WO2016057599A1 - Synthetic blend f-poss compositions formed from multiple feedstock materials - Google Patents

Synthetic blend f-poss compositions formed from multiple feedstock materials Download PDF

Info

Publication number
WO2016057599A1
WO2016057599A1 PCT/US2015/054367 US2015054367W WO2016057599A1 WO 2016057599 A1 WO2016057599 A1 WO 2016057599A1 US 2015054367 W US2015054367 W US 2015054367W WO 2016057599 A1 WO2016057599 A1 WO 2016057599A1
Authority
WO
WIPO (PCT)
Prior art keywords
chain length
feedstock
fluorinated
carbon chain
poss
Prior art date
Application number
PCT/US2015/054367
Other languages
French (fr)
Inventor
John Charles Warner
Original Assignee
Nbd Nanotechnologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nbd Nanotechnologies, Inc. filed Critical Nbd Nanotechnologies, Inc.
Priority to EP15849377.5A priority Critical patent/EP3204450A4/en
Priority to JP2017512899A priority patent/JP2017538791A/en
Publication of WO2016057599A1 publication Critical patent/WO2016057599A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/21Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/045Polysiloxanes containing less than 25 silicon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/22Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/549Silicon-containing compounds containing silicon in a ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating 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
    • C09D183/04Polysiloxanes
    • C09D183/08Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • the present disclosure relates, in exemplary embodiments, to compositions of matter comprising synthetic blends of at least two feedstocks that produce a distribution of fluorinated polyhedral oligomeric silsesquioxane molecule structures.
  • the present disclosure also relates, in exemplary embodiments, to methods of making such synthetic blends.
  • Fluorinated polyhedral oligomeric silsesquioxane (“F-POSS”) molecules are a subclass of polyhedral oligomeric silsesquioxanes (“POSS”) which consists of a silicon- oxide core [S1O 1 .5] with a periphery of long-chain fluorinated alkyl groups. Such alkyl groups include fluorinated triethoxysilanes. F-POSS molecules possess some of the lowest known surface energies leading to the creation of superhydrophobic and oleophobic surfaces.
  • F-POSS material ordinarily forms a siloxy cage that acts like an inorganic glass-like material, but have organic R group substituents at the matrix apices, which provides unusual properties and applications. See formula [1] below.
  • Each R substituent can be labeled as, for example, Rl, R2, R3, R4, R5, R6, R7 or R8. See formula [2] below.
  • F-POSS materials have been formed having only one molecule as the R substituent for all apices. See for example, the following U.S. Patents and published applications: 6,716,919 (issued to Lichtenhan et al), 7,195,015 (issued to Mabry et al), 2008/0221262 (filed by Mabry et al), and 2013/0072609 (filed by Haddad et al.).
  • the fluorine atoms of neighboring F-POSS molecules have a tendency to attract each other resulting in F-POSS molecules not typically being readily dispersible or dissociable in other materials.
  • F-POSS molecules typically have low solubility in non-fluorinated solvents. It would be desirable to have an F-POSS material that was more easily dispersed or dissociated in other materials.
  • the disclosure provides an F-POSS compound of the formula
  • R 1 and R 2 are each independently long-chain
  • n is an integer from 0 to 8, provided that R and R are different.
  • the disclosure provides an F-POSS composition comprising a mixture of compounds of the formula
  • R 1 and R 2 are each independently long-chain fluorinated alkyl, and integer from 0 to 8, provided that R 1 and R 2 are different.
  • the disclosure provides an F-POSS composition produced by a process comprising: [010] contacting a first feedstock comprising a first fluorinated trialkoxysilane with a second feedstock comprising a second fluorinated trialkoxysilane, wherein the first fluorinated trialkoxysilane and the second fluorinated trialkoxysilane are different.
  • the disclosure provides a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS”) comprising, a mixture of feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons;
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is greater than y,
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • the disclosure provides a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS”) comprising, a mixture of feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is a number of carbon atoms;
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is a number of carbon atoms, wherein x is not equal to y
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • the disclosure provides a polymer synthetic blend composition, comprising: polymerized units of a first feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; and a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, and y is a range of 4- 10, wherein x is greater than y.
  • the disclosure provides a method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents, comprising:
  • each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • a paint composition comprising:
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and,
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is greater than y,
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • the compounds of the present disclosure can be described as embodiments in any of the following enumerated clauses. It will be understood that any of the embodiments described herein can be used in connection with any other embodiments described herein to the extent that the embodiments do not contradict one another.
  • a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane comprising: a mixture of feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons;
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is greater than y
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • the first feedstock is 1H, 1H, 2H, 2H nonafluorohexyltriethoxysilane.
  • a polymer synthetic blend composition comprising: a mixture of at least two feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons;
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is not equal to y
  • the polymer blend composition resulting from the mixing of the at least two feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • a polymer synthetic blend composition comprising: polymerized units of a first feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; and a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, and y is a range of 4-10, wherein x is greater than y.
  • a method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents comprising:
  • each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane comprising: a mixture of feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons;
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is greater than y
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane comprising: a mixture of feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons;
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is greater than y,
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a first portion of the distribution of molecules formed have substituent R having a Clx:C2y ratio of 1 :0, a second portion of the distribution of molecules formed have substituent R having a Clx:C2y ratio of 0: 1, and a third portion of the molecules have substituent R having a C lx:C2y ratio in a range of from 1 :7 to 7: 1.
  • a paint composition comprising: [061] a. at least one polymer base paint material; and
  • a polymer synthetic blend composition comprising polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS”), comprising: a mixture of feedstock materials comprising
  • a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and,
  • a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C 2 y, where y is the number of carbons, wherein x is greater than y,
  • the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein C 1 is greater than C2 [066] 15.
  • the paint composition of clause 14, wherein the polymer base paint material comprises at least one material selected from the group consisting of a polyurethane, polyester, polypropylene, polybutylene, poly(L-lactic acid), polycellulosic, polyhydroxy alkanate, lignose cellulose, polyethylene oxide, epoxy, epoxy resin, alkyd resin, polyether, and mixtures of at least two of the foregoing. [067] 16.
  • the paint composition of clause 14 or 15, wherein the paint composition has a water contact angle of at least 110 degrees and a hexadecane contact angle of at least 70 degrees. [068] 17.
  • a method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents comprising:
  • each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C 2 y wherein CI is greater than C2.
  • each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
  • R 1 and R 2 are each independently long-chain fluorinated alkyl, and n is an integer from 0 to 8, provided that R 1 and R 2 are different.
  • each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
  • each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
  • compounds comprises a distribution of compounds having a ratio of R to R between 0:8 to 8:0.
  • trialkoxysilane is of the formula R 1 Si(OR A ) 3
  • the second fluorinated trialkoxysilane is of the formula R 2 Si(OR B ) 3
  • each of R 1 and R2 are independently a long-chain fluorinated alkyl
  • each R A and R B is independently Ci-C 6 alkyl, provided that R 1 and R 2 are different.
  • each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
  • each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
  • Fig. 1 is an analysis plot of l H NMR analysis for a synthetic blend SBl according to Example lA(i).
  • Fig. 2 is an analysis plot of 19 F NMR analysis for the synthetic blend SBl according to Example lA(i).
  • Fig. 3 is a graph of Differential Scanning Calorimetry of SBl according to Example lA(i).
  • Fig. 4 is an analysis plot of l H NMR analysis for a synthetic blend SB2 according to Example lA(ii).
  • Fig. 5 is an 19 F NMR analysis for the synthetic blend SB2 according to Example lA(ii).
  • Fig. 6 is a graph of Differential Scanning Calorimetry of SB2 according to Example lA(ii).
  • Fig. 7 is an analysis plot of l H NMR analysis for a synthetic blend SB3 according to Example lA(iii).
  • Fig. 8 is an analysis plot of 19 F NMR analysis for the synthetic blend SB3 according to Example lA(iii).
  • Fig. 9A is a graph of a first Differential Scanning Calorimetry analysis of SB3 prepared according to Example lB(iii).
  • Fig. 9B is a graph of a second Differential Scanning Calorimetry analysis of SB3 prepared according to Example lB(iii).
  • Fig. 10 is an analysis plot 19 F NMR analysis comparing the synthetic blends SB1, SB2 and SB3 of Examples lA(i), lA(ii) and lA(iii).
  • Fig. 11 is a graph of the melting points (in °C) of synthetic blends.
  • Fig. 12 is a chart of the approximate percent composition of SB1, SB2 and SB3 as prepared based on feedstock.
  • Fig. 13A is a photograph of coated steel containing SB3 at 1 wt%.
  • Fig. 13B is a photograph of coated steel containing SB3 at 5 wt%.
  • Fig. 13C is a photograph of coated steel containing SB3 at 10 wt%.
  • Fig. 13D is a photograph of coated steel containing SB3 at 25 wt%.
  • Fig. 14 is a graph of the contact angle of water of synthetic blends SB1, SB2 and SB3 on Windmaster 7035 paint.
  • Fig. 15 is a graph of the contact angle of hexadecane of synthetic blends SB1, SB2 and SB3 on Windmaster 7035 paint.
  • Fig. 16 is a graph of the contact angles of water and hexadecane of synthetic blend SB3 in 50/50 % blends of PEMA on glass substrates with 1% weight loadings in AK-225.
  • Silsesquioxanes have a cage-like structure, which is most commonly a cube, hexagonal prism, octagonal prism, decagonal prism, or dodecagonal prism.
  • the cube-like (“T8") cage structure is formed.
  • the present disclosure provides F-POSS compositions made of a blend of feedstock materials.
  • a first feedstock comprises a first fluorinated triethoxysilane and a second feedstock comprises a second fluorinated triethoxysilane.
  • Each fluorinated triethoxysilane has a distinct carbon chain length C.
  • C is in a range of 4-10. In exemplary embodiments, C is in a range of 4-10. In exemplary embodiments, C is 4, 6, 8 or 10.
  • a first feedstock may be a C6 fluoroalkyl molecule and the second feedstock may be a C8 fluoroalkyl molecule.
  • a first feedstock may be 1H, 1H, 2H, 2H nonafluorohexyltriethoxysilane.
  • a second feedstock may be 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (a.k.a. 1H, 1H, 2H, 2H decatriafluorooctyltriethoxysilane).
  • long-chain fluorinated alkyl means any straight chain or branched chain alkyl group having from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms as counted from the point of attachment of the chain of carbon atoms to the silicon atom at any apex of the silicon-oxide core, where at least one hydrogen atom in the straight chain or branched chain alkyl group is replaced by a fluorine atom. Any number of hydrogen atoms in the straight chain or branched chain alkyl group can be replaced with fluorine atoms within the meaning of "long-chain fluorinated alkyl" as used herein.
  • the terminal methyl group of a straight chain alkyl group having six carbon atoms in the chain can have each of the pendent hydrogen atoms replaced by a fluorine atom (e.g. a trifluoromethyl) to provide a long chain fluorinated alkyl group having the formula -CH 2 CH 2 CH 2 CH 2 CH 2 CF 3 .
  • the last two carbon atoms of a straight chain alkyl group having six carbon atoms in the chain can have each of the pendent hydrogen atoms replaced by a fluorine atom (e.g.
  • a trifluoroethyl to provide a long chain fluorinated alkyl group having the formula -CH 2 CH 2 CH 2 CH 2 CF 2 CF 3 .
  • This exemplary pattern can be continued to include within the definition of "long chain fluorinated alkyl" groups of the formula -CH 2 CH 2 CH 2 CF 2 CF 2 CF 3 , -CH 2 CH 2 CF 2 CF 2 CF 3 ,
  • an alkyl group where every hydrogen atoms in the chain is replaced by a fluorine atom is known as a "perfluorinated" alkyl group.
  • perfluorinated is used in connection with a group where some carbon atoms are defined to have hydrogen atoms bonded thereto, while other carbon atoms have all fluorine atoms bonded thereto.
  • the nomenclature 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane describes a compound in which the two terminal carbon atoms at the point of covalent attachment of the chain to the F-POSS have hydrogen atoms bound to the carbon atom, while the remainder of the carbon atoms in the chain have fluorine atoms bonded thereto and are thus are perfluorinated.
  • the "long chain fluorinated alkyl" group can be identified by the shorthand X/Y, where X is the number of terminal carbon atoms in the longest continuous chain of carbon atoms as counted from the point of attachment of the chain of carbon atoms to the silicon atom at any apex of the silicon-oxide core, and Y is the remaining number of carbon atoms in the longest continuous chain of carbon atoms on which hydrogen atoms are not replaced by fluorine atoms.
  • a long chain fluorinated alkyl group of the formula -CH 2 CH 2 CF 2 CF 2 CF 2 CF 3 can be given the shorthand 4/2.
  • Other exemplary long chain fluorinated alkyl groups include but are not limited to 3/3, 6/2, 4/4, 8/2, 6/4 and the like. It will be appreciated that such long chain fluorinated alkyl groups can also be referred to as 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl, 6/4 fluorinated alkyl, and the like
