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WO2014152824A1 - Composition de polyhétérosiloxane et composition de silicone contenant un polyhétérosiloxane - Google Patents

Composition de polyhétérosiloxane et composition de silicone contenant un polyhétérosiloxane Download PDF

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Publication number
WO2014152824A1
WO2014152824A1 PCT/US2014/027892 US2014027892W WO2014152824A1 WO 2014152824 A1 WO2014152824 A1 WO 2014152824A1 US 2014027892 W US2014027892 W US 2014027892W WO 2014152824 A1 WO2014152824 A1 WO 2014152824A1
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Prior art keywords
composition
polyheterosiloxane
photosensitizer
silicone
metal
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PCT/US2014/027892
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English (en)
Inventor
Lizhi Liu
David Deshazer
Martin Grasmann
Nanguo Liu
Katherine M. SHAHINIAN
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Dow Silicones Corp
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Dow Corning Corp
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Priority claimed from PCT/US2013/046784 external-priority patent/WO2013192404A1/fr
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of WO2014152824A1 publication Critical patent/WO2014152824A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • This disclosure provides a sensitized polyheterosiloxane composition that includes at least one non-lanthanide metal and siloxy units having the formula (R ⁇ SiO ⁇ ), (R ⁇ SiO ⁇ ), (R ⁇ iO ⁇ ), and/or (S1O4/2).
  • Each R 1 is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms.
  • the mole fractions of the at least one non-lanthanide metal and the siloxy units relative to each other is of the formula: [at least one non-lanthanide metal] a [R 1 3 Si0 1 /2]m[R 1 2Si02/2]d[R 1 Si03/2]t[Si04/2]q, wherein a is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9, and wherein m, d, t, and q cannot all be zero and the sum of a+m+d+t+q ⁇ 1.
  • the composition also includes a photosensitizer present in an amount of less than 3 moles of photosensitizer per one mole of the at least one non- lanthanide metal.
  • the photosensitizer imparts a larger peak emission intensity to said composition at an excitation wavelength of from 200 to 1,000 nm as compared to a control polyheterosiloxane composition free of the photosensitizer.
  • the sensitized polyheterosiloxane composition is free of lanthanide metals.
  • This disclosure also provides a silicone composition including a (sensitized) polyheterosiloxane composition and a curable silicone.
  • the photosensitizer imparts a larger peak emission intensity to the silicone composition at an excitation wavelength of from 200 to 1,000 nm as compared to a control composition free of the photosensitizer.
  • the silicone composition is free of lanthanide metals.
  • This disclosure also provides a cured product of the silicone composition and an article that includes a substrate and a coating disposed on the substrate, wherein the coating includes the cured product of the silicone composition.
  • Figure 1 A is an excitation spectrum of Example 1;
  • Figure IB is an emission spectrum of Example 1;
  • Figure 2A is an excitation spectrum of Example 2
  • Figure 2B is an emission excitation spectrum of Example 2
  • Figure 3 is an excitation and emission spectrum of Example 3
  • Figure 4 is an excitation and emission spectrum of Example 4.
  • Figure 5 is an excitation and emission spectrum of Example 5
  • Figure 6 is an excitation and emission spectrum of Example 6
  • Figure 7 is an excitation and emission spectrum of Example 7.
  • Figure 8 is an excitation and emission spectrum of Example 8.
  • This disclosure provides a sensitized polyheterosiloxane composition that is free of lanthanide metals, i.e., free of one or more lanthanide metals.
  • This disclosure also describes a silicone composition that includes a (sensitized) polyheterosiloxane composition and a curable silicone (i.e., a curable silicone composition different from the silicone composition introduced immediately above).
  • a curable silicone i.e., a curable silicone composition different from the silicone composition introduced immediately above.
  • the terminology "sensitized polyheterosiloxane composition” and “polyheterosiloxane composition” may be used interchangeably.
  • the silicone composition as a whole and/or the (sensitized) polyheterosiloxane composition is free of lanthanide metals, i.e., free of one or more lanthanide metals.
  • the terminology "free of may describe that the silicone composition and/or the polyheterosiloxane composition includes less than 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, or 0.0001, weight percent of lanthanide metals per 100 parts by weight of the respective composition.
  • the silicone composition and/or the polyheterosiloxane composition may be entirely free of lanthanide metals.
  • One or more of the physical properties and/or components of the polyheterosiloxane composition, as described, may also be descriptive of the physical properties and/or components of the silicone composition.
  • the polyheterosiloxane composition includes at least one non-lanthanide metal which may be any known in the periodic table.
  • the polyheterosiloxane composition includes two or more non-lanthanide metals.
  • the at least one non-lanthanide metal may be (Ml) and/or (M2) described below.
  • the polyheterosiloxane composition includes (A) a first non- lanthanide metal (Ml), (B) a second non-lanthanide metal (M2), and (C) siloxy units having the formula (R ⁇ SiC ⁇ ), (R ⁇ SiO ⁇ ), (E ⁇ SiO ⁇ ), and/or (Si0 4/2 ).
  • the polyheterosiloxane composition may include one (A) first non-lanthanide metal (Ml), two first non-lanthanide metals (Ml), or a plurality of first non-lanthanide metals (Ml).
  • the first non-lanthanide metal (Ml) is not particularly limited.
  • (Ml) may be chosen from Ti, Zr, Al, and Zn, or Ti, Zr, and Al, or Ti, Al, W, Ge, Zr, Hf, Mn, Nb, Y, Ta, and V, or W, Ti, Zr, Al, Zn, Hf, Ta, Y, and Nb, or Ti, Zr, Al, Ge, Ta, Nb, and Sn, and/or any single metals or combinations thereof.
  • (Ml) is chosen from Sn, Cr, Ba, Sb, Cu, Ga, In, Mg, Mo, Te, W, Sr, and/or any single metals or combinations thereof.
  • (Ml) is chosen from Al, Zr, and combinations thereof.
  • (Ml) is Al. In another embodiment, (Ml) is Zr. In still another embodiment, (Ml) is a combination of Al and Zr. Any one or more of the aforementioned metals may be used singly or in combination with themselves or any one or more metals described below. Similarly, any one or more of any metals described below may be used single or in combination with themselves or any one or more of the aforementioned metals.
  • the oxidation state of (Ml) is typically independently from 1 to 5, 1 to 4, 1 to 2, 2 to 3, 2 to 4, or any range or combination of ranges or values therebetween. If more than one (A) first non- lanthanide metal (Ml) is utilized, then each (Ml) may independently have the same or different oxidation states.
  • the polyheterosiloxane composition may include one (B) second non-lanthanide metal (M2), two second non-lanthanide metals (M2), or a plurality of second non-lanthanide metals (M2).
  • the second non-lanthanide metal (M2) is not limited.
  • each of (Ml) and (M2) are independently non-lanthanide metals and are different from each other.
  • (M2) may be one or more of those non-lanthanide metals described above or may be any other non-lanthanide metal in the periodic table.
  • (Ml) and (M2) may be one of the following:
  • more than one non-lanthanide metal may be utilized.
  • a mixture of non-lanthanide metals may be utilized.
  • the polyheterosiloxane composition also includes (C) siloxy units having the formula (R ⁇ SiC a), (R ⁇ SiO ⁇ ), (R ⁇ iO ⁇ ), and/or (S1O 4 /2). These units may be alternatively described as organopolysiloxane segments and are known in the art as M, D, T, and Q units, respectively.
  • the polyheterosiloxane composition may include one or more M, D, T, and/or Q units, e.g.
  • Each R 1 is typically independently a hydrocarbon or halogenated hydrocarbon group including 1 to 30, 1 to 20, 1 to 15, 1 to 12, 1 to 10, 1 to 5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, carbon atoms, or any value or range of values therebetween. Any R 1 may be the same or different from any other R 1 .
  • Non-limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, octadecyl, cyclohexyl, aryl, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl, halogenated hydrocarbon, 3,3,3- trifluoropropyl, 3-chloropropyl, and dichlorophenyl, groups. At least one of R 1 may be phenyl.
  • the number of siloxy units may vary. The number and type of siloxy units may affect the molecular weight of the organopolysiloxane segment, and hence the molecular weight of the polyheterosiloxane composition.
  • the (C) siloxy units may include greater than 50 mole or weight percent of R ⁇ iO ⁇ siloxy units where R 1 is phenyl; R ⁇ SiO ⁇ siloxy units where one R 1 substituent is phenyl, and the other R 1 substituent is methyl; or R ⁇ SiO ⁇ and R ⁇ iO ⁇ siloxy units where one R 1 substituent in the R ⁇ SiO ⁇ siloxy unit is phenyl, and the other R 1 substituent is methyl, and where R 1 is phenyl in the R ⁇ iO ⁇ siloxy unit.
  • One or more siloxy units may have the formula [(C 6 H 5 )Si0 3 / 2 ]d, [(C 6 H5)2Si0 2/2 ] d [(C 6 H 5 )Si03/2]t, or [(CH 3 )(C 6 H 5 )Si0 2/2 ] d [(C 6 H 5 )Si0 3/2 ] t .
  • the polyheterosiloxane composition may include at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or at least 98 or 99,%, or any value or range of values therebetween, of the at least one non-lanthanide metal (e.g. (A) and (B)) and (C) based on a total weight of the polyheterosiloxane composition.
  • the polyheterosiloxane composition may include approximately 100% of the at least one non-lanthanide metal (e.g. (A) and (B)) and (C) based on a total weight of the polyheterosiloxane composition.
  • any range of values including those above, or any one or more values between those above, may also be utilized. Any remaining percent by weight of the polyheterosiloxane composition may include one or more solvents, one or more counterions, e.g. benzoates, naphtoates, and acetates, and/or one or more components used to form the polyheterosiloxane composition.
  • each of the at least one non-lanthanide metal and/or (A), (B), and (C) are typically described relative to mole fractions of each to a total number of moles, e.g. of (A), (B), and (C).
  • the mole fractions of the at least one non-lanthanide metal, and the siloxy units in the polyheterosiloxane composition relative to each other may be of the formula [At least one non-Lanthanide Metal] a [R 1 3Si0 1 /2]m[R 1 2Si02/2]d[R 1 Si03/2]t[Si0 4 /2]q.
  • (A), (B), and (C) in the polyheterosiloxane composition relative to each other is of the formula [(Ml)] a [(M2)] b [R 1 3Si0 1 /2] m [R 1 2Si02/2]d[R 1 Si0 3 /2]t[Si0 4 /2] q .
  • the subscript m denotes the mole fraction of the optional "M” unit (R ⁇ SiO ⁇ ).
  • the subscript d denotes the mole fraction of the optional "D" unit (R ⁇ SiCh ⁇ )-
  • the subscript t denotes the mole fraction of the optional "T” unit (R ⁇ iO ⁇ ).
