1-57, wherein the multifunctionalized POSS molecule is a first POSS molecule, and at least one R1 is configured to form a bond to a second POSS molecule.
59. The compound of claim 58, wherein the at least one R1 comprises an acrylate group and/or a methacrylate group.
60. The compound of any one of claims 58-59, wherein the at least one R1 is -O-Si(R2)2- (R3)x-C(O)-O-(R3)x-.
61. The compound of any one of claims 58-60, wherein the at least one R1 is -O-Si(CH3)2- (CH2)(CH)(CH3)-C(O)-O(CH2)2C(CH3)(CH2)-.
62. The compound of any one of claims 58-61, wherein the second POSS molecule is multifunctionalized.
63. A composition, comprising: a low surface energy material comprising the compound of any one of claims 1-62.
64. The composition of claim 63, wherein the low surface energy material comprises the compound in an amount greater than or equal to 0.1 weight percent (wt.%) and less than or equal to 10 wt.% versus a total weight of the low surface energy material.
65. The composition of any one of claims 63-64, wherein the low surface energy material has a coefficient of friction of less than or equal to 0.1.
66. An article, comprising: a substrate comprising at least one surface; and the composition of any one of claims 63-65 disposed on at least a portion of the at least one surface such that the composition coats at least the portion of the at least one surface.
67. A polyhedral oligomeric silsesquioxane (POSS)-based compound, the compound comprising: a POSS molecule of the structure: -74 -
Figure imgf000076_0001
wherein: each R1 is the same or different and is selected from the group consisting of -O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,-O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x-, -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)x-NH-R2, — (R3)x-N3, -(N)=C=O, -(R3)x-(R2)y, -(R3),- OH, -(R3)x-(C2H4O), and -(R3)X-SH, optionally substituted, with the proviso that at least one R1 is -O-Si(R2)2-(R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted, each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted, each x is the same or different and is greater than or equal to 0 and less than or equal to
10, each y is the same or different and is greater than or equal to 1 and less than or equal to 3, n is greater than or equal to 2 and less than or equal to 100, and the POSS molecule is substantially non-fluorinated.
68. The compound of claim 67, wherein the at least one R1 is -O-Si(CH3)2-(CH2)2-Si(CH3)2- O-[Si(CH3)2-O]n-Si(CH3)3.
69. The compound of any one of claims 67-68, wherein a first R1 is different from a second
R1.
70. The compound of any one of claims 67-68, wherein each R1 is -O-Si(R2)2-(R3)x-Si(R2)2- O-[Si(R2)2-O]n-Si(R2)3.
71. The compound of claim 70, wherein each R1 is -O-Si(CH3)2-(CH2)2-Si(CH3)2-O- [Si(CH3)2-O]n-Si(CH3)3.
72. A composition, comprising: a low surface energy material comprising the compound of any one of claims 67-71.
73. The composition of claim 72, wherein the low surface energy material comprises the compound in an amount greater than or equal to 0.1 weight percent (wt.%) and less than or equal to 10 wt.% versus a total weight of the low surface energy material.
74. The composition of any one of claims 72-73, wherein the low surface energy material has a coefficient of friction of less than or equal to 0.1.
75. An article, comprising: a substrate comprising at least one surface; and the composition of any one of claims 72-74 disposed on at least a portion of the at least one surface such that the composition coats at least the portion of the at least one surface.
76. A polyhedral oligomeric silsesquioxane (POSS)-based compound, the compound comprising: a POSS molecule of the structure:
Figure imgf000078_0001
wherein: each R1 is the same or different and is selected from the group consisting of -O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,-O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)y,-(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, (R3)x-(R2)y, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, optionally substituted, with the proviso that at least one R1 is O-Si(R2)2-(R3)x-O-C(O)-C(CH3)(CH2),-O- Si(R2)2-(R3)x-C(O)-O-(R3)x-, or -O-Si(R2)2-(R3)x-O-CH2CHCH2, each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted, each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted, each x is the same or different and is greater than or equal to 0 and less than or equal to
10, each y is the same or different and is greater than or equal to 1 and less than or equal to 3, n is greater than or equal to 2 and less than or equal to 100, and the POSS molecule is substantially non-fluorinated.
77. The compound of claim 76, wherein the at least one R1 is -O-Si(CH3)2- (CH2)(CH)(CH3)(CH2)2-O-C(O)-C(CH3)(CH2) or -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)- O(CH2)2C(CH3)(CH2)-.
78. The compound of any one of claims 76-77, wherein a first R1 is different from a second
R1.
79. The compound of any one of claims 76-77, wherein each R1 is -O-Si(CH3)2- (CH2)(CH)(CH3)(CH2)2-O-C(O)-C(CH3)(CH2) or -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)- O(CH2)2C(CH3)(CH2)-.
80. The compound of claim 79, wherein each R1 is -O-Si(CH3)2-(CH2)(CH)(CH3)(CH2)2-O- C(O)-C(CH3)(CH2) or -O-Si(CH3)2-(CH2)(CH)(CH3)-C(O)-O(CH2)2C(CH3)(CH2)-.
81. The compound of any one of claims 76-80, wherein the POSS molecule is a first POSS molecule and the at least one R1 is configured to form a bond to a second POSS molecule.
82. The compound of claim 81, wherein the at least one R1 is -O-Si(R2)2-(R3)x-C(O)-O- (R3)x-.
83. The compound of any one of claims 81-82, wherein the at least one R1 is -O-Si(CH3)2- (CH2)(CH)(CH3)-C(O)-O(CH2)2C(CH3)(CH2)-.