  • each of the groups attached to the apices of the silicon-oxide core is of the long chain fluorinated alkyl group type defined by the X/Y.
  • 6/2 F-POSS refers to an F-POSS molecule of Formula [1], wherein each of the R groups at the apices of the silicon-oxide core is a 6/2 long chain fluorinated alkyl group as defined herein.
  • the F-POSS molecule has a matrix structure having eight apices, each apex comprising silicon. Each apex has a substituent moiety R, which comprises a C-F chain having a carbon chain length Cn, where n is the number of carbons in the chain.
  • R substituent moiety
  • 6/2 F-POSS is a C8 molecule as the R substituent has 8 carbons. This F- POSS is designated as 6/2 as it has 6 C-F groups and 2 C-H groups.
  • 4/2 F-POSS is a C6 molecule as the R substituent has 6 carbons comprising 4 C-F groups and 2 C-H groups.
  • a blend of several distinct F- POSS molecules is synthesized from a first feedstock fluorinated triethoxysilane and a second feedstock fluorinated triethoxysilane, each feedstock being a different fluorinated triethoxysilane.
  • the end product synthesized is a distribution of F-POSS molecules having portions made up of distinct F-POSS molecules with one of several R substituents (e.g., R 1 ,
  • F-POSS molecules have a matrix structure having all eight apices with a substituent R 1 and having the same carbon chain length C. A portion of the molecules will have all eight apices with a substituent R .
  • Formula [5] below shows a molecular formula with (n)R 1 units and (8-n)R 2 units, where n is the number of units, and
  • each R and/or R unit is covalently attached to a silicon atom apex of the cube-like structure. It will be appreciated that n in the formula [5] is an integer from 0 to 8.
  • a portion of the molecules have a matrix structure in which one or more apices have a substituent R 1 and the remainder have a substituent R 2 , where R 1 and R2 have different carbon chain lengths (e.g. CI and C2).
  • the blend of molecules may, in exemplary embodiments, form a Gaussian distribution of molecules having different carbon chain lengths (e.g. CI and C2).
  • the distribution of R 1 :R 2 ratios generally comprises a Gaussian distribution.
  • the distribution of ratios can be predetermined to an extent, or tuned, based on reaction conditions and amounts used of each substituent.
  • a synthetic blend F-POSS was formed of 50% C4 and 50% C6 chain length R substituent molecules.
  • R 1 and R 2 are as defined above, n is an integer from 0 to 8, and each R A and R B is independently an Ci-C 6 alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n- butyl, sec-butyl, iso-butyl, n-pentyl, sec-pentyl, and the like. In some embodiments, each R A and R B is ethyl.
  • each feedstock comprising fluoroalkyl molecule having a different carbon chain length
  • a first feedstock may be a fluoroalkyl molecule having a carbon chain length C4
  • the second feedstock may have the carbon chain length C6
  • the third feedstock may have the carbon chain length C8.
  • the distribution of F-POSS molecules formed therefrom will have some F-POSS molecules having the C4 substituent at all eight apices; other molecules in the distribution will have all eight apices having the C6 substituent at all eight apices; still other molecules will have all eight apices having the C8 substituent; and, still other molecules in the distribution blend will have one apex with C4, a second apex with C6, and a third apex with C8, the other apices each having a C4, C6, or C8 substituent; with various other molecules in the distribution blend having different ratios of C4, C6 and C8 at the apices.
  • Exemplary ratios in a blend of F-POSS molecules prepared from three feedstocks of chain length C4, C6 and C8 include, but are not limited to, 0:0:8, 0: 1 :7, 1 :0:7, 1 : 1 :6, 0:2:6, 2:0:6, 1 :2:5, 2: 1 :5, 0:3:5, 3:0:5, 0:4:4, 4:0:4, 1 :3:4, 3: 1 :4, 2:2:4, 0:4:4, 4:0:4, 2:4:2, 4:2:2, 1 :4:3, 3:4: 1, 5:0:3, 5:3:0, 5: 1 :2, 5:2: 1, 6:0:2, 6:2:0, 6: 1 : 1, 7:0: 1, 7: 1 :0, 0:8:0, 8:0:0, and the like.
  • a feature of exemplary embodiments of the presently disclosed synthetic blend material is that the attraction of F-POSS molecules to each other is reduced due to the variation in different F-POSS molecules in the blend distribution.
  • Some F-POSS molecules synthesized from two different R substituent feedstocks will have all eight apices with the same R substituent, while some molecules will have at least two apices with different R substituents.
  • the attractive force of the fluorines of neighboring F-POSS molecules for each other is weakened. This weakened attraction can result in an improved ability of the F-POSS molecules to dissociate or to disperse in other materials.
  • Formulating a paint material with a fluorinated material has heretofore been difficult because the strong attraction of F-POSS to itself reduces the dissociation in the paint base and often results in aggregation or phase separation, which provides aesthetically unpleasing coating, and also reduces the desirable properties of the paint, such as, but not limited to, surface texture, smoothness, reflectivity, durability, abrasion resistance, and the like.
  • the synthetic blend of F-POSS molecules can be effectively dispersed in a paint material because the F-POSS molecules are less attracted to each other and will disperse more effectively. This can result in a more even coat and improve physical properties, as well as aesthetic properties.
  • the synthetic blend F- POSS material of the present disclosure can be formulated into a polymer-based paint.
  • the paint is a polyurethane-based paint.
  • the paint is a polyethylene- or polystyrene -based paint.
  • the paint may contain or be based on at least one of the following: polyester, polypropylene, polybutylene, poly(L-lactic acid), polycellulosic, polyhydroxy alkanate, lignose cellulose, polyethylene oxide, epoxy, epoxy resin, alkyd resin, polyether, and mixtures and combinations of at least two of the foregoing.
  • the polymer synthetic blend composition may have a solubility in the polymer base paint material of about 70% solids comprised of polyurethanes diluted in at least one of the following: toluene, methyl ethyl ketone, IP A, xylene and the like.
  • nano-scale roughness increases the hydrophobicity of the material, which may provide an increased water contact angle and hydrocarbon contact angle that enhances performance.
  • C4 F-POSS material is less expensive to produce than C6 or C8 F-POSS, without appreciable compromise of performance.
  • the shorter the carbon chain length the less repellent the material.
  • C4 F-POSS may not have the requisite desirable properties to be effective in some applications.
  • synthetic blend F-POSS materials have been synthesized containing C4 substituents. Such materials have exhibited hexadecane contact angle performance equivalent to C8 F-POSS materials. While not wishing to be bound by any particular theory, such performance enhancement may perhaps be due to the resulting nanostructure of the matrix. See Figs. 16 and 17 described hereinbelow.
  • compositions when formulated as the SB3 blend, discussed further hereinbelow in the Examples, are that the composition may provide reduced ice adhesion in formulations.
  • synthetic blend molecules presently disclosed in exemplary embodiments is that the blends demonstrated physical properties not predictable by considering each of the feedstock materials alone. For example, with respect to solubility, discussed in Examples lB(i-iii), where a 4/2 feedstock and a 6/2 feedstock are used to make the synthetic blend F-POSS composition, the resulting molecular distribution has 0% 6/2 and 100% 4/2 at one side of the graph, and 100% 6/2 and 0%> 4/2 at the opposite side of the graph.
  • blend ratio of 6/2 and 4/2 changes, a straight line is not achieved.
  • the blend ratio change is not a linear relationship.
  • solubility increases, but predictably as determined by the endpoints of the blend ratio.
  • the cause of the particular behavior is the activity occurring at a particular level of order in the noncovalent extended matrix.
  • a unique feature of synthetic blend materials in various exemplary embodiments is that the properties may be customized by adjusting the carbon chain length ratio of the feedstock molecules.
  • compositions disclosed herein may be useful in the formulation of protective coatings, such as, but not limited to, repelling oil, water or the like.
  • protective coatings such as, but not limited to, repelling oil, water or the like.
  • Exemplary embodiments of compositions disclosed herein may be useful in improving the stability and longevity of formulations containing fluorinated, halogenated or other additive materials that ordinarily would not have adequately stable or durable homogeneity.
  • a non- fluorinated POSS structure may be formed according to methods described herein adapted to replace the fluorine component in at least one of the feedstock materials with another component, or to not use fluorine at all.
  • an alkyl group substituted for the fluorine could make the composition formed more compatible with hydrocarbon systems.
  • POSS cage structures other than the T8 form may be formed by modifying the methods disclosed herein.
  • the feedstock molecules can be chosen based on desired properties to be included in the formed composition.
  • Feedstock molecules may be selected for any of a number of properties or characteristics, including, but not limited to, optimization of compatibilization, inclusion of chromophore or other color-imparting substituent, smell, detectable marker, anti-microbial, or the like.
  • a first feedstock may be one that imparts compatibilization (such as the first feedstock described hereinabove), and a second feedstock may contain a substituent that imparts a color or smell.
  • the resulting F-POSS (or other) molecular distribution will include the characteristics of the feedstock materials.
  • SB1 A 3: 1 ratio of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane ("6/2"): 1H, ⁇ H, 2H, 2H-Nonafluorohexyltriethoxysilane ("4/2")
  • SB2 A 1 : 1 ratio of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane: ⁇ H, ⁇ H, 2H, 2H- Nonafluorohexyltriethoxysilane
  • SB3 A 1 :3 ratio of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane: lH, ⁇ H, 2H, 2H- Nonafluorohexyltriethoxysilane
  • the solvent in the reaction mixture was decanted, the precipitate washed repeatedly with ethanol, then dried under vacuum oven overnight at 45-50 °C.
  • the crude product was then dissolved in AK-225G solvent, and then the organic layer washed three times with ddH 2 0, dried over anhydrous magnesium sulfate, filtered, concentrated and dried under vacuum overnight at 80 °C.
  • the resulting purified product was still a semi-solid substance.
  • the solvent in the reaction mixture was decanted, the precipitate washed repeatedly with ethanol, then dried under vacuum overnight at 45-50 °C.
  • the crude product was then dissolved in AK-225G solvent, and then the organic layer washed three times with ddH 2 0, dried over anhydrous magnesium sulfate, filtered, concentrated and dried under vacuum overnight at 80 °C.
  • the resulting purified product was still a semi-solid substance.
  • Example lA(iii)— SB3 (ratio of [25% 6/2]: [75% 4/2]) [0145] 1.28g of the 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (Sigma Aldrich, 667420- 25g) and 3. lg of IH, IH, 2H, 2H-Nonafluorohexyltriethoxysilane (TCI America, T2860) (1 :3 molar ratios) were taken in 10 mL ethanol, to which was added 0.3 mL of KOH solution (7.4 mg/mL). The mixture was stirred at room temperature for 24 h resulting in the precipitation of a white semi-solid product.
  • Peaks from 4/2 side chain ⁇ -77.73 (for -CF 3 ), -121.10 (for -CF 2 -), -131.26 (for - CF 2 -) and -133.71 (for -CF 2 -) Peaks from 6/2 side chain: ⁇ -77.37 (for -CF 3 ), -120.80 (for - CF 2 -), -128.29 (for -CF 2 -), -129.49 (for -CF 2 -), -130.01 (for -CF 2 -) and -133.71 (for -CF 2 - , overlapped with the 4/2 side chain).
  • the peak height for that at -77.37 ppm is greater than that at -77.73 ppm (-CF 3 from 4/2 side chain).
  • these two peak heights and integrations were almost 1 : 1 in the 50/50 blend.
  • a similar trend is observed for the peak heights at -120.80 ppm (from 6/2 side chain) and -121.10 (from 4/2 side chain).
  • 19 F NMR analysis for the synthetic blend SB2 F-POSS is shown in Fig. 5.
  • 19 F NMR spectrum for SB2 showed the following chemical shifts: -77.55, -77.88, -120.96, -121.27, - 128.35, -129.56, -130.09, -131.35 and -133.79.
  • the integrations for the peaks at -77.55 and - 77.88 ppm (highlighted by a blue rectangle in the figure above), which showed very similar peak heights, were obtained at the ratio of approx. 1 : 1.
  • DSC of SB2 is shown in Fig. 6.
  • the melting points of pure 4/2 and 6/2 F-POSS are about 30°C higher than those of the synthetic blend SB2.
  • the fact that the melting points of the synthetic blend F-POSS are different suggests that different compounds with different properties were chemically formed by varying the molar ratios of the precursors.
  • 19 F NMR analysis for the synthetic blend SB3 F-POSS is shown in Fig. 8.
  • 19 F NMR spectrum for the synthetic blend SB3 showed the following chemical shifts: -77.51, -77.86, - 120.94, -121.24, -128.34, -129.55, -130.10, -131.35 and -133.74.
  • DSC of SB3 is shown in Figs. 9A and 9B.
  • the melting points of pure 4/2 and 6/2 F- POSS are about 30°C higher than those of the synthetic blends SB3.
  • the fact that the melting points of the synthetic blend F-POSS are different suggests that different compounds with different properties were chemically formed by varying the molar ratios of the precursors.
  • Example 1C Comparison of 6/2:4/2 Synthetic Blends
  • Table 1 below and Fig. 11 show the difference in melting temperatures for the various synthetic blend materials.
  • Example 2 Formulation of Synthetic Blends in Paint
  • Two-component paint was prepared according to manufacturer's directions by mixing Windmastic TopCoat Repair Kit 7035 Grey Part A base paint (Carboline, UN1293) with Windmastic TopCoat Repair Kit Part B Resin (Carboline, UN1866) 6: l(v/v).
  • To ensure accurate measurements of paint six volumes (mLs) of Part A were weighed several times and the weights averaged 8.6g; one volume (mL) of Part B was weighed several times averaging 0.97g. Weight-to-weight ratios were then used throughout each experiment for the formulation of the control paint.
  • the 2 component paint (8.6g of Part A and 0.97g of Part B) were added to a Flacktek Speedmixer lOmL polypropylene translucent container. The paint was then mixed for 10 minutes at 2700rpm in the Flacktek DAC400 FVZ Speedmixer.
  • FIGs. 13A-D Representative images of coated steel containing the synthetic blend SB3 at each weight % loading in paint are shown in Figs. 13A-D (Fig. 13A— 1 wt%; Fig. 13B— 5 wt%; Fig. 13C— 10 wt%; and Fig. 13D— 25 wt%).
  • Example 3 Performance of Synthetic Blends in Paint
  • Fig. 14 shows plots of the water contact angle of paint only, and of SB1, SB2 and SB3.
  • Contact angles of hexadecane, shown in Fig. 15, were measured using the same instrument fitted with a manual syringe dispensing similar volumes.
  • Fig. 16 is a graph of the contact angle of water (1 10 degrees) and the contact angle of hexadecane (80 degrees) of synthetic blend SB3 in 50/50 % blends of PEMA on glass substrates with 1% weight loadings in AK-225.