  • the subscript q denotes the mole fraction of the optional "Q" unit (Si0 4 / 2 ).
  • a and/or b is each typically independently from 0.001 to 0.9, 0.010 to 0.9, 0.001 to 0.7, 0.1 to 0.7, 0.1 to 0.6, 0.2 to 0.5, 0.2 to 0.8, 0.3 to 0.7, 0.4 to 0.6, or about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, or any value or range of values therebetween.
  • a and/or b may be each independently from 0.001 to 0.9, 0.001 to 0.5, 0.01 to 0.3, or 0.05 to 0.25.
  • a may be from 0.1 to 0.9 and b may be from 0.001 to 0.5.
  • the total metal content of the polyheterosiloxane composition may be from 0.1 to 0.9, from 0.2 to 0.8, from 0.3 to 0.7, from 0.4 to 0.6, about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, mole fraction, or any value or range of values therebetween.
  • m is typically from zero to 0.9, 0.1 to 0.6, or 0.2 to 0.5 or any value or range of values therebetween
  • d is typically from zero to 0.9, 0.1 to 0.5, or 0.1 to 0.3 or any value or range of values therebetween.
  • t and q is typically independently from zero to 0.9, 0.010 to 0.9, 0.001 to 0.7,
  • the polyheterosiloxane composition may include residual amounts of groups that are not described by the aforementioned formula.
  • the polyheterosiloxane composition may include up to about 5 mole percent of other units, such as those that include Si-OH bonds.
  • the polyheterosiloxane composition may have a formula [(Ml)] a [(M2)] b [R 1 3Si0 1 /2] m [R 1 2Si0 2 /2]d wherein Ml may be a combination of metals or, Ml may be a single metal, e.g. Al, wherein a is 0.54, b is 0.00, d is 0.27, and m is 0.1, or, e.g. Zr, wherein a is 0.5, b is 0.0, m is zero, d is 0.35, t is 0.155, and q is zero.
  • a may be from 0.01 to 0.8
  • b may be from 0.00 to 0.5
  • c may be from zero to 0.8
  • d may be from zero to 0.8, with the provisos that c and d both cannot be zero and the sum of a+b+c+d ⁇ 1.
  • the polyheterosiloxane composition has a formula such as Alo.5 4 Do. 27 To.o9Mo. 1 Ligando.ooi;Alo. 3 Do.5 2 5To. 17 5Ligando.o 2 ;Alo. 6 D 0 . 3 To.
  • Ligando.oo5 1 Ligando.oo5; AI0.54D0.27T0.09M0.1 Ligando.ooi; Zro.5Do.35To.15Ligando.001 ; or Zro.54Do.34To.12Ligando.001, wherein the ligand may originate from a photosensitizer.
  • the number of moles of each component of the polyheterosiloxane composition may be determined using common analytical techniques.
  • the number of moles of the siloxy units may be determined by 29 Si liquid or solid state NMR, 48 Ti NMR, 27 Al NMR, FT-IR, TEM EDX, ICP, XRF, GCMS, GC functionality, ICP, etc.
  • the number of moles of each component may be calculated from the amounts of each used in the process to prepare the polyheterosiloxane composition, and accounting for any losses (such as removal of volatile species) that may occur.
  • the polyheterosiloxane composition may also include from 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, from 1 to 15, from 1 to 10, or from 1 to 5, or any value or range of values therebetween, percent by weight, alkoxy groups.
  • Residual alkoxide (-OR) groups may also be present in polyheterosiloxane structures and may be bonded to (Ml) and Si, as determined using Si and 1 1 3 J C NMR, e.g. in an organic solvent.
  • Residual counter ions from metal salts may also be present and may be bonded or chelated to (Ml) and (M2).
  • One or more atoms of the at least one non-lanthanide metal may be bonded to the same or different silicon atoms, e.g. through an oxygen bond.
  • at least one oxygen atom of the siloxy units is bonded to at least one of (Ml) and/or (M2) and/or one or more (C) siloxy units.
  • Two or more oxygen atoms of one or more siloxy units may be bonded to (Ml) or (M2) or to both (Ml) and (M2).
  • Atoms of (Ml) may be bonded to other atoms of (Ml) or (M2).
  • Atoms of (Ml) may be linked via oxygen atoms to atoms of (Ml) and/or (M2), e.g. M1-0-M1-0-M2 or M1-0-M2.
  • Atoms of (Ml) may also have a one or more substituents bonded thereto such as residual or un-reacted substituents used to form the polyheterosiloxane composition.
  • Atoms of (M2) may be bonded to other atoms of (M2), (Ml), and/or one or more (C) siloxy units. Atoms of (M2) may be linked via oxygen atoms to atoms of (M2) and/or (Ml), e.g. M2-0-M2-0-M1 or M2-0-M1. Atoms of (M2) may also have a one or more substituents bonded thereto such as residual or un-reacted substituents used to form the polyheterosiloxane composition.
  • the polyheterosiloxane composition may include various heterosiloxane structures including, but not limited to, structures having Si-O-Si, Si-O-Ml, Ml-O-Ml, and M1-0-M2 bonds as well as Si-0-M2 and M2-0-M2 bonds.
  • a concentration of metal to metal bonds e.g. Ml-O-Ml, M1-0-M2, M2-0-M2 is controlled so as to minimize formation of metal aggregates or particles of sufficient size to either render the polyheterosiloxane composition insoluble in organic solvents or are of insufficient size to be detected using TEM techniques.
  • the polyheterosiloxane composition may have "metal-rich” domains and "siloxane- rich” domains.
  • metal-rich domains describes structural segments wherein a plurality of bonds include (Ml) or (M2) (i.e., Ml-O-Ml, M1-0-M2, M2-0-M2, Ml-O-Si, or M2-0-Si).
  • siloxane-rich describes structural segments wherein a plurality of bonds are siloxane (Si-O-Si) bonds.
  • the "metal-rich" domains may be present such that the amount of metal to metal bonds (Ml-O-Ml, M1-0-M2, M2-0-M2) is minimized so as to minimize formation of metal aggregates or particles of sufficient size to minimize their solubility in hydrocarbons.
  • the polyheterosiloxane composition may also include -(Si-0-Ml-0-M2)- bonds.
  • Ti and/or Al can act as a bridge to Ml to bridge siloxy units with non-lanthanide- oxygen units. Use of 17 O NMR, 48 Ti NMR and/or 27 Al NMR may increase resolution or ability to quantify Si-0 and non-lanthanide-0 bonds.
  • the metal rich domains may not be of sufficient size to be observed using high resolution transmission electron micrographs (TEM).
  • TEM transmission electron micrographs
  • the (Ml) and (M2) metals may be sufficiently distributed in the polyheterosiloxane composition and have a domain size smaller than
  • the polyheterosiloxane composition is typically soluble in a hydrocarbon solvent, such as an aromatic hydrocarbon solvent, and may be soluble in other organic solvents as well.
  • soluble describes that the polyheterosiloxane composition dissolves in, for example toluene, to form a homogeneous solution having a concentration of at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or about 100, weight percent of the polyheterosiloxane composition in toluene at 23°C.
  • the polyheterosiloxane composition may also be soluble in other organic solvents, such as chloroform, carbon tetrachloride, THF, and butyl acetate.
  • the polyheterosiloxane composition typically has a weight average molecular weight (M w ) from 1,000 to 1,000,000, from 2,000 to 400,000, from 2,000 to 200,000, from 5,000 to 750,000, from 10,000 to 500,000, from 20,000 to 350,000, from 30,000 to 300,000, from 40,000 to 250,000, from 50,000 to 200,000, from 60,000 to 175,000, from 70,000 to 150,000, from 80,000 to 140,000, from 90,000 to 130,000, from 100,000 to 1250,000, g/mol, or any value or range of values therebetween.
  • the molecular weight may be determined using modified GPC techniques to minimize possible interactions between the sample and the column system.
  • the molecular weight may be determined by GPC analysis using triple detectors (light scattering, refractometer, and viscometer) with a column (PL 5u 100a 100 x 7.8mm) designed for rapid analysis or Flow Injection Polymer Analysis (FIPA).
  • triple detectors light scattering, refractometer, and viscometer
  • FIPA Flow Injection Polymer Analysis
  • the polyheterosiloxane composition is typically photoluminescent and may emit visible or ultraviolet light when exposed to, or excited by, visible or ultraviolet light.
  • the polyheterosiloxane composition typically exhibits a quantum yield of at least 0.05%, as determined using the formula described in greater detail below.
  • the polyheterosiloxane composition exhibits a quantum yield of at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, %, or even greater, of from 5 to 75, 10 to 70, 15 to 65, 20 to 60, 25 to 55, 30 to 50, 35 to 45, 40 to 60, 40 to 50, 45 to 55, or 50 to 60, %, or any value or range of values therebetween.
  • any of the aforementioned values may be a minimum or a maximum for a range of quantum yield for the polyheterosiloxane composition and all combinations of the aforementioned values are hereby expressly contemplated.
  • the polyheterosiloxane composition may alternatively exhibit a quantum yield of 0.5, 1, 5, or 10% or any value or range of values set forth above or between those values set forth above.
  • quantum yields may be from 35 to 55% measured, for example, using an integrating sphere attached to a Flurolog-3 fluorescence spectrometer.
  • quantum yields may be from 5.9% to 7.4%.
  • the quantum yield may be alternatively described as any value, or range of values, both whole and fractional, within or between any one or more values described above. In various embodiments, the aforementioned quantum yield may vary by +1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, %.
  • a limited size of the metal rich domains may lead to enhanced photoluminescence. For example, concentrations of non-lanthanide ions may exceed conventional concentration quenching thresholds without reduction in quantum yield. Photoluminescence may be assessed by measuring the absorption spectrum, the photoluminescent emission (PL) spectrum, or the photoluminescent excitation (PLE) spectrum of the polyheterosiloxane composition.
  • the absorption spectrum may be measured with standard spectrometers such as a Varian Carry 5000 spectrophotometer (Agilent Technologies, Palo Alto, CA, USA).
  • the PL excitation and emission spectra may be measured using a spectrofluorometer.
  • Any spectrofluorometer recognized in the art, e.g. the Fluorolog-2 or -3 spectrofluorometer (FL2 or FL3) (HORIBA Jobin-Yvon Inc. Edison, NJ, USA), or any one or more described below may be utilized to determine any one or more physical properties described herein.
  • Quantum Yield can be described as a percentage of overall light conversion (photons absorbed to photons emitted) of a material. While it is possible to determine the QY of a material by comparing the absorption, PL and PLE spectra of a test polyheterosiloxane composition to a reference polyheterosiloxane composition, the QY may be measured more directly using a spectrometer coupled integration sphere, where the absorption and PL spectra of a polyheterosiloxane composition are referenced against a blank reference sample.