84. A composition, comprising: a low surface energy material comprising the compound of any one of claims 76-83.
85. The composition of claim 84, wherein the low surface energy material comprises the compound in an amount greater than or equal to 0.1 weight percent (wt.%) and less than or equal to 10 wt.% versus a total weight of the low surface energy material.
86. The composition of any one of claims 84-85, wherein the low surface energy material has a coefficient of friction of less than or equal to 0.1.
87. An article, comprising: a substrate comprising at least one surface; and the composition of any one of claims 84-86 disposed on at least a portion of the at least one surface such that the composition coats at least the portion of the at least one surface.
88. A polyhedral oligomeric silsesquioxane (POSS)-based compound, the compound comprising: a POSS molecule of the structure:
Figure imgf000080_0001
> wherein: each R1 is the same or different and is selected from the group consisting of-O-Si(R2)2- (R3)x-Si(R2)2-O-[Si(R2)2-O]n-Si(R2)3, -O-Si(R2)2-(R3)x-Si(OSi(R2)3)3,-O-Si(R2)2-(R3)x-O-C(O)- C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- -O-Si(R2)2-(R3)x-O-CH2CHCH2, -(R3)x-C6H5, - (R3)x-C6H4-(R3)x-(R2)3,-(R3)x-NH2, -(R3)x-NH-R2, -(R3)x-N3, -(N)=C=O, -(R3)x-(R2)3, -(R3)x- OH, -(R3)x-(C2H4O), and -(R3)x-SH, optionally substituted, each R1’ is the same or different and is a bridging moiety to another silicon atom of the POSS molecule, wherein each R1’ is selected from the group consisting of -O-Si(R2)2-(R3)x-O- C(O)-C(CH3)(CH2), -O-Si(R2)2-(R3)x-C(O)-O-(R3)x- and -O-Si(R2)2-(R3)x-O-CH2CHCH2, optionally substituted, each R2 is the same or different and is selected from the group consisting of hydrogen, deuterium, -C1-C10 alkyl, -C2-C10 alkenyl, -C3-C10 alkynyl, and aryl, optionally substituted, each R3 is the same or different and is selected from the group consisting of a bond, oxygen, C(O), -C1-C10 alkylene-, -C2-C10 alkenylene-, -C3-C10 alkynylene-, and aryl, optionally substituted, each x is the same or different and is greater than or equal to 0 and less than or equal to
10, each y is the same or different and is greater than or equal to 1 and less than or equal to 3, n is greater than or equal to 2 and less than or equal to 100, m is greater than or equal to 2 and less than or equal to 100, and the POSS molecule is substantially non-fluorinated.
89. The compound of claim 88, wherein m is greater than or equal to 2 and less than or equal to 4.
90. The compound of any one of claims 88-89, wherein m is greater than or equal to 2 and less than or equal to 3.
91. The compound of any one of claims 88-90, wherein m is 2.
92. A composition, comprising: a low surface energy material comprising the compound of any one of claims 88-91.
93. The composition of claim 92, wherein the low surface energy material comprises the compound in an amount greater than or equal to 0.1 weight percent (wt.%) and less than or equal to 10 wt.% versus a total weight of the low surface energy material.
94. The composition of any one of claims 92-93, wherein the low surface energy material has a coefficient of friction of less than or equal to 0.1.
95. An article, comprising: a substrate comprising at least one surface; and the composition of any one of claims 92-94 disposed on at least a portion of the at least one surface such that the composition coats at least the portion of the at least one surface.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080279797A1 (en) * 2007-05-09 2008-11-13 Prithwiraj Maitra Cosmetic nanocomposites based on in-situ cross-linked POSS materials
US20140066538A1 (en) * 2011-02-28 2014-03-06 Fujifilm Corporation Ink composition, image forming method, and printed matter
WO2019040922A1 (en) * 2017-08-24 2019-02-28 Nbd Nanotechnologies, Inc. Adhesion promoters and their use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080279797A1 (en) * 2007-05-09 2008-11-13 Prithwiraj Maitra Cosmetic nanocomposites based on in-situ cross-linked POSS materials
US20140066538A1 (en) * 2011-02-28 2014-03-06 Fujifilm Corporation Ink composition, image forming method, and printed matter
WO2019040922A1 (en) * 2017-08-24 2019-02-28 Nbd Nanotechnologies, Inc. Adhesion promoters and their use

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FERNáNDEZ M. DOLORES; FERNáNDEZ M. JESúS; COBOS MóNICA: "Effect of polyhedral oligomeric silsesquioxane (POSS) derivative on the morphology, thermal, mechanical and surface properties of poly(lactic acid)-based nanocomposites", JOURNAL OF MATERIAL SCIENCE, KLUWER ACADEMIC PUBLISHERS, DORDRECHT, vol. 51, no. 7, 29 December 2015 (2015-12-29), Dordrecht , pages 3628 - 3642, XP035598314, ISSN: 0022-2461, DOI: 10.1007/s10853-015-9686-5 *
ISHIDA AYANO, FUJII SHUNICHI, SUMIDA AKIFUMI, KAMITANI TASUKU, MINAMI SAORI, URAYAMA KENJI, IMOTO HIROAKI, NAKA KENSUKE: "Supramolecular organogel formation behaviors of beads-on-string shaped poly(azomethine)s dependent on POSS structures in the main chains", POLYMER CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE, vol. 12, no. 21, 1 June 2021 (2021-06-01), Cambridge , pages 3169 - 3176, XP093325315, ISSN: 1759-9954, DOI: 10.1039/D1PY00346A *

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