Abstract

The present disclosure relates, in exemplary embodiments, to compositions of matter comprising synthetic blends of at least two feedstocks that produce a distribution of fluorinated polyhedral oligomeric silsesquioxane molecule structures. The present disclosure also relates, in exemplary embodiments, to methods of making such synthetic blends.

Description

PATENT COOPERATION TREATY
PATENT APPLICATION
SYNTHETIC BLEND F-POSS COMPOSITIONS FORMED FROM MULTIPLE
FEEDSTOCK MATERIALS
INVENTOR:
JOHN C. WARNER
CROSS REFERENCE TO RELATED APPLICATION
[001] This application claims the benefit of U.S. Provisional Patent Application No. 62/060,622, filed October 7, 2014, the contents of which is incorporated herein by reference in their entirety.
FIELD
[002] The present disclosure relates, in exemplary embodiments, to compositions of matter comprising synthetic blends of at least two feedstocks that produce a distribution of fluorinated polyhedral oligomeric silsesquioxane molecule structures. The present disclosure also relates, in exemplary embodiments, to methods of making such synthetic blends.
BACKGROUND
[003] Fluorinated polyhedral oligomeric silsesquioxane ("F-POSS") molecules are a subclass of polyhedral oligomeric silsesquioxanes ("POSS") which consists of a silicon- oxide core [S1O1.5] with a periphery of long-chain fluorinated alkyl groups. Such alkyl groups include fluorinated triethoxysilanes. F-POSS molecules possess some of the lowest known surface energies leading to the creation of superhydrophobic and oleophobic surfaces. A feature of F-POSS material is that it ordinarily forms a siloxy cage that acts like an inorganic glass-like material, but have organic R group substituents at the matrix apices, which provides unusual properties and applications. See formula [1] below. Each R substituent can be labeled as, for example, Rl, R2, R3, R4, R5, R6, R7 or R8. See formula [2] below.
Figure imgf000003_0001
[004] It is believed that heretofore F-POSS materials have been formed having only one molecule as the R substituent for all apices. See for example, the following U.S. Patents and published applications: 6,716,919 (issued to Lichtenhan et al), 7,195,015 (issued to Mabry et al), 2008/0221262 (filed by Mabry et al), and 2013/0072609 (filed by Haddad et al.).The fluorine atoms of neighboring F-POSS molecules have a tendency to attract each other resulting in F-POSS molecules not typically being readily dispersible or dissociable in other materials. F-POSS molecules typically have low solubility in non-fluorinated solvents. It would be desirable to have an F-POSS material that was more easily dispersed or dissociated in other materials.
SUMMARY
[005] In one aspect, the disclosure provides an F-POSS compound of the formula
Figure imgf000004_0001
[006] or a mixture thereof, wherein R 1 and R 2 are each independently long-chain
1 2
fluorinated alkyl, and n is an integer from 0 to 8, provided that R and R are different.
[007] In another aspect, the disclosure provides an F-POSS composition comprising a mixture of compounds of the formula
Figure imgf000004_0002
[008] wherein R 1 and R 2 are each independently long-chain fluorinated alkyl, and integer from 0 to 8, provided that R 1 and R 2 are different. [009] In another aspect, the disclosure provides an F-POSS composition produced by a process comprising: [010] contacting a first feedstock comprising a first fluorinated trialkoxysilane with a second feedstock comprising a second fluorinated trialkoxysilane, wherein the first fluorinated trialkoxysilane and the second fluorinated trialkoxysilane are different.
[Oi l] In another aspect, the disclosure provides a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS") comprising, a mixture of feedstock materials comprising
[012] a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and,
[013] b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y,
[014] wherein the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
[015] In another aspect, the disclosure provides a polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS") comprising, a mixture of feedstock materials comprising
[016] a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is a number of carbon atoms; and,
[017] b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is a number of carbon atoms, wherein x is not equal to y, [018] wherein the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2. [019] In another aspect, the disclosure provides a polymer synthetic blend composition, comprising: polymerized units of a first feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; and a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4- 10, wherein x is greater than y.
[020] In another aspect, the disclosure provides a method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents, comprising:
[021] a. providing a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; [022] b. providing a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4- 10, wherein x is greater than y; and
[023] c. reacting the first feedstock with the second feedstock under conditions so as to form a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2. [024] In another aspect, the disclosure provides a paint composition, comprising:
[025] a. at least one polymer base paint material; and [026] b. a polymer synthetic blend composition comprising polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising
[027] i. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and,
[028] ii. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y,
[029] whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2. [030] The compounds of the present disclosure can be described as embodiments in any of the following enumerated clauses. It will be understood that any of the embodiments described herein can be used in connection with any other embodiments described herein to the extent that the embodiments do not contradict one another.
[031] 1. A polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising
[032] a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and,
[033] b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y, [034] whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2. [035] 2. The polymer synthetic blend composition of clause 1 , wherein the first feedstock is 1H, 1H, 2H, 2H nonafluorohexyltriethoxysilane.
[036] 3. The polymer synthetic blend composition of clause 1 or 2 , wherein the second feedstock is 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane.
[037] 4. The polymer synthetic blend composition of any one of clauses 1 to 3, wherein the first feedstock and the second feedstock are present in a molar ratio in a range of from 1 :3 to 3: 1.
[038] 5. The polymer synthetic blend composition of any one of clauses 1 to 4, wherein the melting temperature of the polymer blend composition is at least about 30 degrees lower than the melting temperature of either the first feedstock or the second feedstock alone. [039] 6. The polymer synthetic blend composition of any one of clauses 1 to 5, wherein x is in a range of 1-16 and y is in a range of 1-16.
[040] 7. The polymer synthetic blend composition of any one of clauses 1 to 6, wherein x is in a range of 4-10 and y is in a range of 4-10.
[041] A polymer synthetic blend composition, comprising: a mixture of at least two feedstock materials comprising
[042] a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons;
[043] b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is not equal to y, and [044] whereby the polymer blend composition resulting from the mixing of the at least two feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
[045] 8. The polymer synthetic blend composition of clause 7, wherein x is in a range of 1- 16 and y is in a range of 1-16. [046] 9. The polymer synthetic blend composition of clause 7 or 8, wherein x is in a range of 4-10 and y is in a range of 4-10.
[047] 10. A polymer synthetic blend composition, comprising: polymerized units of a first feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; and a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4-10, wherein x is greater than y.
[048] 11. A method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents, comprising:
[049] a. providing a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10;
[050] b. providing a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4- 10, wherein x is greater than y; and
[051] c. reacting the first feedstock with the second feedstock under conditions so as to form a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
[052] 12. A polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising
[053] a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and
[054] b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y, [055] whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
[056] 13. A polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising
[057] a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and
[058] b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y,
[059] whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a first portion of the distribution of molecules formed have substituent R having a Clx:C2y ratio of 1 :0, a second portion of the distribution of molecules formed have substituent R having a Clx:C2y ratio of 0: 1, and a third portion of the molecules have substituent R having a C lx:C2y ratio in a range of from 1 :7 to 7: 1.
[060] 14. A paint composition, comprising: [061] a. at least one polymer base paint material; and
[062] b. a polymer synthetic blend composition comprising polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising
[063] i. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and,
[064] ii. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y,
[065] whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein C 1 is greater than C2 [066] 15. The paint composition of clause 14, wherein the polymer base paint material comprises at least one material selected from the group consisting of a polyurethane, polyester, polypropylene, polybutylene, poly(L-lactic acid), polycellulosic, polyhydroxy alkanate, lignose cellulose, polyethylene oxide, epoxy, epoxy resin, alkyd resin, polyether, and mixtures of at least two of the foregoing. [067] 16. The paint composition of clause 14 or 15, wherein the paint composition has a water contact angle of at least 110 degrees and a hexadecane contact angle of at least 70 degrees. [068] 17. The paint composition of any one of clauses 14 to 16, wherein the polymer synthetic blend composition has a solubility in the at least one polymer base paint material of 70% solids comprised of polyurethanes diluted in at least one material selected from the group consisting of toluene, methyl ethyl ketone, IPA and xylene.
[069] 18. A method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents, comprising:
[070] a. providing a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10;
[071] b. providing a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4- 10, wherein x is greater than y; and
[072] c. reacting the first feedstock with the second feedstock under conditions so as to form a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
[073] 19. An F-POSS compound of the formula
Figure imgf000012_0001
[074] or a mixture thereof, wherein R 1 and R 2 are each independently long-chain
1 2
fluorinated alkyl, and n is an integer from 0 to 8, provided that R and R are different. [075] 20. The F-POSS compound of clause 19, wherein each long-chain fluormated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
[076] 21. The F-POSS compound of clause 19 or 20, wherein each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
[077] 22. The F-POSS compound of any one of clauses 19 to 21, wherein R1 is 4/2 fluorinated alkyl and R is 6/2 fluorinated alkyl.
[078] 23. An F-POSS composition comprising a mixture of compounds of the formula
Figure imgf000013_0001
[079] wherein R 1 and R 2 are each independently long-chain fluorinated alkyl, and n is an integer from 0 to 8, provided that R 1 and R 2 are different.