  • Representative equipment is an Ocean Optics USB4000 spectrometer fiber- optically coupled to an approximately 4 cm integration sphere, illuminated by a light emitting diode (LED) and run by Ocean Optics' Spectra Suite software (Ocean Optics, Dunedin, FL, USA).
  • equipment such as Fluorolog-2 or -3 spectrofluorometers (FL2 or FL3) (HORIBA Jobin-Yvon Inc. Edison, NJ, USA) may be utilized with appropriate accessories.
  • a combination of a UV-Vis spectrum and a PL/PLE spectra may be utilized.
  • the absorption and emission of a sample are measured under the illumination of an LED with a center wavelength of 395 nm.
  • the test sample is typically placed in the approximately 4 cm integration sphere in a glass vial with an absorption cut-off less than 350 nm.
  • Incident light is typically measured by integrating the photon count in the range 350-450 nm, and emitted light in the range 480-850 nm.
  • a different LED light source and/or photoluminescent material may require changing the integration ranges.
  • the polyheterosiloxane composition may emit visible and infrared light having a wavelength in the range of 400 to 1700 nm when excited by light having a wavelength of 200 to
  • the polyheterosiloxane composition may emit visible light having a wavelength of 580 to 750 nm when excited by light having a wavelength of 250 to 550 nm.
  • the polyheterosiloxane composition may emit visible light having a wavelength of 610 to 620 nm when excited by ultraviolet light having a wavelength of 390 to 400 nm.
  • the quantum yield may be at least 1%, alternatively 2%, alternatively 5%, alternatively 10%, alternatively 20%, alternatively 30%, alternatively 40%, alternatively 50%, or alternatively 60%.
  • the polyheterosiloxane composition may alternatively emit visible light when excited by a UV light source.
  • the emitted light may have a wavelength ranging from 450 to 750 nm while the excitation light source may have a wavelength ranging from 250 to 520 nm.
  • the polyheterosiloxane composition may alternatively emit visible light having a wavelength of 450 to 650 nm when excited by UV light.
  • the polyheterosiloxane composition alternatively may emit infrared light having a wavelength of 1450 to 1650 nm when excited by a light source having a wavelength from 650 to 5,000 nm.
  • the polyheterosiloxane composition may emit near IR light having a wavelength of 1000 to 1100 nm when excited by a light source having a wavelength from 650 to 5,000 nm.
  • the polyheterosiloxane composition may alternatively emit light having a wavelength of 400 to 1700 nm when excited by a light source having a wavelength of 200 to 1000 nm.
  • the emitted light has a longer wavelength than the excitation light source. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • the human eye tends to be most sensitive at wavelengths of light from 450 to 650 nm. Typically, light having wavelengths above and below this range is of lesser value for lighting applications. In addition, when a full range of wavelengths is not present, lighting quality and color quality tends to be reduced. Red emission in the range of 600 nm to 650 nm provides for suitable color rendering with.
  • the 1931 CIE (International Commission on Illumination) color space is defined by tristimulus values, X, Y and Z. In this model, Y represents luminance, Z corresponds to the human eye' s blue response, and X is a mix of color responses and orthogonal to Y. They are calculated according to the formulas:
  • ⁇ '( ⁇ ), y X) and z '( lj are color matching functions with peaks at approximately 450 nm, 550 nm and 600 nm respectively, and ⁇ ( ⁇ ) is the spectra power distribution.
  • Steady state emission and excitation measurements are typically collected using a Horiba Jobin- Yvon Fluorolog 3 spectrofluorometer with three slit double grating excitation and emission monochromators and with dispersions of 2.1 nm/mm (1200 grooves/mm).
  • the spectra are obtained with a 450 W xenon continuous wave lamp and detected at an angle of 90 degrees to the excitation source for solutions in 1 cm quartz cuvettes and at 30 degrees for measurements of powders in the solid state or thin films via a photomultiplier tube detector.
  • Measured films are typically discs 3 mm thick with 5% wt resins, for example, 5% wt Si+Metal+Ligand resins, in varying silicone hosts.
  • Samples in solution are typically measured for concentrations between 1.5% and 5% to yield optical densities below 0.10. Measurement procedures and references follow from Mavrodineau, Schultz and Menis 'Accuracy in Spectrophotometry and Luminescence Measurements' , NBS Special Publications p. 378 (1973), and were updated as needed in compliance with the user manuals of cited instrumentation. In the measurement, the background thermal noise (or the dark offset) is corrected all the time. There is also a reference photodiode to collect the variations of intensities in the excitation source (Rc). An intensity standard reference material (2940- C from NIST) is used to monitor variations in the photomultiplier tube detector (PMT) signal (Rs).
  • PMT photomultiplier tube detector
  • Luminescent quantum yields are typically measured with a six (6) inch integrating sphere accessory attached via optical fibers to the spectrofluorometer. These data are typically collected in two steps, wherein a first step includes measuring the absorption of a blank reference material in the integrating sphere while avoiding saturation of the detector by using the appropriate neutral density filters for the selected bandpass. The bandpass for these measurements is typically set between 1.5 and 2 nm, and the range scanned includes both the excitation source and the emission of the material. The second step typically includes replacing the blank reference with the sample while the measurement is repeated. These datasets are then typically analyzed in the vendor provided software, where the difference in the emission and the excitation is used to produce the resulting quantum yield for the material.
  • Absorption spectra are typically determined by monitoring the strongest absorption peak of the polyheterosiloxane composition and collecting data via the optically dilute method.
  • Optical densities are typically less than 0.1 and are typically collected on a UV-Vis in 10 mm quartz cuvettes. Data is typically obtained for three different concentrations, e.g. 4 wt , 3.2 wt and 2.5 wt , with targeted absorptions, e.g. of 0.100, 0.081 and 0.060.
  • the concentrations may be from 1.5 to 8.0 wt , depending on the total metal content of the polyheterosiloxane composition.
  • QY [ ⁇ ⁇ ( ⁇ ⁇ )/ ⁇ ⁇ ( ⁇ ⁇ )][/( ⁇ ⁇ )//( ⁇ ⁇ )][/ ⁇ 2 // ⁇ ⁇ 2 ][ ⁇ ) ⁇ / ⁇ ) ⁇ ] QY, wherein QY is the quantum yield of the sample, QY r is the quantum yield of the reference, A is the absorbance at the excitation wavelength ⁇ , n is the refractive index, and D is the integrated emission intensity.
  • the subscripts r and x indicate a reference value and an experimental value, respectively.
  • quinine sulfate in 1.0 N sulfuric acid can be used as a reference with an excitation at 340 nm and will produce emission between 370 nm and 660 nm.
  • This solution has an established quantum yield of 0.546.
  • Other references include fluorescein (470 nm excitation, 480-700 nm emission, QY 0.91) and rhodamine (535 nm excitation, 550 - 750 nm emission, QY 1.00). These reference materials are all commonly used and referenced in the literature, e.g. in Eaton, D., International Union of Pure and Applied Chemistry Organic Chemistry Division Commission on Photochemistry; and/or the Journal of photochemistry and photobiology. B, Biology, 1988. 2(4): p. 523, each of which are expressly incorporated herein by reference relative to these particular materials.
  • FTIR spectra can be recorded between 4000 cm “1 and 400 cm “1 with a resolution of 4 cm “1 on a Nicolet 6700 FT-IR spectrometer.
  • the spectra can be collected by directly measuring powder samples via attenuated total reflection (ATR) using a ZnSe or diamond cell.
  • the polyheterosiloxane composition may include, includes less than 10, 9, 8, 7, 6, 5, 4,
  • the composition also includes a (D) photosensitizer.
  • the (D) photosensitizer may impart a larger peak emission intensity to the polyheterosiloxane composition or the silicone composition as a whole (when the silicone composition includes a polyheterosiloxane composition and a curable silicone) at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 to 470, 340 to 460, 350 to 450, 360 to 440, 370 to 430, 380 to 420, 390 to 410, or about 400, nm, as compared to a control (polyheterosiloxane) composition free of the photosensitizer, i.e., an identical composition but for the (D) photosensitizer.
  • a control (polyheterosiloxane) composition free of the photosensitizer i.e., an identical composition but for the (D) photosensitizer.
  • the photosensitizer may be present in the polyheterosiloxane composition in an amount of less than 3 moles of (D) photosensitizer per one mole of one or more non-lanthanide metals, e.g. (Ml) and/or (M2).
  • the (D) photosensitizer may present in an amount greater than zero but less than 3 moles of the (D) photosensitizer per one mole of one or more non- lanthanide metals, e.g. (Ml) and/or (M2).
  • the (D) photosensitizer is present in amounts of less than 2.5, less than 2, less than 1.5, less than 1, less than 0.75, less than 0.5, less than 0.25, less than 0.1, less than 0.05, less than 0.01, less than 0.005, less than 0.001, less than 0.0005, less than 0.0004, etc. moles of (D) photosensitizer per one mole of the non-lanthanide metal.
  • the (D) photosensitizer is present in amounts of from 0.0001 to 0.0002, 0.0001 to 0.0003, 0.0001 to 0.0004, 0.0001 to 0.0005, 0.0001 to 0.0006, 0.0001 to 0.0007, 0.0008 to 0.0009, 0.0001 to 0.001, 0.0004 to 0.004, 0.001 to 0.1, 0.001 to 0.009, 0.001 to 0.008, 0.001 to 0.007, 0.001 to 0.006, 0.001 to 0.005, 0.001 to 0.004 5 0.001 to 0.003, 0.001 to 0.002, 0.01 to 0.09, 0.01 to 0.08, 0.01 to 0.07, 0.01 to 0.06, 0.01 to 0.05, 0.01 to 0.04, 0.01 to 0.03, 0.01 to 0.02, 0.1 to 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.4, 0.1 to 0.3, or 0.1 to 0.2, moles of (D) photosensitizer
  • the (D) photosensitizer is not particularly limited.
  • the (D) photosensitizer is chosen from (i) a ⁇ -diketone, (ii) a ⁇ -diketonate, (iii) a salicylic acid, (iv) an aromatic carboxylic acid, (v) an aromatic carboxylate, (vi) a polyaminocarboxylic acid, (vii) a polyaminocarboxylate, (viii) a N-heterocyclic aromatic compound, (ix) a Schiff base, (x) a phenol, (xi) an aryloxide, and combinations thereof.
  • the (D) photosensitizer is (i) a ⁇ -diketone, or (ii) a ⁇ -diketonate, or (iii) a salicylic acid, or (iv) an aromatic carboxylic acid, or (v) an aromatic carboxylate, or (vi) a polyaminocarboxylic acid, or (vii) a polyaminocarboxylate, or (viii) a N-heterocyclic aromatic compound, or (ix) a Schiff base, or (x) a phenol, or (xi) an aryloxide, or a combination of one or more of the aforementioned compounds.