[080] 24. The F-POSS composition of clause 23, wherein each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms. [081] 25. The F-POSS composition of clause 23 or 24, wherein each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
[082] 26. The F-POSS composition of any one of clauses 23 to 25, wherein R1 is 4/2 fluorinated alkyl and R is 6/2 fluorinated alkyl. [083] 27. The F-POSS composition of any one of clauses 23 to 26, wherein the mixture of
1 2
compounds comprises a distribution of compounds having a ratio of R to R between 0:8 to 8:0.
[084] 28. The F-POSS composition of clause 27, wherein the distribution is a Gaussian distribution.
[085] 29. An F-POSS composition produced by a process comprising:
[086] contacting a first feedstock comprising a first fluorinated trialkoxysilane with a second feedstock comprising a second fluorinated trialkoxysilane, wherein the first fluorinated trialkoxysilane and the second fluorinated trialkoxysilane are different. [087] 30. The F-POSS composition of clause 29, wherein the first fluorinated
trialkoxysilane is of the formula R1Si(ORA)3, and the second fluorinated trialkoxysilane is of the formula R 2 Si(OR B )3, wherein each of R 1 and R2 are independently a long-chain fluorinated alkyl, each RA and RB is independently Ci-C6 alkyl, provided that R1 and R2 are different. [088] 31. The F-POSS composition of clause 30, wherein each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
[089] 32. The F-POSS composition of clause 30, wherein each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
[090] 33. The F-POSS composition of any one of clauses 29 to 32, wherein R1 is 4/2 fluorinated alkyl and R is 6/2 fluorinated alkyl.
[091] 34. The F-POSS composition of any one of clauses 29 to 33, wherein the composition
1 2
comprises a mixture of compounds in a distribution having a ratio of R to R between 0:8 to 8:0. [092] 35. The F-POSS composition of clause 34, wherein the distribution is a Gaussian distribution.
BRIEF DESCRIPTION OF THE DRAWINGS
[093] The drawings disclose exemplary embodiments in which like reference characters designate the same or similar parts throughout the figures of which:
[094] Fig. 1 is an analysis plot of lH NMR analysis for a synthetic blend SBl according to Example lA(i).
[095] Fig. 2 is an analysis plot of 19F NMR analysis for the synthetic blend SBl according to Example lA(i). [096] Fig. 3 is a graph of Differential Scanning Calorimetry of SBl according to Example lA(i).
[097] Fig. 4 is an analysis plot of lH NMR analysis for a synthetic blend SB2 according to Example lA(ii).
[098] Fig. 5 is an 19F NMR analysis for the synthetic blend SB2 according to Example lA(ii).
[099] Fig. 6 is a graph of Differential Scanning Calorimetry of SB2 according to Example lA(ii).
[0100] Fig. 7 is an analysis plot of lH NMR analysis for a synthetic blend SB3 according to Example lA(iii). [0101] Fig. 8 is an analysis plot of 19F NMR analysis for the synthetic blend SB3 according to Example lA(iii).
[0102] Fig. 9A is a graph of a first Differential Scanning Calorimetry analysis of SB3 prepared according to Example lB(iii). [0103] Fig. 9B is a graph of a second Differential Scanning Calorimetry analysis of SB3 prepared according to Example lB(iii).
[0104] Fig. 10 is an analysis plot 19F NMR analysis comparing the synthetic blends SB1, SB2 and SB3 of Examples lA(i), lA(ii) and lA(iii). [0105] Fig. 11 is a graph of the melting points (in °C) of synthetic blends.
[0106] Fig. 12 is a chart of the approximate percent composition of SB1, SB2 and SB3 as prepared based on feedstock.
[0107] Fig. 13A is a photograph of coated steel containing SB3 at 1 wt%.
[0108] Fig. 13B is a photograph of coated steel containing SB3 at 5 wt%. [0109] Fig. 13C is a photograph of coated steel containing SB3 at 10 wt%.
[0110] Fig. 13D is a photograph of coated steel containing SB3 at 25 wt%.
[0111] Fig. 14 is a graph of the contact angle of water of synthetic blends SB1, SB2 and SB3 on Windmaster 7035 paint.
[0112] Fig. 15 is a graph of the contact angle of hexadecane of synthetic blends SB1, SB2 and SB3 on Windmaster 7035 paint.
[0113] Fig. 16 is a graph of the contact angles of water and hexadecane of synthetic blend SB3 in 50/50 % blends of PEMA on glass substrates with 1% weight loadings in AK-225.
DETAILED DESCRIPTION
[0114] Silsesquioxanes have a cage-like structure, which is most commonly a cube, hexagonal prism, octagonal prism, decagonal prism, or dodecagonal prism. In exemplary embodiments, of the various possible F-POSS cage molecular structures, the cube-like ("T8") cage structure is formed. In exemplary embodiments, the present disclosure provides F-POSS compositions made of a blend of feedstock materials. In one exemplary embodiment, a first feedstock comprises a first fluorinated triethoxysilane and a second feedstock comprises a second fluorinated triethoxysilane. Each fluorinated triethoxysilane has a distinct carbon chain length C. In exemplary embodiments, C is in a range of 4-10. In exemplary embodiments, C is in a range of 4-10. In exemplary embodiments, C is 4, 6, 8 or 10. In exemplary embodiments, a first feedstock may be a C6 fluoroalkyl molecule and the second feedstock may be a C8 fluoroalkyl molecule. In exemplary embodiments, a first feedstock may be 1H, 1H, 2H, 2H nonafluorohexyltriethoxysilane. In exemplary embodiments, a second feedstock may be 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (a.k.a. 1H, 1H, 2H, 2H decatriafluorooctyltriethoxysilane).
[0115] As used herein, the term "long-chain fluorinated alkyl" means any straight chain or branched chain alkyl group having from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms as counted from the point of attachment of the chain of carbon atoms to the silicon atom at any apex of the silicon-oxide core, where at least one hydrogen atom in the straight chain or branched chain alkyl group is replaced by a fluorine atom. Any number of hydrogen atoms in the straight chain or branched chain alkyl group can be replaced with fluorine atoms within the meaning of "long-chain fluorinated alkyl" as used herein. For example, the terminal methyl group of a straight chain alkyl group having six carbon atoms in the chain (e.g. a hexyl group) can have each of the pendent hydrogen atoms replaced by a fluorine atom (e.g. a trifluoromethyl) to provide a long chain fluorinated alkyl group having the formula -CH2CH2CH2CH2CH2CF3. In another example, the last two carbon atoms of a straight chain alkyl group having six carbon atoms in the chain can have each of the pendent hydrogen atoms replaced by a fluorine atom (e.g. a trifluoroethyl) to provide a long chain fluorinated alkyl group having the formula -CH2CH2CH2CH2CF2CF3. This exemplary pattern can be continued to include within the definition of "long chain fluorinated alkyl" groups of the formula -CH2CH2CH2CF2CF2CF3, -CH2CH2CF2CF2CF2CF3,
-CH2CF2CF2CF2CF2CF3, and -CF2CF2CF2CF2CF2CF3. As is commonly known in the art, an alkyl group where every hydrogen atoms in the chain is replaced by a fluorine atom is known as a "perfluorinated" alkyl group. In some embodiments, the term perfluorinated is used in connection with a group where some carbon atoms are defined to have hydrogen atoms bonded thereto, while other carbon atoms have all fluorine atoms bonded thereto. For example, the nomenclature 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane describes a compound in which the two terminal carbon atoms at the point of covalent attachment of the chain to the F-POSS have hydrogen atoms bound to the carbon atom, while the remainder of the carbon atoms in the chain have fluorine atoms bonded thereto and are thus are perfluorinated.
[0116] When less than all of the carbon atoms in the longest continuous chain of carbon atoms have hydrogens replaced by fluorine atoms, the "long chain fluorinated alkyl" group can be identified by the shorthand X/Y, where X is the number of terminal carbon atoms in the longest continuous chain of carbon atoms as counted from the point of attachment of the chain of carbon atoms to the silicon atom at any apex of the silicon-oxide core, and Y is the remaining number of carbon atoms in the longest continuous chain of carbon atoms on which hydrogen atoms are not replaced by fluorine atoms. For example, a long chain fluorinated alkyl group of the formula -CH2CH2CF2CF2CF2CF3 can be given the shorthand 4/2. Other exemplary long chain fluorinated alkyl groups include but are not limited to 3/3, 6/2, 4/4, 8/2, 6/4 and the like. It will be appreciated that such long chain fluorinated alkyl groups can also be referred to as 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl, 6/4 fluorinated alkyl, and the like
[0117] When the shorthand X/Y is used herein in connection with F-POSS, the name provided refers to the F-POSS molecule each of the groups attached to the apices of the silicon-oxide core is of the long chain fluorinated alkyl group type defined by the X/Y. For example, 6/2 F-POSS refers to an F-POSS molecule of Formula [1], wherein each of the R groups at the apices of the silicon-oxide core is a 6/2 long chain fluorinated alkyl group as defined herein.
[0118] As examples, formulae for 6/2 F-POSS [3] and 4/2 F-POSS [4] molecules are shown below.
6/2 F-POSS
Figure imgf000019_0001
R = CH2CH2CF2CF2CF2CF2CF2CF3 [3]
4/2 F-POSS
Figure imgf000019_0002
R = CH2CH2CF2CF2CF2CF3 [4]
[0119] In conventional F-POSS synthesis, the F-POSS molecule has a matrix structure having eight apices, each apex comprising silicon. Each apex has a substituent moiety R, which comprises a C-F chain having a carbon chain length Cn, where n is the number of carbons in the chain. 6/2 F-POSS is a C8 molecule as the R substituent has 8 carbons. This F- POSS is designated as 6/2 as it has 6 C-F groups and 2 C-H groups. 4/2 F-POSS is a C6 molecule as the R substituent has 6 carbons comprising 4 C-F groups and 2 C-H groups. [0120] In exemplary embodiments of the present compositions, a blend of several distinct F- POSS molecules is synthesized from a first feedstock fluorinated triethoxysilane and a second feedstock fluorinated triethoxysilane, each feedstock being a different fluorinated triethoxysilane. The end product synthesized is a distribution of F-POSS molecules having portions made up of distinct F-POSS molecules with one of several R substituents (e.g., R1,
2 3
R , R , etc.). A portion of the F-POSS molecules have a matrix structure having all eight apices with a substituent R1 and having the same carbon chain length C. A portion of the molecules will have all eight apices with a substituent R . Formula [5] below shows a molecular formula with (n)R 1 units and (8-n)R 2 units, where n is the number of units, and
1 2
each R and/or R unit is covalently attached to a silicon atom apex of the cube-like structure. It will be appreciated that n in the formula [5] is an integer from 0 to 8.
Figure imgf000020_0001
[0121] A portion of the molecules have a matrix structure in which one or more apices have a substituent R 1 and the remainder have a substituent R 2 , where R 1 and R2 have different carbon chain lengths (e.g. CI and C2). In the present compositions, the blend of molecules may, in exemplary embodiments, form a Gaussian distribution of molecules having different
1 2
ratios of R and R . For example, in one exemplary embodiment, one portion of the blend
1 2
may be made up of an F-POSS molecule with a molar ratio of R :R = 0:8, in other words, all
2 1 2
eight apices have R . Another portion may have a molar ratio of R :R = 1 :7, in other words,
2 1
seven of the apices have R and one apex has R . Another portion has a ratio of 2:6. And, other portions have ratios of 3:5, 4:4, 5:3, 6:2, 7: 1 and 8:0. In exemplary embodiments, the distribution of R 1 :R 2 ratios generally comprises a Gaussian distribution. In exemplary embodiments, the distribution of ratios can be predetermined to an extent, or tuned, based on reaction conditions and amounts used of each substituent. [0122] In one exemplary embodiment, a synthetic blend F-POSS was formed of 50% C4 and 50% C6 chain length R substituent molecules.