  • the photosensitizer is a ⁇ -diketone or a ⁇ -diketonate.
  • the (D) photosensitizer is an aromatic carboxylic acid or aromatic carboxylate.
  • the (D) photosensitizer may be a salicylic acid or a salicylate.
  • the photosensitizer may be any one of the aforementioned types of compounds and/or may be further defined as a mixture of two or more of any of the aforementioned types of compounds.
  • Non-limiting examples of suitable (D) photosensitizers include 1,3- diphenylpropandione; 2-thenoyltrifluoroacetone, 2-dithenoylpropandione, 1 -phenyl- 3- (2- fluoryl)propandione ; 1 - (4-biphenyl) - 3 - (2-fluoryl)propandione ; 1 - (2-naphtyl) - 3 - (2- fluoryl)propandione; l-(l-naphtyl)-3-(2-fluoryl)propandione; l-(2,3,4,5-tetrafluorophenyl)-3-(2- fluoryl)propandione; l l-(2-fluoryl)-4,4,4-trifluorobutane-l,3-dione; l-(2,3,4,5-tetrafluorophenyl)-3- (2-fluoryl)propandione;
  • Suitable photosensitizers may have one or more of the structures below:
  • Rl trifluoromethyl
  • R2 5-bromo-2-thiophene
  • R3 H
  • R alkyl or aryl
  • R F, CI, Br, I, ORl (Rl: alkyl, aryl), N02, aryl, alkyl, NRl, OH, COOH, COORl
  • X H, alkyl, aryl, COOH, COORl
  • R F, CI, Br, I, ORl (Rl: alkyl, aryl), N02, aryl, alkyl, NRl, OH, COOH, COORl
  • R F, CI, Br, I, OR1 (Rl: alkyl, aryl), N02, aryl, alkyl, NR1, OH, COOH, COOR1
  • This disclosure also provides a silicone composition including the sensitized polyheterosiloxane composition and a silicone fluid, e.g. a non-curable silicone fluid, as appreciated in the art.
  • a silicone composition including the sensitized polyheterosiloxane composition and a curable silicone.
  • This disclosure also provides an embodiment wherein the polyheterosiloxane composition is combined with a silicone fluid, e.g. a non-curable silicone fluid, as appreciated in the art, before, during, or after combination with the curable silicone.
  • the silicone fluid is typically PDMS but is not limited in this way.
  • the silicone fluid has a viscosity at 25 °C of from about 0.001 to about 50 Pa s, typically from about 0.02 to about 10 Pa- s, and more typically from about 0.05 to about 5 Pa- s.
  • the silicone fluid can be linear, branched, cyclic, or a mixture thereof. Mixtures of the aforementioned fluids may also be used. Many of the linear, branched, and cyclic silicone fluids have melting points below about 25° C. Such materials are also commonly described as silicone liquids, silicone fluids, or silicone oils. A detailed description of non-limiting silicone fluids can be found in many references, including "Chemistry and Technology of Silicones" by W. Knoll, Academic Press, 1968, which, in one embodiment, is incorporated herein by reference relative to the silicone fluids.
  • Non-limiting examples of linear silicone fluids suitable for use herein include trimethylsiloxy-terminated dimethylsiloxane fluids sold by Dow Corning Corporation under the trade name "Dow Corning ® 200 Fluids". These silicone fluids are manufactured to yield essentially linear oligomers and/or polymers typically having a viscosity of from 0.001 to about 50 Pa s at 25 °C. Such fluids are primarily linear but can include cyclic and/or branched structures. In one embodiment, the silicone fluid is a trimethylsiloxy-terminated polydimethylsiloxane having a viscosity of about 0.1 Pa- s at 25 °C.
  • Suitable cyclic silicone fluids include the cyclic polydimethylsiloxanes sold by Dow Corning Corporation under the trade names "Dow Corning ® 244, 245, 344, and 345 Fluids", depending on the relative proportions of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Mixtures of the straight-chain and cyclic dimethyl may also be utilized. Even additional non-limiting examples of suitable silicone fluids are Me 3 SiO[(OSiMe 3 ) 2 SiO]SiMe3 and Me 3 SiO[(OSiMe 3 )MeSiO]SiMe 3 .
  • the sensitized polyheterosiloxane composition includes the (A) first metal (Ml), the (B) second metal (M2), the (C) siloxy units having the formula (R SiOi/2), (R ⁇ SiC ⁇ ), (R ⁇ iO ⁇ ), and/or (S1O4/2), wherein each R 1 is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms, wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)] a [(M2)] b [R 1 3 SiOi/2] m [R 1 2Si0 2 /2]d[R 1 Si0 3 /2]t[Si04/2] q , wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is
  • the polyheterosiloxane composition is not particularly limited relative to an amount present in the silicone composition.
  • the polyheterosiloxane composition in present in the silicone composition in amounts from 50 to 1,000, from 100 to 950, from 150 to 900, from 200 to 850, from 250 to 800, from 300 to 750, from 350 to
  • the polyheterosiloxane composition in present in the silicone composition in amounts from 0.1 to 1, from 0.2 to 0.9, from 0.3 to 0.8, from 0.4 to 0.7, or from 0.5 to 0.6, parts by weight per 100 parts by weight of the silicone composition.
  • the polyheterosiloxane composition in present in the silicone composition in amounts from 1 to 10, 2 to 9, 3 to 8, 4 to 7, or 5 to 6, parts by weight per 100 parts by weight of the silicone composition.
  • the polyheterosiloxane composition in present in the silicone composition in amounts from 10 to 80, from 15 to 75, from 20 to 70, from 25 to 65, from 30 to 60, from 35 to 55, from 40 to 50, or from 45 to 50, parts by weight per 100 parts by weight of the silicone composition.
  • the silicone composition also includes a curable silicone.
  • the curable silicone is not particularly limited and may be further defined as a curable silicone fluid, gel, etc.
  • examples of curable silicones include, but are not limited to, hydrosilylation-curable silicones, condensation-curable silicones, radiation-curable silicones, peroxide-curable silicones, and acid or amine cured silicones, e.g. epoxy curable silicones.
  • thermoset silicone polymer can be further described as curing to form a thermoset silicone polymer or a thermoplastic silicone polymer.
  • thermoplastic polymer describes a silicone polymer that has the physical property of converting to a fluid (flowable) state when heated and of becoming rigid (non-flowable) when cooled.
  • thermoplastic polymers do not “cure” as that term is typically understood in the art, for purposes of this disclosure, the terminology “curable” or “cure” can describe the hardening of the thermoplastic polymer.
  • thermoset polymer may describe a cured (i.e., cross-linked) silicone polymer that does not convert to a fluid state on heating.
  • thermaloset polymer typically describes a silicone polymer having the property of becoming permanently rigid (non-flowable) when cured (i.e., cross -linked).
  • a hydrosilylation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule; an organosilicon compound in an amount sufficient to cure the organopolysiloxane, wherein the organosilicon compound has an average of at least two silicon-bonded hydrogen atoms or silicon-bonded alkenyl groups per molecule capable of reacting with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the organopolysiloxane; and a catalytic amount of a hydro silylation catalyst.
  • a condensation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule and, optionally, a cross-linking agent having silicon-bonded hydrolysable groups and/or a condensation catalyst.
  • the cross-linking agent has the formula R ⁇ qSiX_i_q, wherein is a Ci to Cg hydrocarbyl group or a Ci to Cg halogen- substituted hydrocarbyl group, X is a hydrolysable group, and q is 0 or 1.
  • a radiation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded radiation- sensitive groups per molecule and, optionally, a cationic or free-radical photoinitiator depending on the nature of the radiation-sensitive groups in the silicone organopolysiloxane.
  • a peroxide-curable silicone typically includes an organopolysiloxane having silicon-bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.
  • An epoxy-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded epoxy-functional organic groups.
  • a proton source such as an amine, SiH, acid generator, or a cationic photo-acid generator, are utilized.
  • the silicone composition including the polyheterosiloxane composition and the curable silicone can be cured by exposing the silicone composition to ambient temperature, elevated temperature, moisture, or radiation, depending on the type of curable silicone.
  • the silicone composition (which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing the silicone composition to a temperature of from room temperature (-23 + 2 °C) to 250 °C, alternatively from room temperature to 150 °C, alternatively from room temperature to 115 °C, at atmospheric pressure.
  • the silicone composition is generally heated for a length of time sufficient to cure (cross-link) the organopolysiloxane.
  • the film is typically heated at a temperature of from 100 to 150 °C for a time of from 0.1 to 3 h.
  • the conditions for curing the silicone composition depend on the nature of the silicon-bonded groups in the organopolysiloxane.
  • the silicone composition can be cured (i.e., cross-linked) by heating the silicone composition.
  • the silicone composition can typically be cured by heating it at a temperature of from 50 to 250 °C, for a period of from 1 to 50 h.
  • the condensation-curable silicone comprises a condensation catalyst
  • the silicone composition can typically be cured at a lower temperature, e.g., from room temperature (-23 ⁇ 2 °C) to 150 °C.
  • the silicone composition (which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing the silicone composition to moisture or oxygen at a temperature of from 100 to 450 °C for a period of from 0.1 to 20 h.
  • the condensation-curable silicone contains a condensation catalyst
  • the silicone composition can typically be cured at a lower temperature, e.g., from room temperature (-23 ⁇ 2 °C) to 400 °C.
  • the silicone composition (which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing the silicone composition to moisture at a temperature of from room temperature (-23 + 2 °C) to 250 °C, alternatively from 100 to 200 °C, for a period of from 1 to 100 h.
  • the silicone composition can typically be cured by exposing it to a relative humidity of 30% at a temperature of from about room temperature (-23 + 2 °C) to 150 °C, for a period of from 0.5 to 72 h. Cure can be accelerated by application of heat, exposure to high humidity, and/or addition of a condensation catalyst to the silicone composition.
  • the silicone composition is a radiation-curable silicone
  • the silicone composition (which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing the silicone composition to an electron beam.
  • the accelerating voltage is from about 0.1 to 100 keV
  • the vacuum is from about 10 to 10-3 Pa
  • the electron current is from about 0.0001 to 1 ampere
  • the power varies from about 0.1 watt to 1 kilowatt.
  • the dose is typically from about 100 microcoulomb/cm ⁇ to 100 coulomb/cm ⁇ , alternatively from about 1 to 10 coulombs/cm ⁇ .
  • the time of exposure is typically from about 10 seconds to 1 hour.
  • the silicone composition(which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing it to radiation having a wavelength of from 150 to 800 nm, alternatively from 200 to 400 nm, at a dosage sufficient to cure (cross-link) the organopolysiloxane.
  • the light source is typically a medium pressure mercury-arc lamp.
  • the dose of radiation is typically from 30 to 1,000 mJ/cm ⁇ , alternatively from 50 to 500 mJ/cm ⁇ .