[0123] In some embodiments, the processes described herein can be represented by the following general scheme:
Figure imgf000021_0001
[0124] wherein R1 and R2 are as defined above, n is an integer from 0 to 8, and each RA and RB is independently an Ci-C6 alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n- butyl, sec-butyl, iso-butyl, n-pentyl, sec-pentyl, and the like. In some embodiments, each RA and RB is ethyl. [0125] In exemplary embodiments, three or more feedstocks can be used, each feedstock comprising fluoroalkyl molecule having a different carbon chain length, i.e., a first feedstock may be a fluoroalkyl molecule having a carbon chain length C4, the second feedstock may have the carbon chain length C6, and the third feedstock may have the carbon chain length C8. The distribution of F-POSS molecules formed therefrom will have some F-POSS molecules having the C4 substituent at all eight apices; other molecules in the distribution will have all eight apices having the C6 substituent at all eight apices; still other molecules will have all eight apices having the C8 substituent; and, still other molecules in the distribution blend will have one apex with C4, a second apex with C6, and a third apex with C8, the other apices each having a C4, C6, or C8 substituent; with various other molecules in the distribution blend having different ratios of C4, C6 and C8 at the apices. Exemplary ratios in a blend of F-POSS molecules prepared from three feedstocks of chain length C4, C6 and C8 include, but are not limited to, 0:0:8, 0: 1 :7, 1 :0:7, 1 : 1 :6, 0:2:6, 2:0:6, 1 :2:5, 2: 1 :5, 0:3:5, 3:0:5, 0:4:4, 4:0:4, 1 :3:4, 3: 1 :4, 2:2:4, 0:4:4, 4:0:4, 2:4:2, 4:2:2, 1 :4:3, 3:4: 1, 5:0:3, 5:3:0, 5: 1 :2, 5:2: 1, 6:0:2, 6:2:0, 6: 1 : 1, 7:0: 1, 7: 1 :0, 0:8:0, 8:0:0, and the like. It will be appreciated that a blend made by the processes described herein can possess any of the ratios above, and any other ratios possible within the distribution provided by the process. It will be further appreciated that it is possible to "tune" the distribution ratio of R substituents based on amounts of feedstocks, reaction conditions and other parameters. Properties
[0126] A feature of exemplary embodiments of the presently disclosed synthetic blend material is that the attraction of F-POSS molecules to each other is reduced due to the variation in different F-POSS molecules in the blend distribution. Some F-POSS molecules synthesized from two different R substituent feedstocks will have all eight apices with the same R substituent, while some molecules will have at least two apices with different R substituents. By making neighboring F-POSS molecules potentially having different R substituents and "look" different to each other, the attractive force of the fluorines of neighboring F-POSS molecules for each other is weakened. This weakened attraction can result in an improved ability of the F-POSS molecules to dissociate or to disperse in other materials.
[0127] Formulating a paint material with a fluorinated material has heretofore been difficult because the strong attraction of F-POSS to itself reduces the dissociation in the paint base and often results in aggregation or phase separation, which provides aesthetically unpleasing coating, and also reduces the desirable properties of the paint, such as, but not limited to, surface texture, smoothness, reflectivity, durability, abrasion resistance, and the like. In exemplary embodiments, the synthetic blend of F-POSS molecules can be effectively dispersed in a paint material because the F-POSS molecules are less attracted to each other and will disperse more effectively. This can result in a more even coat and improve physical properties, as well as aesthetic properties. In exemplary embodiments, the synthetic blend F- POSS material of the present disclosure can be formulated into a polymer-based paint. In exemplary embodiments, the paint is a polyurethane-based paint. In exemplary embodiments, the paint is a polyethylene- or polystyrene -based paint. In exemplary embodiments, the paint may contain or be based on at least one of the following: polyester, polypropylene, polybutylene, poly(L-lactic acid), polycellulosic, polyhydroxy alkanate, lignose cellulose, polyethylene oxide, epoxy, epoxy resin, alkyd resin, polyether, and mixtures and combinations of at least two of the foregoing.
[0128] In exemplary embodiments, the polymer synthetic blend composition may have a solubility in the polymer base paint material of about 70% solids comprised of polyurethanes diluted in at least one of the following: toluene, methyl ethyl ketone, IP A, xylene and the like.
[0129] Another feature of exemplary embodiments of the presently disclosed synthetic blend material is that films and other structures formed therefrom have a degree of "nano-scale roughness" at the molecular level. This nano-scale roughness increases the hydrophobicity of the material, which may provide an increased water contact angle and hydrocarbon contact angle that enhances performance.
[0130] With conventional single R substituent F-POSS molecules, conventional wisdom suggests that C4 F-POSS material is less expensive to produce than C6 or C8 F-POSS, without appreciable compromise of performance. Generally speaking, the shorter the carbon chain length, the less repellent the material. However, conventionally, C4 F-POSS may not have the requisite desirable properties to be effective in some applications. In exemplary embodiments, synthetic blend F-POSS materials have been synthesized containing C4 substituents. Such materials have exhibited hexadecane contact angle performance equivalent to C8 F-POSS materials. While not wishing to be bound by any particular theory, such performance enhancement may perhaps be due to the resulting nanostructure of the matrix. See Figs. 16 and 17 described hereinbelow.
[0131] Another feature of exemplary embodiments of the presently disclosed synthetic blend composition when formulated as the SB3 blend, discussed further hereinbelow in the Examples, is that the composition may provide reduced ice adhesion in formulations. [0132] In one aspect of synthetic blend molecules presently disclosed in exemplary embodiments is that the blends demonstrated physical properties not predictable by considering each of the feedstock materials alone. For example, with respect to solubility, discussed in Examples lB(i-iii), where a 4/2 feedstock and a 6/2 feedstock are used to make the synthetic blend F-POSS composition, the resulting molecular distribution has 0% 6/2 and 100% 4/2 at one side of the graph, and 100% 6/2 and 0%> 4/2 at the opposite side of the graph. As the blend ratio of 6/2 and 4/2 changes, a straight line is not achieved. The blend ratio change is not a linear relationship. As the ratio 6/2:4/2 approaches 1 : 1, solubility increases, but predictably as determined by the endpoints of the blend ratio. Without intending to be bound by any particular theory of the mechanism of action, it may be that the cause of the particular behavior is the activity occurring at a particular level of order in the noncovalent extended matrix.
[0133] A unique feature of synthetic blend materials in various exemplary embodiments is that the properties may be customized by adjusting the carbon chain length ratio of the feedstock molecules.
Applications
[0134] Exemplary embodiments of compositions disclosed herein may be useful in the formulation of protective coatings, such as, but not limited to, repelling oil, water or the like. Exemplary embodiments of compositions disclosed herein may be useful in improving the stability and longevity of formulations containing fluorinated, halogenated or other additive materials that ordinarily would not have adequately stable or durable homogeneity.
[0135] In other exemplary embodiments, rather than an F-POSS structure, a non- fluorinated POSS structure may be formed according to methods described herein adapted to replace the fluorine component in at least one of the feedstock materials with another component, or to not use fluorine at all. For example, an alkyl group substituted for the fluorine could make the composition formed more compatible with hydrocarbon systems.
[0136] POSS cage structures other than the T8 form may be formed by modifying the methods disclosed herein. [0137] In exemplary embodiments, the feedstock molecules can be chosen based on desired properties to be included in the formed composition. Feedstock molecules may be selected for any of a number of properties or characteristics, including, but not limited to, optimization of compatibilization, inclusion of chromophore or other color-imparting substituent, smell, detectable marker, anti-microbial, or the like. For example, a first feedstock may be one that imparts compatibilization (such as the first feedstock described hereinabove), and a second feedstock may contain a substituent that imparts a color or smell. The resulting F-POSS (or other) molecular distribution will include the characteristics of the feedstock materials.
[0138] The following examples are set forth for purposes of illustration only. Parts and percentages appearing in such examples are by weight unless otherwise stipulated.
EXAMPLES
Example 1— 6/2:4/2 Fluorinated Polyhedral Oligomeric Silsesquioxane (F-POSS) Synthetic Blends
Example 1 A— Synthesis of Materials
[0139] Novel proprietary siloxane-caged compounds containing side groups with varying lengths of fluorinated hydrocarbons, essentially a 6/2:4/2 hybrid, were synthesized. For ease of reference, the following nomenclature was used to identify the new synthetic blend (SB) compounds:
[0140] SB1 : A 3: 1 ratio of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane ("6/2"): 1H, \H, 2H, 2H-Nonafluorohexyltriethoxysilane ("4/2")
[0141] SB2: A 1 : 1 ratio of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane: \H, \H, 2H, 2H- Nonafluorohexyltriethoxysilane [0142] SB3: A 1 :3 ratio of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane: lH, \H, 2H, 2H- Nonafluorohexyltriethoxysilane
Example lA(i)— SB1 (ratio of [75% 6/2]: [25% 4/2])
[0143] 3.83g of 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (Sigma Aldrich, 667420-25g) and 1.03g of \H, \H, 2H, 2H-Nonafiuorohexyltriethoxysilane (TCI America, T2860) (3: 1 molar ratio) were taken in 10 mL ethanol, to which was added 0.3 mL of KOH solution (7.4 mg/mL). The mixture was stirred at room temperature for 24 hrs resulting in the precipitation of a white semi-solid product. The solvent in the reaction mixture was decanted, the precipitate washed repeatedly with ethanol, then dried under vacuum oven overnight at 45-50 °C. The crude product was then dissolved in AK-225G solvent, and then the organic layer washed three times with ddH20, dried over anhydrous magnesium sulfate, filtered, concentrated and dried under vacuum overnight at 80 °C. The resulting purified product was still a semi-solid substance.
Example lA(ii)— SB2 (ratio of [50% 6/2]: [50% 4/2])
[0144] 2.55g of the 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (Sigma Aldrich, 667420- 25g)and 2.05g of IH, IH, 2H, 2H-Nonafiuorohexyltriethoxysilane (TCI America, T2860) (1 : 1 molar ratio) were taken in 10 mL ethanol, to which was added 0.3 mL of KOH solution (7.4 mg/mL). The mixture was stirred at room temperature for 24 h resulting in the precipitation of a white semi-solid product. The solvent in the reaction mixture was decanted, the precipitate washed repeatedly with ethanol, then dried under vacuum overnight at 45-50 °C. The crude product was then dissolved in AK-225G solvent, and then the organic layer washed three times with ddH20, dried over anhydrous magnesium sulfate, filtered, concentrated and dried under vacuum overnight at 80 °C. The resulting purified product was still a semi-solid substance.
Example lA(iii)— SB3 (ratio of [25% 6/2]: [75% 4/2]) [0145] 1.28g of the 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (Sigma Aldrich, 667420- 25g) and 3. lg of IH, IH, 2H, 2H-Nonafluorohexyltriethoxysilane (TCI America, T2860) (1 :3 molar ratios) were taken in 10 mL ethanol, to which was added 0.3 mL of KOH solution (7.4 mg/mL). The mixture was stirred at room temperature for 24 h resulting in the precipitation of a white semi-solid product. The solvent in the reaction mixture was decanted, the precipitate washed repeatedly with ethanol, then dried under vacuum overnight at 45-50 °C. The crude product was then dissolved in AK-225G solvent, and then the organic layer washed three times with ddH20, dried over anhydrous magnesium sulfate, filtered, concentrated and dried under vacuum overnight at 80 °C. The resulting purified product was still a semi-solid substance. Example IB— Characterization of Materials
Example lB(i)— SBl (ratio of [75% 6/2] : [25% 4/2])
[0146] 1H NMR analysis for the synthetic blend SBl F-POSS is shown in Fig. 1. 1H NMR in acetone-d6 (with few drops of AK-225G) showed shifts at 2.44-2.33 ppm (m, 16H) and 0.91- 0.83 (m, 16H), with some minor impurity/precursor peaks between 4.5-3.5 ppm. This product was not as readily soluble in acetone + AK-225G (NMR solvent mixture) as the 4/2 F-POSS, solubility being more similar to that of the 6/2 F-POSS.
[0147] 19F NMR analysis for the synthetic blend SBl is shown in Fig. 2. 19F NMR spectrum for SBl showed the following chemical shifts: -77.37, -77.73, -120.80, -121.10, -128.29, - 129.49, -130.01, -131.26 and -133.71. Using the spectrum for the 50/50 synthetic blend as a reference, peak assignments can be made for -CF2- and -CF3 groups for the two different side chains in the SBl blend:
[0148] Peaks from 4/2 side chain: δ -77.73 (for -CF3), -121.10 (for -CF2-), -131.26 (for - CF2-) and -133.71 (for -CF2-) Peaks from 6/2 side chain: δ -77.37 (for -CF3), -120.80 (for - CF2-), -128.29 (for -CF2-), -129.49 (for -CF2-), -130.01 (for -CF2-) and -133.71 (for -CF2- , overlapped with the 4/2 side chain). Interestingly, as highlighted by the rectangular boxes in Fig. 2, the peak height for that at -77.37 ppm (-CF3 from 6/2 side chain) is greater than that at -77.73 ppm (-CF3 from 4/2 side chain). Incidentally, these two peak heights and integrations were almost 1 : 1 in the 50/50 blend. A similar trend is observed for the peak heights at -120.80 ppm (from 6/2 side chain) and -121.10 (from 4/2 side chain).
[0149] DSC of SBl is shown in Fig. 3. The melting points of pure 4/2 and 6/2 F-POSS are about 30°C higher than those of SBl . The fact that the melting points of the synthetic blend F-POSS are different suggests that different compounds with different properties were chemically formed by varying the molar ratios of the precursors. Example lB(ii)— SB2 (ratio of [50% 6/2] : [50% 4/2])
[0150] 1H NMR analysis for the synthetic blend SB2 F-POSS is shown in Fig. 4. 1H NMR in acetone-d6 (with few drops of AK-225G) showed shifts at 2.39-2.34 ppm (m, 16H) and 0.89- 0.82 (m, 16H), with some minor impurity/precursor peaks between 4.5-3.5 ppm. This product was more readily soluble in acetone + AK-225G (NMR solvent mixture) than the 75%-25% 6/2-4/2 blend (203-64-1).
[0151] 19F NMR analysis for the synthetic blend SB2 F-POSS is shown in Fig. 5. 19F NMR spectrum for SB2 showed the following chemical shifts: -77.55, -77.88, -120.96, -121.27, - 128.35, -129.56, -130.09, -131.35 and -133.79. The integrations for the peaks at -77.55 and - 77.88 ppm (highlighted by a blue rectangle in the figure above), which showed very similar peak heights, were obtained at the ratio of approx. 1 : 1. This suggests that these two peaks each represent the -CF3 groups on the 6/2 and the 4/2 side chains, the peak assignments based on the positioning of the -CF3 peaks in the pure 6/2 and 4/2 F-POSS materials and their precursors. Similarly, the two peaks at -120.96 and -121.27 ppm (also highlighted by a rectangle in Fig. 5) have very similar peak heights, and can be assigned to one each of the 6/2 and the 4/2 F-POSS.
[0152] DSC of SB2 is shown in Fig. 6. The melting points of pure 4/2 and 6/2 F-POSS are about 30°C higher than those of the synthetic blend SB2. The fact that the melting points of the synthetic blend F-POSS are different suggests that different compounds with different properties were chemically formed by varying the molar ratios of the precursors.
Example lB(iii)— SB3 (ratio of [25% 6/2]: [75% 4/2])
[0153] 1H NMR analysis for the synthetic blend SB3 F-POSS is shown in Fig. 7. 1H NMR in acetone-d6 (with few drops of AK-225G) showed shifts at 2.45-2.34 ppm (m, 16H) and 0.91- 0.80 (m, 16H), with slight impurity/precursor peaks between 4.5-3.5 ppm. This product was readily soluble in acetone + AK-225G (NMR solvent mixture), solubility being very similar to that of the 4/2 F-POSS.
[0154] 19F NMR analysis for the synthetic blend SB3 F-POSS is shown in Fig. 8. 19F NMR spectrum for the synthetic blend SB3 showed the following chemical shifts: -77.51, -77.86, - 120.94, -121.24, -128.34, -129.55, -130.10, -131.35 and -133.74. Using the spectrum for the 50/50 synthetic blend as a reference, peak assignments can be made for -CF2- and -CF3 groups for the two different side chains in the 75/25 blend: [0155] Peaks from 4/2 side chain: δ -77.86 (for -CF3), -121.24 (for -CF2-), -131.35 (for - CF2-) and -133.74 (for -CF2-) Peaks from 6/2 side chain: δ -77.51 (for -CF3), -120.94 (for - CF2-), -128.34 (for -CF2-), -129.55 (for -CF2-), -130.10 (for -CF2-) and -133.74 (for -CF2- , overlapped with the 4/2 side chain) Interestingly, as highlighted by the rectangular boxes in the figure above, the peak height for that at -77.51 ppm (-CF3 from 6/2 side chain) is smaller than that at -77.86 ppm (-CF3 from 4/2 side chain). Incidentally, these two peak heights and integrations were almost 1 : 1 in the 50/50 blend. A similar trend is observed for the peak heights at -120.94 ppm (from 6/2 side chain) and -121.24 (from 4/2 side chain).
[0156] DSC of SB3 is shown in Figs. 9A and 9B. The melting points of pure 4/2 and 6/2 F- POSS are about 30°C higher than those of the synthetic blends SB3. The fact that the melting points of the synthetic blend F-POSS are different suggests that different compounds with different properties were chemically formed by varying the molar ratios of the precursors.
Example 1C— Comparison of 6/2:4/2 Synthetic Blends Example lC(i)— 19F NMR
[0157] 19F NMR analysis comparing the synthetic blends SB1, SB2 and SB3 F-POSS is shown in Fig. 10. The changing peak heights for the two sets of peaks (highlighted above) in the three synthetic blends are shown in Fig. 10. Although peaks for the SB1 and the SB3 synthetic blends could not be integrated due to skewed baselines, the trend is clear from the figure below suggesting a decrease in the percentage of the 6/2 side chains with an increase in the percentage for the 4/2 side chains.
Example lC(ii)— Melting Points
[0158] Table 1 below and Fig. 11 show the difference in melting temperatures for the various synthetic blend materials. Table 1
Figure imgf000030_0001
Example ID - Percent Composition Based on Feedstock
[0159] The approximate percent composition of SB1, SB2 and SB3 as prepared above, based on the feedstock, is shown in Table 2 below and in Fig. 12.
Table 2
Approximate Percent Composition Based on Feedstock
Figure imgf000030_0002
Example 2— Formulation of Synthetic Blends in Paint [0160] Two-component paint was prepared according to manufacturer's directions by mixing Windmastic TopCoat Repair Kit 7035 Grey Part A base paint (Carboline, UN1293) with Windmastic TopCoat Repair Kit Part B Resin (Carboline, UN1866) 6: l(v/v). To ensure accurate measurements of paint, six volumes (mLs) of Part A were weighed several times and the weights averaged 8.6g; one volume (mL) of Part B was weighed several times averaging 0.97g. Weight-to-weight ratios were then used throughout each experiment for the formulation of the control paint. The 2 component paint (8.6g of Part A and 0.97g of Part B) were added to a Flacktek Speedmixer lOmL polypropylene translucent container. The paint was then mixed for 10 minutes at 2700rpm in the Flacktek DAC400 FVZ Speedmixer.
[0161] Approximately 0.1 g of SB1, SB2 and SB3 were weighed into lOmL Speedmixer polypropylene containers. Paint was added to the container such that the final concentration (weight %) of synthetic blend F-POSS was 1%, 5%, 10% or 25% in the paint. The containers, including the paint only control, were then placed into the Flacktek Speedmixer for 10 minutes at 2700rpm.
[0162] Each formulation was then coated onto 4"x4" QPanel 0.32" Dull matte finish steel plates (Guardco) using a 4 mil coating bar. The plates were dried overnight at room temperature. No unusual coating properties were observed with any of the synthetic blend formulations in paint, and perhaps offered better film forming properties.
[0163] Representative images of coated steel containing the synthetic blend SB3 at each weight % loading in paint are shown in Figs. 13A-D (Fig. 13A— 1 wt%; Fig. 13B— 5 wt%; Fig. 13C— 10 wt%; and Fig. 13D— 25 wt%). Example 3— Performance of Synthetic Blends in Paint
[0164] Contact angles of water were measured using a Krauss DSA100S drop shape analyzer with an automatic syringe dispenser in 5uL volumes Fig. 14 shows plots of the water contact angle of paint only, and of SB1, SB2 and SB3. Contact angles of hexadecane, shown in Fig. 15, were measured using the same instrument fitted with a manual syringe dispensing similar volumes.
[0165] SB1, SB2 and SB3 performed significantly better than the control of paint alone. There was no significant difference observed between the synthetic blends. The synthetic blends performed equally as well as 6/2 F-POSS or 4/2 F-POSS individually, even at 1% (wt) loading in paint. Results of the synthetic blends show significant increases in hexadecane contact angles compared to 6/2 F-POSS or 4/2 F-POSS alone. [0166] Fig. 16 is a graph of the contact angle of water (1 10 degrees) and the contact angle of hexadecane (80 degrees) of synthetic blend SB3 in 50/50 % blends of PEMA on glass substrates with 1% weight loadings in AK-225.
[0167] Although only a number of exemplary embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims.
[0168] While the methods, equipment and systems have been described in connection with specific embodiments, it is not intended that the scope be limited to the particular embodiments set forth, as the embodiments herein are intended in all respects to be illustrative rather than restrictive.
[0169] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect.
[0170] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. [0171] Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. [0172] "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0173] Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises," means "including but not limited to," and is not intended to exclude, for example, other additives, components, integers or steps. The word "exemplary" or "illustrative" means "an example of and is not intended to convey an indication of a preferred or ideal embodiment. "Such as" is not used in a restrictive sense, but for explanatory purposes. [0174] Disclosed are components that can be used to perform the disclosed methods, equipment and systems. These and other components are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc., of these components are disclosed that while specific reference of each various individual and collective combinations and permutation of these may not be explicitly disclosed, each is specifically contemplated and described herein, for all methods, equipment and systems. This applies to all aspects of this application including, but not limited to, steps in disclosed methods. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods. [0175] It should further be noted that any patents, applications and publications referred to herein are incorporated by reference in their entirety.