  • the silicone composition can be externally heated during or after exposure to radiation to enhance the rate and/or extent of cure.
  • the curable silicone is a peroxide-curable silicone
  • the silicone composition is a peroxide-curable silicone
  • the polyheterosiloxane composition (which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing it to a temperature of from room temperature (-23 ⁇ 2 °C) to 180 °C, for a period of from 0.05 to 1 h.
  • the silicone composition is an epoxy-curable silicone
  • the polyheterosiloxane composition (which includes the polyheterosiloxane composition and the curable silicone) can be cured by exposing it to a temperature of from room temperature (-23 ⁇ 2 °C) to 180 °C, for a period of from 0.05 to 1 h.
  • the curable silicone is typically present in an amount of at least about 50 weight percent based on a total weight of the silicone composition. In various embodiments, the curable silicone is present in an amount of at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99, weight percent based on a total weight of the silicone composition.
  • the curable silicone is present in an amount of from 95 to 99.9, from 90 to 95, from 85 to 90, from 80 to 85, from 75 to 80, from 70 to 75, from 65 to 70, from 60 to 65, from 55 to 60, from 50 to 55, from 90 to 99.9, from 85 to 95, from 75 to 85, from 65 to 75, from 55 to 65, from 70 to 95, from 80 to 95, from 20 to 55, 25 to 50, 30 to 45, or 35 to 40, weight percent based on a total weight of the silicone composition. All amounts, and ranges of amounts, both whole and fractional, within the ranges set forth above are herein expressly contemplated but are not described for the sake of brevity.
  • the curable silicone may be utilized as a single component or as a series of components, e.g. as a one part, two part, or multi-part component system.
  • various compounds in the curable silicone may be segregated into "A” and "B" portions such that when the "A" and "B” portions are combined, the curable silicone can cure.
  • This disclosure also provides a method of forming the polyheterosiloxane composition.
  • the method includes the step of reacting (A a metal (M3) alkoxide, (B0 an optional hydrolyzable metal (M4) salt or metal (M4) alkoxide, (C a silicon-containing material having silicon-bonded hydroxy groups, and (F) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (A and optionally (B0, so long as at least one of ( ⁇ ') and (B0 is a non-lanthanide metal and the polyheterosiloxane composition, and the composition as a whole, are free of lanthanide metals.
  • This step forms a polyheterosiloxane composition (i.e., a polyheterosiloxane composition that is not yet "sensitized” because the photosensitizer is not yet added/present).
  • the method may also include one or more steps as described in WO2011/002826, which is expressly incorporated herein by reference.
  • ( ⁇ '), optionally ( ⁇ '), (C), and (F) may react together in any order to form the polyheterosiloxane composition.
  • ( ⁇ '), optionally ( ⁇ '), (C), and (F) may react individually or with more of each other batch wise (e.g. simultaneously) and/or sequentially.
  • One or more portions of ( ⁇ '), optionally ( ⁇ '), (C), and (F) may react individually or with more of portions of each other batch wise (e.g. simultaneously) and/or sequentially.
  • ( ⁇ ') may not be utilized and alkoxides may be utilized in the absence of a hydrolyzable metal. In another embodiment, ( ⁇ ') is utilized, e.g. with an alkoxide.
  • the (A metal (M3) alkoxide is not particularly limited and may be further defined as one or a mixture of alkoxides of one or more of the metals described above, so long as at least one of ( ⁇ ') and ( ⁇ ') is a non-lanthanide metal and the composition is free of lanthanide metals.
  • One metal (M3) alkoxide, two different alkoxides of the same metal (M3), two alkoxides of different metals (M3), or a plurality of alkoxides of one or more metals (M3), may be utilized.
  • the metal (M3) is not particularly limited but is typically is the same as (Ml).
  • the metal (M3) of the metal alkoxide may be independently selected and may be the same as (Ml) or (M2) or may be different, so long as at least one of ( ⁇ ') and ( ⁇ ') is a non-lanthanide metal and the composition is free of lanthanide metals.
  • the metal (M3) alkoxide may have the general formula (I) R ⁇ MSOn X p (OR 2 ) v i _k_ p _
  • subscript vl is the oxidation state of metal (M3), typically from 1 to 7, 1 to 5, or
  • subscript k is typically a value from 0 to 3, alternatively 0 to 2, and alternatively 0.
  • subscript n is typically a value from 0 to 2, alternatively 0 to 1, and alternatively 0, and subscript p is typically a value from 0 to 3, alternatively 0 to 2, and alternatively 0. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • R1 is typically a monovalent alkyl group having from 1 to 18, from 2 to 17, from 3 to 16, from 4 to 15, from 5 to 14, from 6 to 13, from 7 to 12, from 8 to 11, from 9 to 10, or from 1 to 8 carbon atoms or any value or range of values therebetween.
  • Non-limiting examples of the alkyl group of R1 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl groups. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • Each R ⁇ is typically an independently selected monovalent alkyl group having from 1 to 6, 2 to 5, or 3 to 4 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) -(R ⁇ C jR ⁇ , where j is a value from 1 to 4 and alternatively 1 to 2.
  • Each R3 is typically an independently selected divalent alkylene group having from 2 to 6, 3 to 5, or
  • Each R ⁇ is typically an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6, 2 to 5, or 3 to 4 carbon atoms.
  • Non-limiting examples of the alkyl groups of R ⁇ include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and hexyl groups.
  • Non-limiting examples of the aryl groups of R ⁇ include phenyl and benzyl.
  • Non-limiting examples of the divalent alkylene group include " CH2CH2- and -CH2CH(CH3)- .
  • Non-limiting examples of the alkyl groups having from 1 to 6 carbon atoms of R4 are as described above for R2.
  • Non-limiting examples of the polyether group of Formula (VI) include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, methoxyethoxyethyl, and ethoxyethoxyethyl groups.
  • R2 is typically an alkyl group having from 1 to 6 carbon atoms e.g. a methyl, ethyl, propyl, and butyl group, or a propyl and butyl group. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • X is typically chosen from carboxylate ligands, organosulfonate ligands, organophosphate ligands, ⁇ -diketonate ligands, and chloride ligands, alternatively carboxylate ligands and ⁇ -diketonate ligands.
  • the carboxylate ligands for X typically have a formula R ⁇ COO " where Rl5 is chosen from hydrogen, alkyl groups, alkenyl groups, and aryl groups.
  • alkyl groups for R!5 include alkyl groups having from 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms as described above for R1.
  • Non-limiting examples of alkenyl groups for Rl5 include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, 2-propenyl, allyl, hexenyl, and octenyl groups.
  • Non-limiting examples of aryl groups for Rl5 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and benzyl groups.
  • Rl5 is methyl, 2-propenyl, allyl, and phenyl, ⁇ -diketonate ligands for X can have the following structures:
  • R!6, R!8, and R ⁇ l are typically chosen from monovalent alkyl and aryl groups.
  • alkyl groups for R 16, Rl8, and R 21 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 4 carbon atoms such as methyl, ethyl, trifluoromethyl, and t-butyl groups.
  • Non-limiting examples of aryl groups for R 16 Rl8 and R 21 include aryl groups having from 6 to
  • R!9 is typically chosen from alkyl groups, alkenyl groups and aryl groups.
  • alkyl groups for R!9 include CI to CI 8 alkyl groups, alternatively CI to C8 alkyl groups such as methyl, ethyl, propyl, hexyl and octyl groups.
  • alkenyl groups for R!9 include alkenyl groups having from 2 to 18 carbon atoms, alternatively C2 to C8 carbon atoms such as allyl, hexenyl, and octenyl groups.
  • aryl groups for R!9 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups.
  • R 17 and R 2 0 are typically hydrogen or alkyl, alkenyl, and aryl groups.
  • alkyl groups for R!7 and R ⁇ O include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.
  • alkenyl groups for R!7 and R ⁇ O include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.
  • alkenyl groups for R!7 and R ⁇ O include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.
  • alkenyl groups for R!7 and R ⁇ O include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.
  • R!7 and R ⁇ O include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, allyl, hexenyl, and octenyl groups.
  • alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, allyl, hexenyl, and octenyl groups.
  • aryl groups for aryl groups for
  • R!7 and R ⁇ O include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups.
  • R!6, R 17, Rl8, R19 R20, and R 21 are each independently selected and can be the same or different from each other. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • Non-limiting examples of metal alkoxides described by Formula (I) include titanium tetrapropoxides, titanium butoxide, titanium tetrabutoxides, zirconium tetrapropoxides, and zirconium tetrabutoxides from DuPont, aluminum tripropoxides, aluminum tributoxides, aluminum phenoxide, antimony (III) ethoxide, barium isopropoxide, cadmium ethoxide, cadmium methoxide, cadmium methoxyethoxide, chromium (III) isopropoxide, copper (II) ethoxide, copper (II) methoxyethoxyethoxide, gallium ethoxide, gallium isopropoxide, diethyldiethoxygermane, ethyltriethoxygermane, methyltriethoxygermane, tetra-n-butoxygermane, hafn
  • A may be chosen from titanium tetraisopropoxide, titanium butoxide, titanium tetrabutoxide, zirconium tetrabutoxide, or aluminum sec-butoxide.
  • one or more of the aforementioned compounds, or their analogs as appreciated in the art may be substituted with one or more metals chosen from Ti, Zr, Al, and Zn, or Ti, Zr, and Al, or Ti, Al, W, Ge, Zr, Hf, Mn, Nb, Y, Ta, and V, or W, Ti, Zr, Al, Zn, Hf, Ta, Y, and Nb, or Ti, Zr, Al, Ge, Ta, Nb, and Sn, or Sn, Cr, Ba, Sb, Cu, Ga, In, Mg, Mo, Te, W, Sr, Al, Zr, and/or any single metals or combinations thereof.
  • the optional (B hydrolyzable metal (M4) salt or metal (M4) alkoxide is not particularly limited and may be further defined as one or a mixture of salts of one or more of the metals described above.
  • One hydrolyzable metal (M4) salt or metal (M4) alkoxide, two different salts of the same metal (M4) or metal (M4) alkoxide, two salts of different metals (M4) or metal (M4) alkoxides, or a plurality of salts of one or more metals (M4) or metal (M4) alkoxides, may be utilized.
  • Non-limiting examples of metal (M4) alkoxides may be any of those options for the metal (M3) alkoxide or may be different.
  • the hydrolyzable metal (M4) is the same as the (M2).
  • the hydrolyzable metal (M4) may be a non-lanthanide metal.
  • the hydrolyzable metal (M4) may be the same as (Ml) or (M2) or metal (M3) or may be different.
  • hydrolyzable metal (M4) may be independently selected and may any one of the aforementioned options for (Ml) and/or (M2) and/or metal (M3).