Claims

CLAIMS WHAT IS CLAIMED IS:
1. A polymer synthetic blend composition of fluorinated polyhedral oligomeric
silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and, b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y, whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein C 1 is greater than C2.
2. The polymer synthetic blend composition of claim 1, wherein the first feedstock is IH, IH, 2H, 2H nonafluorohexyltriethoxysilane.
3. The polymer synthetic blend composition of claim 1 or 2 , wherein the second feedstock is IH, IH, 2H, 2H perfluorooctyltriethoxysilane.
4. The polymer synthetic blend composition of any one of claims 1 to 3, wherein the first feedstock and the second feedstock are present in a molar ratio in a range of from 1 :3 to 3: 1.
5. The polymer synthetic blend composition of any one of claims 1 to 4, wherein the melting temperature of the polymer blend composition is at least about 30 degrees lower than the melting temperature of either the first feedstock or the second feedstock alone.
6. The polymer synthetic blend composition of any one of claims 1 to 5, wherein x is in a range of 1-16 and y is in a range of 1-16.
7. The polymer synthetic blend composition of any one of claims 1 to 6, wherein x is in a range of 4-10 and y is in a range of 4-10. A polymer synthetic blend composition, comprising: a mixture of at least two feedstock materials comprising a. a first feedstock comprising a first f uorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is not equal to y, and whereby the polymer blend composition resulting from the mixing of the at least two feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
8. The polymer synthetic blend composition of claim 7, wherein x is in a range of 1-16 and y is in a range of 1-16.
9. The polymer synthetic blend composition of claim 7 or 8, wherein x is in a range of 4-10 and y is in a range of 4-10.
10. A polymer synthetic blend composition, comprising: polymerized units of a first feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; and a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4-10, wherein x is greater than y.
11. A method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents, comprising: a. providing a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; b. providing a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4-10, wherein x is greater than y; and c. reacting the first feedstock with the second feedstock under conditions so as to form a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
12. A polymer synthetic blend composition of fluorinated polyhedral oligomeric
silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y, whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
13. A polymer synthetic blend composition of fluorinated polyhedral oligomeric
silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising a. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons; and b. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y, whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a first portion of the distribution of molecules formed have substituent R having a Clx:C2y ratio of 1 :0, a second portion of the distribution of molecules formed have substituent R having a Clx:C2y ratio of 0: 1, and a third portion of the molecules have substituent R having a C lx:C2y ratio in a range of from 1 :7 to 7: 1.
14. A paint composition, comprising: a. at least one polymer base paint material; and b. a polymer synthetic blend composition comprising polymer synthetic blend composition of fluorinated polyhedral oligomeric silsesquioxane ("F-POSS"), comprising: a mixture of feedstock materials comprising i. a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and, ii. a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, wherein x is greater than y, whereby the polymer blend composition resulting from the mixing of the first and second feedstocks comprises a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein C 1 is greater than C2
15. The paint composition of claim 14, wherein the polymer base paint material comprises at least one material selected from the group consisting of a polyurethane, polyester, polypropylene, polybutylene, poly(L-lactic acid), polycellulosic, polyhydroxy alkanate, lignose cellulose, polyethylene oxide, epoxy, epoxy resin, alkyd resin, polyether, and mixtures of at least two of the foregoing.
16. The paint composition of claim 14 or 15, wherein the paint composition has a water contact angle of at least 1 10 degrees and a hexadecane contact angle of at least 70 degrees.
17. The paint composition of any one of claims 14 to 16, wherein the polymer synthetic blend composition has a solubility in the at least one polymer base paint material of 70% solids comprised of polyurethanes diluted in at least one material selected from the group consisting of toluene, methyl ethyl ketone, IPA and xylene.
18. A method of forming an F-POSS polymer synthetic blend material having a distribution of apex substituents, comprising: a. providing a first feedstock comprising a first fluorinated triethoxysilane having a carbon chain length of Cix, where x is the number of carbons, and x is a range of 4-10; b. providing a second feedstock comprising a second fluorinated triethoxysilane having a carbon chain length of C2y, where y is the number of carbons, and y is a range of 4-10, wherein x is greater than y; and c. reacting the first feedstock with the second feedstock under conditions so as to form a distribution of molecules, each molecule comprising a matrix structure having eight apices, each apex having a substituent R, each substituent R having a carbon chain length Cn in which n is in a range of 4-10, such that a portion of the distribution of molecules has all substituents R having the same carbon chain length Cn and a portion of the distribution of molecules has at least one substituent Rl having a carbon chain length Cix and R2 having a carbon chain length C2y wherein CI is greater than C2.
19. An F-POSS compound of the formula
Figure imgf000039_0001
or a mixture thereof, wherein R1 and R2 are each independently long-chain fluorinated alkyl, and n is an integer from 0 to 8, provided that R1 and R2 are different.
20. The F-POSS compound of claim 19, wherein each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
21. The F-POSS compound of claim 19 or 20, wherein each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
22. The F-POSS compound of any one of claims 19 to 21 , wherein R1 is 4/2 fluorinated alkyl and R is 6/2 fluorinated alkyl.
23. An F-POSS composition comprising a mixture of compounds of the formula
Figure imgf000039_0002
wherein R 1 and R 2 are each independently long-chain fluorinated alkyl, and n is an integer
1 2
from 0 to 8, provided that R and R are different.
24. The F-POSS composition of claim 23, wherein each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
25. The F-POSS composition of claim 23 or 24, wherein each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
26. The F-POSS composition of any one of claims 23 to 25, wherein R1 is 4/2 fluorinated alkyl and R is 6/2 fluorinated alkyl.
27. The F-POSS composition of any one of claims 23 to 26, wherein the mixture of
1 2
compounds comprises a distribution of compounds having a ratio of R to R between 0:8 to 8:0.
28. The F-POSS composition of claim 27, wherein the distribution is a Gaussian distribution.
29. An F-POSS composition produced by a process comprising: contacting a first feedstock comprising a first fluorinated trialkoxysilane with a second feedstock comprising a second fluorinated trialkoxysilane, wherein the first fluorinated trialkoxysilane and the second fluorinated trialkoxysilane are different.
30. The F-POSS composition of claim 29, wherein the first fluorinated trialkoxysilane is of the formula R1Si(ORA)3, and the second fluorinated trialkoxysilane is of the formula
R 2 Si(OR B )3, wherein each of R 1 and R2 are independently a long-chain fluorinated alkyl, each RA and RB is independently Ci-C6 alkyl, provided that R1 and R2 are different.
31. The F-POSS composition of claim 30, wherein each long-chain fluorinated alkyl is independently from 5 to 12 carbon atoms in the longest continuous chain of carbon atoms.
32. The F-POSS composition of claim 30, wherein each long-chain fluorinated alkyl is independently selected from the group consisting of 4/2 fluorinated alkyl, 3/3 fluorinated alkyl, 6/2 fluorinated alkyl, 4/4 fluorinated alkyl, 8/2 fluorinated alkyl and 6/4 fluorinated alkyl.
33. The F-POSS composition of any one of claims 29 to 32, wherein R1 is 4/2 fluorinated alkyl and R is 6/2 fluorinated alkyl.
34. The F-POSS composition of any one of claims 29 to 33, wherein the composition
1 2
comprises a mixture of compounds in a distribution having a ratio of R to R between 0:8 to 8:0.
35. The F-POSS composition of claim 34, wherein the distribution is a Gaussian distribution.
PCT/US2015/054367 2014-10-07 2015-10-07 Synthetic blend f-poss compositions formed from multiple feedstock materials WO2016057599A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP15849377.5A EP3204450A4 (en) 2014-10-07 2015-10-07 Synthetic blend f-poss compositions formed from multiple feedstock materials
JP2017512899A JP2017538791A (en) 2014-10-07 2015-10-07 Synthetic blend F-POSS composition formed from multiple raw materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462060622P 2014-10-07 2014-10-07
US62/060,622 2014-10-07

Publications (1)

Publication Number Publication Date
WO2016057599A1 true WO2016057599A1 (en) 2016-04-14

Family

ID=55632337

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/054367 WO2016057599A1 (en) 2014-10-07 2015-10-07 Synthetic blend f-poss compositions formed from multiple feedstock materials

Country Status (4)

Country Link
US (3) US9409933B2 (en)
EP (1) EP3204450A4 (en)
JP (1) JP2017538791A (en)
WO (1) WO2016057599A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10233336B2 (en) 2015-11-16 2019-03-19 Nbd Nanotechnologies, Inc. Transparent self-healing omniphobic coatings
CN112142983A (en) * 2020-10-06 2020-12-29 青岛羚智涂料科技有限责任公司 Antifogging modifier for water-based paint and preparation method thereof
CN112210284A (en) * 2020-10-06 2021-01-12 青岛羚智涂料科技有限责任公司 Water-based antifogging coating and preparation method thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10442823B2 (en) 2014-10-07 2019-10-15 Nbd Nanotechnologies, Inc. Functionalized F-POSS monomer compositions and uses thereof
KR102035831B1 (en) 2016-03-17 2019-11-18 주식회사 엘지화학 Polyhedral oligomeric silsesquioxane and method for preparing the same
JP2020518107A (en) 2017-04-26 2020-06-18 オーティーアイ ルミオニクス インコーポレーテッドOti Lumionics Inc. Method for patterning a coating on a surface and device containing the patterned coating
JP2019052148A (en) * 2017-09-14 2019-04-04 エヌビーディー ナノテクノロジーズ, インコーポレイテッドNbd Nanotechnologies, Inc. Functionalized f-poss monomer compositions and uses thereof
WO2019082105A1 (en) 2017-10-26 2019-05-02 Sabic Global Technologies B.V. Cross-linked polymer/polyhedral oligomeric silsesquioxane (poss) composite material; methods of making; and uses thereof
CN111465665B (en) * 2017-12-13 2022-02-15 3M创新有限公司 Curable fluorinated silsesquioxane compositions
CN110591554B (en) * 2019-08-05 2021-06-01 广州中国科学院工业技术研究院 Protective coating with self-repairing characteristic
JP7395307B2 (en) * 2019-10-01 2023-12-11 キヤノン株式会社 Imprint method, imprint device, and article manufacturing method
CN111499869A (en) * 2020-04-27 2020-08-07 株洲绿智新材料科技有限公司 Fluorinated semi-cage silsesquioxane and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1100838C (en) * 1999-03-05 2003-02-05 旭丽股份有限公司 Organosilicon modified polyurethane paint
US6716919B2 (en) 2000-03-24 2004-04-06 Hybrid Plastics Nanostructured chemicals as alloying agents in polymers
US7193015B1 (en) 2000-03-24 2007-03-20 Mabry Joseph M Nanostructured chemicals as alloying agents in fluorinated polymers
US20080221262A1 (en) 2000-03-24 2008-09-11 Mabry Joseph M Fluorinated POSS as alloying agents in nonfluorinated polymers
US20100222503A1 (en) * 2008-10-30 2010-09-02 Laine Richard M Properties Tailoring In Silsesquioxanes
US20130072609A1 (en) 2011-09-21 2013-03-21 Government Of The United States As Represented By The Secretary Of The Air Force Sythesis of functional fluorinated polyhedral oligomeric silsesquioxane (f-poss)
US20140238263A1 (en) * 2011-06-01 2014-08-28 The University Of North Carolina At Chapel Hill Superhydrophobic coatings and methods for their preparation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9052653B2 (en) * 2008-08-05 2015-06-09 Xerox Corporation Fuser member coating having polysilsesquioxane outer layer
CN101875707B (en) * 2009-04-30 2012-09-26 比亚迪股份有限公司 Fluorin-containing POSS acrylate polymer, preparation method thereof and paint
US8219013B2 (en) * 2009-05-05 2012-07-10 Xerox Corporation Fuser member having composite outer layer
US9760048B2 (en) * 2013-04-25 2017-09-12 Xerox Corporation Surface coating and fuser member

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1100838C (en) * 1999-03-05 2003-02-05 旭丽股份有限公司 Organosilicon modified polyurethane paint
US6716919B2 (en) 2000-03-24 2004-04-06 Hybrid Plastics Nanostructured chemicals as alloying agents in polymers
US7193015B1 (en) 2000-03-24 2007-03-20 Mabry Joseph M Nanostructured chemicals as alloying agents in fluorinated polymers
US20080221262A1 (en) 2000-03-24 2008-09-11 Mabry Joseph M Fluorinated POSS as alloying agents in nonfluorinated polymers
US20100222503A1 (en) * 2008-10-30 2010-09-02 Laine Richard M Properties Tailoring In Silsesquioxanes
US20140238263A1 (en) * 2011-06-01 2014-08-28 The University Of North Carolina At Chapel Hill Superhydrophobic coatings and methods for their preparation
US20130072609A1 (en) 2011-09-21 2013-03-21 Government Of The United States As Represented By The Secretary Of The Air Force Sythesis of functional fluorinated polyhedral oligomeric silsesquioxane (f-poss)

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MABRY ET AL.: "Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS", ANGEW. CHEM. INT. ED., vol. 47, 2008, pages 4137 - 4140, XP055357479 *
MABRY: "Nanostructured Materials", IN-HOUSE REPORT, AIR FORCE RESEARCH LABORATORY, August 2012 (2012-08-01), pages 1 - 63, XP055428450 *
See also references of EP3204450A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10233336B2 (en) 2015-11-16 2019-03-19 Nbd Nanotechnologies, Inc. Transparent self-healing omniphobic coatings
US11066560B2 (en) 2015-11-16 2021-07-20 Nbd Nanotechnologies, Inc. Transparent self-healing omniphobic coatings
CN112142983A (en) * 2020-10-06 2020-12-29 青岛羚智涂料科技有限责任公司 Antifogging modifier for water-based paint and preparation method thereof
CN112210284A (en) * 2020-10-06 2021-01-12 青岛羚智涂料科技有限责任公司 Water-based antifogging coating and preparation method thereof
CN112142983B (en) * 2020-10-06 2021-10-15 杨笃云 Antifogging modifier for water-based paint and preparation method thereof

Also Published As

Publication number Publication date
US20190177344A1 (en) 2019-06-13
US10584137B2 (en) 2020-03-10
US10208070B2 (en) 2019-02-19
US20170183364A1 (en) 2017-06-29
EP3204450A1 (en) 2017-08-16
EP3204450A4 (en) 2018-06-20
US20160096853A1 (en) 2016-04-07
US9409933B2 (en) 2016-08-09
JP2017538791A (en) 2017-12-28

Similar Documents

Publication Publication Date Title
US10584137B2 (en) Synthetic blend F-POSS compositions formed from multiple feedstock materials
EP1444290B1 (en) Compositions for aqueous delivery of fluorinated silanes
EP2780426B1 (en) Fluorinated coatings with lubricious additive
TWI558678B (en) Oleophobic coatings
WO2013012699A2 (en) Polyurethane based coating compositions
JP5986874B2 (en) Coating composition
JP5992875B2 (en) Fluorine-based surface treatment agent and article treated with the surface treatment agent
US10683313B2 (en) Polyhedral oligomeric silsesquioxane and preparation method thereof
WO2017074709A1 (en) Solvent-based repellent coating compositions and coated substrates
US9745490B2 (en) PVC-based metallopolymer nanocomposites, and coating composition and coating film comprising same
EP1724332A1 (en) Fluorinated organosilicon compounds and fluorochemical surfactants
US11702433B2 (en) Functionalized F-POSS monomer compositions and uses thereof
US10174059B2 (en) Functionalized F-POSS monomer compositions and uses thereof
WO2017184511A1 (en) Two-component polyurethane topcoat
US20200317564A1 (en) Article having amphiphobic coating film and method for preparation thereof
WO2015137344A1 (en) Composite material of resin-fluorine-containing boric acid composite particles
JP6140348B2 (en) Fluorine-based surface treatment agent and article treated with the surface treatment agent
US9932424B2 (en) Compositions and methods for compatibilizing fluorinated materials in nonfluorinated solvent systems
CN104858120B (en) Use the organic film laminated body manufacture method of organic film formation solids
Chi et al. Preparation and properties of polyamido-amine dendrimer/polyurushiol composite coatings by stepwise electrophoresis deposition
WO2024048468A1 (en) Hydrophilic gliding agent, surface treatment method using hydrophilic gliding agent, and base material having hydrophilic gliding film formed thereon
JP2024032373A (en) Hydrophilic and water-sliding treatment agent, surface treatment method using the hydrophilic and water-sliding treatment agent, and base material on which a hydrophilic and water-sliding film is formed
Patel et al. Novel surface coating materials based on castor oil-epoxy resin reaction products
CN117043300A (en) Surface treatment agent and method for producing substrate having surface treatment layer
CN114450363A (en) Two-pack type coating composition and coated article

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15849377

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017512899

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2015849377

Country of ref document: EP