  • at least one of metal (M3) and hydrolyzable metal (M4) is typically a non- lanthanide metal.
  • the optional ( ⁇ ) hydrolyzable metal (M4) salt may be further described as (B' l) a non- hydrated metal salt having a general formula (IV) R ⁇ e M4(Z)( v 2- e )/w or a hydrated metal salt having a general formula (V) M4(Z) v 2/ w -xH20.
  • v2 is the oxidation state of hydrolyzable metal (M4) and w is the oxidation state of ligand Z where Z is typically independently chosen from carboxylates, ⁇ -diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate.
  • Each is typically an independently selected alkyl group having 1 to 18 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, or an aryl group having from 6 to 8 carbon atoms while e is typically a value from 0 to 3 and x is typically a value from 0 to 12, or from 0.5 to 12, and typically describes the average number of 3 ⁇ 4() molecules associated with each metal salt molecule.
  • the oxidation state of hydrolyzable metal (M4) may be as described above or may be different. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • subscript w is the oxidation state of ligand Z and typically can range from 1 to 3, alternatively from 1 to 2.
  • the Z group in Formulas (IV) and (V) describes various counter ligands that may be attached to hydrolyzable metal (M4).
  • each Z is independently chosen from carboxylate ligands, ⁇ -diketonate ligands, fluoride ligand, chloride ligand, bromide ligand, iodide ligand, organic sulfonate ligands, nitrate ligand, nitrite ligand, sulphate ligand, sulfite ligand, cyanide ligand, phosphate ligand, phosphite ligand, organic phosphite ligands, organic phosphate ligands, and oxalate ligand.
  • the carboxylate ligands and ⁇ -diketonate ligands for Z may be as described above for X. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • the carboxylate ligands may also be chosen from acrylate, methacrylate, butylenate, ethylhexanoate, undecanoate, undecylenate, dodecanoate, tridecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, cis-9-octadecylenate (C18), cis-13-docoylsenoate (C22).
  • the carboxylate ligand may be undecylenate or ethylhexanoate.
  • the organic sulfonate ligands for Z may have a formula R ⁇ SOy, where R ⁇ 2 S chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of alkyl groups, alkenyl groups and aryl groups are as described above for R15. Alternatively R ⁇ 2 S tolyl, phenyl, or methyl.
  • the organic phosphate ligands for Z typically have a formula (R23())2 PO2 " or R23( is chosen from monovalent alkyl groups, alkenyl groups and aryl groups.
  • R23 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups.
  • alkyl groups, alkenyl groups and aryl groups are as described above for Alternatively R ⁇ 3 may be phenyl, butyl, or octyl.
  • Organic phosphite ligands for Z may have a formula (R ⁇ O)2 PO ⁇ or R ⁇ O- PC ⁇ " , where R ⁇ 4 S chosen from monovalent alkyl groups, alkenyl groups and aryl groups.
  • R ⁇ 4 S chosen from monovalent alkyl groups, alkenyl groups and aryl groups.
  • alkyl groups, alkenyl groups and aryl groups are as described above for R!5.
  • R2 may be phenyl, butyl, or octyl.
  • Z in Formulas (IV) and (V) may be independently chosen from carboxylate ligands, ⁇ -diketonate ligands, nitrate ligands, sulphate ligands, and chloride ligands.
  • Z may include carboxylate ligands and ⁇ -diketonate ligands.
  • subscript e is typically a value from 0 to 3, alternatively from
  • R ⁇ may be an independently selected alkyl group having 1 to 18 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, or an aryl group having from 6 to 8 carbon atoms.
  • Non-limiting examples of R ⁇ are as described above for R ⁇ .
  • Formula (V) may be a value from 0.5 to 12, and alternatively from 1 to 9. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • Non-limiting examples of ( ⁇ ') include but are not limited to lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, scandium acetate, yttrium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, chromium acetate, molybdenum acetate, tungsten acetate, manganese acetate, technetium acetate, rhenium acetate, iron acetate, ruthenium acetate, osmium acetate, cobalt acetate, rhodium acetate, iridium acetate, nickel acetate, palladium acetate, platinum acetate, copper acetate, silver acetate, zinc acetate, cadmium acetate, mercury acetate, aluminum
  • the hydrolyzable metal (M4) salt or metal (M4) alkoxide may include one or more of the aforementioned compounds, or their analogs as appreciated in the art, substituted with one or more metals chosen from Ti, Zr, Al, and Zn, or Ti, Zr, and Al, or Ti, Al, W, Ge, Zr, Hf, Mn, Nb, Y, Ta, and V, or W, Ti, Zr, Al, Zn, Hf, Ta, Y, and Nb, or Ti, Zr, Al, Ge, Ta, Nb, and Sn, or Sn, Cr, Ba, Sb, Cu, Ga, In, Mg, Mo, Te, W, Sr, Al, Zr, and/or any single metals or combinations thereof.
  • ( ⁇ ) is chosen from ( ⁇ 1) a non-hydrated metal salt having a general formula (IV) R ⁇ e M4(Z)( v 2- e )/w an d (B ' 2) a hydrated metal salt having a general formula
  • (V) M4(Z) v 2/ w -xH20 wherein (M4) is a non-lanthanide metal, v2 is the oxidation state of M4, w is the oxidation state of Z, Z is independently chosen from alkoxides, carboxylates, ⁇ -diketonates, chlorides, organic sulfonates, nitrates, and oxalates, each is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, or aryl group having from 6 to 18 carbon atoms, e is a value from 0 to 3 and x is a value from 0 to 12.
  • (A and ( ⁇ ) are reacted with water to form a mixed metal oxide solution including metal (M3)-0-(M4) oxo-bonds.
  • This solution may then be reacted with (C to form the polyheterosiloxane composition, wherein the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups of (AO, and optionally (B0-
  • the percent may be further described as mole or weight percent as a theoretical calculated stoichiometric amount.
  • the silicon-containing material can be (C' l) a siloxane having silicon-bonded hydroxy groups, (C'2) a silane having silicon-bonded hydroxy groups, or combinations thereof.
  • the (C' l) siloxane can be a disiloxane, trisiloxane, or polysiloxane, or combinations thereof.
  • the (C'2) silane can be a monosilane, disilane, trisilane, or polysilane or combinations thereof.
  • the structure of the (C' l) siloxane or (C'2) silane can be linear, branched, cyclic, or resinous. Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms. In acyclic polysilanes and polysiloxanes, the silicon-bonded hydroxy groups can be located at terminal, pendant, or at both terminal and pendant positions.
  • Non-limiting examples of (C'l) siloxanes having silicon-bonded hydroxy groups include MQ resins, OH-functional polydialkylsiloxanes, polydimethylsiloxane, polyalkylphenylsiloxanes polyphenylmethyldisiloxanes, polyarylalkysiloxanes, polydiphenylsiloxanes, polydiarylsiloxanes, polytrifluorumethylsiloxanes, polydiphenylsiloxane dimethylsiloxane copolymers, polyarylsiloxanes, polytrifluoropropylmethylsiloxane, and combinations thereof.
  • Non-limiting examples of (C'2) silanes having silicon-bonded hydroxyl groups include phenylsilanetriol, diphenylsilanediol, phenylmethylsilanediol, dimethylsilanediol, trimethylsilanol, triphenylsilanol, phenyldimethoxysilanol, phenylmethoxysilanediol, methyldimethoxysilanol, methylmethoxysilanediol, phenyldiethoxysilanol, phenylethoxysilanediol, methyldiethoxysilanol, and methylethoxysilanediol, and combinations thereof.
  • (C) is further defined a hydrolysis product of at least one of: (C'i) a organosiloxane, (C'ii) a silane, and combinations thereof.
  • the hydrolysis product is further defined as the product of water and at least one of (C'i), (C'ii), and combinations thereof.
  • At least one of (C'i) and (C'ii) has a hydrolyzable group.
  • (C'i) may have a hydrolyzable group
  • (C'ii) may have a hydrolyzable group
  • both (C'i) and (C'ii) each have a hydrolyzable group.
  • One or both of (C'i) and (C'ii) can have more than one hydrolyzable group.
  • the (C) hydrolysis product i.e., the product formed from reaction with water, may include R 5 g (R 6 0)f(HO) j SiO(4-(f +g+j ))/2 and/or hydrolyzed silane R 5 h (HO) k SiZ'i, wherein, for example, R 5 is hydrogen or a hydrocarbyl group.
  • a hydrolyzed organosiloxane R 5 g (R 6 0)f(HO) j SiO(4_(f +g+j ))/2 or hydrolyzed silane R 5 h (HO) k SiZ'i can be used directly or diluted with aromatic solvents (toluene) and alcohol before added to a mixture of ( ⁇ ') and optionally ( ⁇ ').
  • One or both of (C'i) and/or (C'ii) may be treated with stoichiometric amounts of water containing catalytic amounts of a strong acid, e.g. HC1 or any "strong acid", or any highly diluted aqueous acid to initiate or promote hydrolysis.
  • a hydrolysis product may be accelerated by mixing hydrolysable (C'i) or (C'ii) with highly diluted aqueous acid or sonication of a mixture of both.
  • a silane (C'ii) e.g.
  • a base typically an amine such as triethylamine or pyridine
  • a hydrolyzed silane e.g. R 5 h Si(OH)i, can be isolated or used directly in solution when added to the reaction mixture of A' and B' .
  • diluted aqueous acid such as 0.1 N HC1
  • the mixture may be mixed or sonicated until two phases of aqueous acid and (C'i) and/or (C'ii) become one phase.
  • a hydrolysis reaction can be monitored based on its exothermic nature. If necessary, the hydrolyzed organosiloxane and silane can be diluted with toluene and alcohol, such as ethanol or butanol, to maintain a uniform one-phase solution before being added to the reaction mixture of A' and B'.
  • toluene and alcohol such as ethanol or butanol
  • the mixture may then be stirred for additional time and precipitated amine or pyridine hydrochloride may be filtered off and the filtrate reduced to 1/10 volume, e.g. using a rotary evaporator at 80°C and 15 mm Hg.
  • pentane or other suitable hydrocarbon may be added to precipitate any residual amine or pyridine hydrochloride followed by filtering and volume reduction. A resulting solid may then be collected via filtration and washed with cold pentane or hydrocarbon and re-crystallized from pentane/diethylether. The product may be isolated as white solid.
  • (C'i), which may be reacted to form the hydrolysis product may be an organosiloxane having an average siloxane unit formula (II) R ⁇ g(R ⁇ O)fSiO(4_(f + g) 2, and/or (C'ii) may be a silane having a general formula (III) R ⁇ SiZ' j .
  • each R 5 is hydrogen or a hydrocarbyl group
  • each R ⁇ is typically an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) -(R30)jR4, where j is a value from 1 to 4, each R ⁇ is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R4 is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, and the subscripts f and g are each independently any values from 0 to 3, wherein 0 ⁇ f+g ⁇ 3.
  • subscript f may be a value from 0.1 to 3 and alternatively from 1 to 3.
  • subscript g may be a value from 0.5 to 3 and alternatively from 1.5 to 2.5.
  • subscripts (f+g) may have a value from 0.6 to 3.9 and alternatively from 1.5 to 3.
  • f may be from 0.1 to 3 and g may be from 0.5 to 3.
  • Examples of (C'i) described by Formula (II) include oligomeric and polymeric organosiloxanes, such as MQ resins.
  • Z' may be a hydrolysable group such as acetoxy, oxime, silazane, CI or
  • OR6 and/or each R ⁇ may be an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group.
  • at least one R5 groups of (C'i) and/or (C'ii) silane is an R group, as described above.
  • h is typically a value from 0 to 3
  • i is typically a value from 1 to 4
  • the alkyl groups having 1 to 18 carbon atoms of R ⁇ in Formulas (II) and (III) are typically as described above for R1- Alternatively, the alkyl group may include 1 to 6 carbon atoms and be, for example, a methyl, ethyl, propyl, butyl, or hexyl group.
  • the alkenyl groups having from 2 to 18 carbon atoms of in Formulas (II) and (III) may be, for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, or octenyl groups.
  • the alkenyl group may include 2 to 8 carbon atoms and be, for example, a vinyl, allyl, or hexenyl group.
  • the aryl groups having 6 to 12 carbon atoms of R5 in formulas (II) and (III) may be phenyl, naphthyl, benzyl, tolyl, xylyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups.
  • the aryl group may include 6 to 8 carbon atoms and be, for example, a phenyl group. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • each Z' may be a chloro atom (CI) or 0R6, where is as described above.
  • Z' may be OR ⁇ .
  • subscript h may be a value from 0 to 3, from 1 to 3, or from 2 to 3.
  • subscript i is a value from 1 to 4, from 1 to 3, or from 1 to 2.
  • subscripts (h+i) may equal 4. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • Examples of the silanes (C'ii), which may be reacted to form the hydrolysis product, described by Formula (III) include methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, phenylmethyldichlorosilane, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, and combinations thereof.
  • an amount of (F) water is utilized (and/or reacted) with ( ⁇ ') and optionally ( ⁇ ') so that polyheterosiloxanes having at least two non-Si metal elements can be formed.
  • water can also be incorporated via hydrated metal salts (B'2), hydrated metal salts may be utilized such that no liquid water may be utilized and the water originates from the hydrated metal salts.
  • 0.5 mole of water may be used for hydrolysis and condensation of 1 mole of alkoxy and other hydrolyzable groups.
  • the amount of water utilized may be from 50 to 200, 70 to 150, from 80 to 120, 60 to 190, 70 to 180, 80 to 170, 90 to 160, 100 to 150, 110 to 140, or 120 to 130, , of the theoretical amount of water necessary for complete hydrolysis and condensation of alkoxy and other hydrolyzable groups, as first described above. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.
  • the water is added slowly to ( ⁇ ') and optionally ( ⁇ ') in an attempt to ensure that the metal alkoxide does not react quickly with the water so as to form a precipitate.
  • the water may be diluted with one or more solvents, such as those described above.
  • the water may also be added at one time or during one or more of the method steps.
  • Other hydrolyzable groups that may be present and need to be hydrolyzed and condensed are any found on the components used, including, but not limited to, chloro.
  • Each of the components ( ⁇ '), optionally ( ⁇ '), and/or (C) may be liquid or solid and it is typical that they are pre-mixed or dispersed. Stirring one or more of the components ( ⁇ '), optionally ( ⁇ '), and/or (C) in a solvent may provide a homogenous dispersion.
  • the terminology "dispersion” describes that the molecules of the various components ( ⁇ '), ( ⁇ '), and/or (C) are homogenously distributed.
  • a solvent may not be needed if one or more components ( ⁇ '), ( ⁇ '), and/or (C) can be dispersed in one or more of each other.
  • Such solvents may be as described and may be polar solvents, non-polar solvents, hydrocarbon solvents including aromatic and saturated hydrocarbons, alcohols, etc.
  • suitable solvents include hydrocarbonethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, methoxyethanol, methoxyethoxyethanol, butyl acetate, toluene, and xylene, alternatively isopropanol, 1-butanol, 2- butanol, and butyl acetate.
  • the dispersing or mixing may be completed by any conventional means such as stirring.
  • reaction of ( ⁇ ') and optionally ( ⁇ ') with (F) water proceeds at room temperature (e.g. 20-30°C) but if desired, elevated temperatures up to about 140°C may be used. Alternatively, the temperature can range from 20°C to 120°C. Typically, the reaction may proceed from 30 minutes to 24 hours and alternatively from 10 minutes to 4 hours.
  • room temperature e.g. 20-30°C
  • elevated temperatures up to about 140°C may be used.
  • the temperature can range from 20°C to 120°C.
  • the reaction may proceed from 30 minutes to 24 hours and alternatively from 10 minutes to 4 hours.
  • An optional method step includes removing the solvent to form the polyheterosiloxane composition.
  • the solvent can be removed by any conventional manner such as heating to elevated temperatures or using reduced pressure.
  • the polyheterosiloxane composition can then be redispersed in a solvent of choice such as toluene, THF, butyl acetate, chloroform, dioxane, 1- butanol, and pyridine. Since the Si-O-M may be susceptible to hydrolytic cleavage in the presence of water, to maximize shelf life it is typical to minimize the exposure of the polyheterosiloxane composition to moisture.
  • the method of forming the sensitized polyheterosiloxane composition may also include the step of (II) introducing a (D) photosensitizer to one or more of ( ⁇ '), ( ⁇ '), (C), (E) as described below, and/or (F), prior to the step of reacting and/or introducing (D) to the polyheterosiloxane composition, to form the sensitized polyheterosiloxane composition.
  • the polyheterosiloxane composition formed by reaction of ( ⁇ '), optionally ( ⁇ '), (C), (E) and/or (F), is not yet “sensitized.” Only after introduction of the (D) photosensitizer to the "polyheterosiloxane composition" is that polyheterosiloxane composition then described as sensitized, i.e., described as the "sensitized polyheterosiloxane composition.”
  • the (D) photosensitizer may be present in the sensitized polyheterosiloxane composition in an amount of less than 3 moles of (D) photosensitizer per one mole of the non- lanthanide metal.
  • the step of introducing is not particularly limited and may include introducing by any method such as pouring, spraying, etc.
  • the step of introducing may occur before, during, or after combination of one or more of ( ⁇ '), ( ⁇ '), (C), (E) and/or (F), and/or before, during, or after reaction of one or more of ( ⁇ '), ( ⁇ '), (C), (E) and/or (F).
  • the step of introducing may occur more than once.
  • amounts of the (D) photosensitizer may be introduced at various points in the method.
  • the (D) photosensitizer is added to the polyheterosiloxane composition after ( ⁇ '), optionally ( ⁇ '), (C), (E) and/or (F) react.
  • the (D) photosensitizer can be added to a vessel in conjunction with ( ⁇ ') and one or more solvents.
  • the (D) photosensitizer can be added to a vessel in conjunction with ( ⁇ ') and/or (C) and one or more solvents.
  • the (D) photosensitizer can be added to a vessel in conjunction with (E) and/or (F).
  • the (D) photosensitizer may impart a larger peak emission intensity to the sensitized polyheterosiloxane composition at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 to 470, 340 to 460, 350 to 450, 360 to 440, 370 to 430, 380 to 420, 390 to 410, or about 400, nm, as compared to a control polyheterosiloxane composition free of the (D) photosensitizer.
  • the method may also include one or more steps as described in PCT application No. PCT/US 10/40510, which is expressly incorporated herein by reference.
  • the method may alternatively include the step of reacting ( ⁇ '), ( ⁇ '), (C), and (E) a compatibilizing organosiloxane having at least one [R 3 81( ⁇ /2 ] unit and having a weight average molecular weight (M w ) of less than 10,000 g/mol.
  • this organosiloxane has at least one
  • the compatibilizing organosiloxane may have more than one [R sSiOm] unit.
  • the compatibilizing organosiloxane also has a weight average molecular weight (M w ) of less than 10,000 g/mol.
  • M w is less than 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000, or 500, g/mol.
  • the M w may be any value or range of values described immediately above or between those values described immediately above.
  • the (E) compatibilizing organosiloxane has an average formula chosen from: DI) (RO)(C6H5)2SiCH 2 CH 2 [(CH3)2SiO] n OSi(CH3)2(CH 2 )3CH 3 ;
  • n is from 3 to 100, 3 to 50, or 3 to 15.
  • the (E) compatibilizing or anosiloxane may have the average formula:
  • the (E) compatibilizing organosiloxane may have the average formula: wherein n is from 3 to 100, alternatively from 20 to 30.
  • the (E) compatibilizing organosiloxane has the formula: (Me 3 SiO) 2 MeSiCH 2 CH 2 Si(CH 3 ) 2 OSi(C 6 H5) 2 (OMe). Even further, the (E) compatibilizing
  • organosiloxane may have the formula (R 3 SiO) n (R )(3_ n) Si-R -Si(R ) 2 OSi(R ) 2 X, wherein n is 1 or 2.
  • Each R may be independently a monovalent d to C 20 hydrocarbyl.
  • the hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group, including halogen substituted hydrocarbyls.
  • Each R may independently be a Q to C 2 o alkyl group, a to C 6 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl.
  • R may be an aryl group, such as phenyl, naphthyl, or an anthryl group, or any combination thereof. Alternatively, each R may independently be phenyl, methyl, or a combination of both.
  • Each R 9 may independently be a divalent hydrocarbon group including 2 to 12 carbon atoms or 2 to 6 carbon atoms and may be described as ethylene, propylene, or isobutylene.
  • Each R 10 may independently be a monovalent Ci to C 30 hydrocarbyl including at least one aryl group, an aryl group, such as phenyl, naphthyl, or an anthryl group, any combination of the aforementioned alkyl or aryl groups, or phenyl (C 6 Hs).
  • the organosiloxane has the following formula: (Me 3 SiO) 2 (Me)SiCH 2 CH 2 Si (CH 3 ) 2 OSi(C6H5) 2 (OMe), wherein Me is a methyl group.
  • the organosiloxane has the formula (R 8 3 SiO) n (R 8 )(3-n)Si-G-Si(R 8 )2OSi(R 10 ) 2 X, wherein n is 1 or 2, R 8 is independently a monovalent Ci to C 2 o hydrocarbyl, G is a siloxane or polysiloxane bridging group comprising at
  • R 12 12 12 12 12 least one siloxy unit selected from a (R 2 Si0 2/2 ), (R S1O 3/2 ), or (Si0 4/2 ) siloxy units, wherein R may be any organic group, R 10 is independently a monovalent Ci to C 30 hydrocarbyl including at least one aryl group, X is a hydrolyzable group chosen from -OR 9 , CI, -OC(0)R 9 , -N(R 9 ) 2 , or -ON CR 9 2 and R 11 is hydrogen or a Ci to C 6 alkyl group.
  • G may also be a combination of hydrocarbyl bridging groups, such as the divalent C 2 to C 12 hydrocarbyl groups described above, and a siloxane or polysiloxane.
  • G is a polydimethylsiloxane of the formula -0(Me 2 Si0 2/2 ) q - where the subscript q is from 1 to 20, alternatively from 1 to 10, or alternatively from 1 to 5.
  • polysiloxane bridging group includes a (R S1O 3/2 ), or (Si0 4 / 2 ) siloxy unit(s), the group may further include additional M siloxy units to provide endcapping groups.
  • one or more T or Q units may be silanol terminated.
  • This disclosure also provides a method of forming a silicone composition.
  • the method may include forming the polyheterosiloxane composition as described above and the step of combining the polyheterosiloxane composition and the curable silicone to form a silicone composition.
  • the polyheterosiloxane can be added to the curable silicone or vice versa.
  • the polyheterosiloxane is present in a solvent and this combination is added to the curable silicone, or vice versa.
  • the polyheterosiloxane composition (and optionally the solvent) may be added to an "A" portion, a "B" portion, or both "A” and “B” portions, of the curable silicone, or vice versa.
  • the polyheterosiloxane composition can also be added to the curable silicone after "A" and "B" portions are already themselves combined.
  • the polyheterosiloxane composition can be added to the curable silicone, or vice versa, even if the curable silicone does not have "A” and "B” portions and is, instead, a single portion.
  • the cured silicone composition is the cured product of the aforementioned silicone composition including the polyheterosiloxane composition and the curable silicone wherein the curable silicone is cured by one or more of the aforementioned curing mechanisms.
  • the cured silicone composition is not particularly limited and may be partially cured or completely cured.
  • the cured silicone composition may be in any three dimensional form including a film, sheet, as a gel, as a molded form, as a cast form, etc.
  • the level of clarity of the cured silicone composition may be predetermined by selecting and customizing the polyheterosiloxane composition and the curable silicone, as well as the methodology and conditions used to prepare the cured silicone composition.
  • the article includes a substrate and a coating disposed on the substrate.
  • the substrate is not particularly limited and may be a solid, liquid, or gel.
  • the substrate in whole or in part, includes or is paper, plastic, a polymer, metal, wood, glass, or combinations thereof.
  • the article is a molded article, e.g. with an overall shape or cross- section profile defined by a negative of the shape of a mold.
  • a mold having the shape of a hemi-spherical bowl may be utilized to produce an article having a shape of a spherical dome.
  • fine features or a pattern may be imparted onto the article, e.g. by utilizing a negative pattern in the mold such that vias would become pads, and vice versa.
  • Molding techniques may include, but are not limited to, injection molding, overmolding, compression molding, casting, and imprint lithography. Feature size in any dimension may be greater than 5 nm, greater than 100 nm, greater than 1 ⁇ , or greater than 10 um.
  • the coating may be disposed on and in direct contact with the substrate or disposed on and separated in space with the substrate.
  • the coating may be disposed on one or more portions of the substrate or on the entire substrate.
  • the coating includes the cured silicone composition, e.g. the cured polyheterosiloxane composition including the curable silicone described above.
  • the coating has an average thickness of from 1 to 10, 2 to 9, 3 to 8, 4 to 7, or 5 to 6, ⁇ or cm. In other embodiments, the coating has an average thickness of from 10 to 100, 15 to 95,
  • the coating has an average thickness of from 100 to 1000, 150 to 950, 200 to 900, 250 to 850, 300 to 800, 350 to 750, 400 to 700, 450 to 650, 500 to 600, or about 650, ⁇ .
  • the coating has an average thickness of from 1000 to 10000, 1500 to 9500, 2000 to 9000, 2500 to 8500, 3000 to 8000, 3500 to 7500, 4000 to 7000, 4500 to 6500, 5000 to 6000, or about 6500, ⁇ .
  • the coating has an average thickness of from 10000 to 100000, 15000 to 95000, 20000 to 90000, 25000 to 85000, 30000 to 80000, 35000 to 75000, 40000 to 70000, 45000 to 65000, 50000 to 60000, or about 65000, ⁇ .
  • the coating is not limited to this thickness.
  • the coating may be disposed over a large area, on the substrate which may be rigid or flexible as recognized by those skilled in the art.
  • the coating may also be described as a film.
  • Non- limiting examples of coatings include bar coatings, Meyer bar coatings, gravure coatings, doctor blade coatings, slot-die coatings, spray coatings, spin coating castings, etc.
  • the coating may be disposed on one or more portions of the substrate, or across an entirety of the substrate.
  • the area coated may be larger than 1 mm in width or length, greater than 1 cm in width or length, greater than 20 cm in width or length, greater than 50 cm in width or length, or greater than 1 m in width or length.
  • the coating may be disposed in such a way as to form a pattern. Methods used to form the coating include, but are not limited to, casting, ink jet printing, screen printing, stencil printing.
  • Photoluminescence of the examples is be measured using a Fluorolog-2 or
  • Fluorolog-3 spectrofluorometer manufactured by Jobin Yvon SPEX, and an Ocean Optics USB4000 spectrometer fiber coupled to an integrating sphere and using Ocean Optics' Spectra Suite software. The specific parameters are as described above.
  • Example 1 Synthesis and Preparation of Silicone Cured Polyheterosiloxane Composition AlxrR 1 SiOv larR 1 SiOml L + 6 J l-dihydroxy-5 J2-naphthacenedione
  • a cured silicone sample is prepared by mixing 0.75 g of the Polyheterosiloxane Composition + 6,l l-dihydroxy-5,12-naphthacenedione with 14.25 g of OE6630 Dow Corning ® in a planetary mixer and degassed under vacuum. The resulting mixture is cured and molded into films in a hot press (5000 psi) for 1 h at 120 °C.
  • Pre-hydrolyzed R ⁇ iO ⁇ siloxane moieties are then formed by mixing 5.87 g of Dow Corning Z-6665 silane and 23.65 g of Dow Corning Toray RMS 757 with 0.1N HC1 (1.26 g), diluted with 70 ml of a 2: 1 ratio of toluene and sec-butanol and added to the stirred reaction mixture. The reaction is heated to 75 °C for one hour, after which the residual amount of water (0.98 g) is added dissolved in 20 ml of a 3: 1 ratio ethanol and toluene.
  • reaction solution and the solution are stirred for further 2 hours at 75 °C before being cooled to ambient and then filtered through 0.45 ⁇ PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at 75°C and 15 mmHg resulting in white solids.
  • a cured silicone sample is prepared by mixing 0.75 g of the Polyheterosiloxane Composition + l-(5-chloro-2-hydroxyphenyl)-3-phenyl-l,3-propandione with 14.25 g of OE6630 Dow Corning ® in a planetary mixer and degassed under vacuum. The resulting mixture is cured and molded into films in a hot press (5000 psi) for 1 h at 120 °C.
  • Photoluminescence of the examples may be measured using a Fluorolog-2 spectrofluorometer, manufactured by Jobin Yvon SPEX, and an Ocean Optics USB4000 spectrometer fiber coupled to an integrating sphere and using Ocean Optics' Spectra Suite software. The specific parameters are as described above.
  • each of the following Examples 1-2 is evaluated to determine photoluminescence. The results of these evaluations are set forth as Figures 1-4, respectively. Each of the Examples 1-2 is also evaluated to determine color. The results of the color determination are set forth immediately below.
  • photoluminescence of the examples may be measured using a Fluorolog-2 spectrofluorometer, manufactured by Jobin Yvon SPEX, and an Ocean Optics USB4000 spectrometer fiber coupled to an integrating sphere and using Ocean Optics' Spectra Suite software.
  • the specific parameters are as described above.
  • each of the following Examples 3-8 is evaluated to determine photoluminescence. The results of these evaluations are set forth as Figures 3-8, respectively. Each of the Examples 3-8 is also evaluated to determine color. The results of the color determination are set forth immediately below.
  • One or more of the values described above may vary by ⁇ 5%, ⁇ 10%, ⁇ 15%, ⁇
  • this disclosure expressly contemplates and herein affirmatively includes one or more components, articles, method steps, analytical determinations, compounds, and/or physical properties described in one or more of PCT Patent Application Numbers PCT/US2013/046813 and PCT/US 2013/046784; one or more of U.S.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne une composition sensibilisée de polyhétérosiloxane contenant au moins un métal non lanthanide, des unités siloxy et un photosensibilisant. Chaque R1 est indépendamment un groupe hydrocarboné ou un groupe hydrocarboné halogéné comprenant de 1 à 30 atomes de carbone. Les fractions molaires dudit métal non lanthanide et desdites unités siloxy les unes par rapport aux autres sont de formule : [au moins un métal non lanthanide]a[R1 3SiO1/2]m[R1 2Si02/2]d[R1Si03/2]t[Si04/2]q, a valant de 0,001 à 0,9, m valant de zéro à 0,9, d valant de zéro à 0,9, t valant de zéro à 0,9, et q valant de zéro à 0,9, m, d, t, et q ne pouvant pas valoir tous zéro et la somme a+m+d+t+q ≈ 1. Le photosensibilisant est présent en une quantité de moins de 3 moles de photosensibilisant pour une mole dudit métal non lanthanide. La composition sensibilisée de polyhétérosiloxane est par ailleurs exempte de lanthanides. Une composition de silicone comprend une silicone vulcanisée et la composition sensibilisée de polyhétérosiloxane. La composition de silicone est par ailleurs exempte de lanthanides.
PCT/US2014/027892 2013-03-14 2014-03-14 Composition de polyhétérosiloxane et composition de silicone contenant un polyhétérosiloxane Ceased WO2014152824A1 (fr)

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US201361851990P 2013-03-14 2013-03-14
US201361782628P 2013-03-14 2013-03-14
US201361783797P 2013-03-14 2013-03-14
US201361782230P 2013-03-14 2013-03-14
US201361784581P 2013-03-14 2013-03-14
US61/782,628 2013-03-14
US61/851,990 2013-03-14
US61/782,230 2013-03-14
US61/783797 2013-03-14
US61/784,581 2013-03-14
PCT/US2013/046784 WO2013192404A1 (fr) 2012-06-20 2013-06-20 Composition de polyhétérosiloxane
USPCT/US2013/046813 2013-06-20
USPCT/US2013/046784 2013-06-20
PCT/US2013/046813 WO2013192419A1 (fr) 2012-06-20 2013-06-20 Composition de polyhétérosiloxane

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