WO2013192419A1

WO2013192419A1 - Polyheterosiloxane composition

Info

Publication number: WO2013192419A1
Application number: PCT/US2013/046813
Authority: WO
Inventors: David Deshazer; Martin Grasmann; Lizhi Liu; Nanguo Liu; Elizabeth Mcquiston; Shawn MEALEY; Randall Schmidt; Kwan SKINNER
Original assignee: Dow Corning Corporation
Priority date: 2012-06-20
Filing date: 2013-06-20
Publication date: 2013-12-27
Also published as: WO2013192404A1

Abstract

This disclosure provides a polyheterosiloxane composition including (A) a first metal (Ml), (B) a second metal (M2), and (C) siloxy units having the formula (R2 3SiO1/2), (R1 2SiO2/2), (R1Si03/2), and/or (Si04/2), wherein each R1 is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms, and wherein each R2 is independently a hydrocarbyl group having from 1 to 20 carbon atoms or an organosiloxane having at least one disiloxy unit. The mole fractions of (A), (B), and (C) relative to each other are of the formula [(M1)]a[(M2)]b[R2 3Si01/2]m[R1 2Si02/2]d[R1Si03/2]t[Si04/2]q, wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from 0.001 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. In this formula, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ≈ 1.

Description

POLYHETEROSILOXANE COMPOSITION

[0001] Incorporation of various metals into polysiloxanes to form polyheterosiloxanes is of great interest for a wide range of applications due to the ability of the metals to increase refractive index, impact resistance, scratch resistance, fire retardancy, anti-corrosion, and anti-stain properties. However, when polyheterosiloxanes are combined with other silicones, compatibility issues may arise. Accordingly, there remains an opportunity to develop improved materials.

SUMMARY OF THE DISCLOSURE

[0002] This disclosure provides a polyheterosiloxane composition including

(A) a first metal (Ml), (B) a second metal (M2), and (C) siloxy units having the formula (R² ₃SiOi/₂), (R^SiOia), (R¹Si0_{3 2}), and/or (Si0_{4 2}), wherein each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms, and wherein each R² is independently a hydrocarbyl group having from 1 to 20 carbon atoms or an organosiloxane having at least one disiloxy unit. The mole fractions of (A), (B), and (C) relative to each other are of the formula [(Ml)]_a[(M2)]_B[R² ₃Si0_1/2]_M[R¹ ₂Si0_2/2]_D[R¹Si0_3/2]_t[Si0_4/2]_q, wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from 0.001 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. In this formula, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1.

[0003] This disclosure also provides a method of forming the polyheterosiloxane composition. The method includes the step of reacting (Α') a metal (M3) alkoxide, (Β') an optional hydrolyzable metal (M4) salt, (C) a silicon- containing material having silicon-bonded hydroxy groups, (D) a compatibilizing organosiloxane having at least one [R² ₃SiOi_/2] unit and having a weight average molecular weight (M_w) of less than 10,000 g/mol, and (E) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α^') and optionally (Β').

DETAILED DESCRIPTION OF THE DISCLOSURE

[0004] This disclosure describes a polyheterosiloxane composition The polyheterosiloxane composition includes (A) a first metal (Ml), (B) a second metal (M2), and (C) siloxy units having the formula (R² ₃Si0_1/2), (R^SIOM), (R¹Si0_3/2), and/or (Si0_4/2). [0005] The polyheterosiloxane composition may include one (A) first metal

(Ml), two first metals (Ml), or a plurality of first metals (Ml). The first metal (Ml) is not particularly limited and may be a lanthanide metal or a non-lanthanide metal. (Ml) may be chosen from Ti, Zr, Al, and Zn, or Ti, Zr, and Al, or Ti, Al, Ge, Zr, Hf, Mn, Nb, Y, Ta, and V, or Ti, Zr, Al, Zn, Hf, Ta, Y, and Nb, or Ti, Zr, Al, Ge, Ta, Nb, and Sn, or La, Pr, Sm, Gd, Tb, Dy, Ho, Tm, and Lu, or Gd, Tb, Dy, Ho, Tm, and Lu, or Eu, Yb, Er, Nd, Dy, Sm, and Tb, and/or any single metals or combinations thereof. In various additional embodiments, (Ml) is chosen from Sn, Cr, Ba, Sb, Cu, Ga, In, Mg, Mo, Te, W, Sr, and/or any single metals or combinations thereof. 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 metal (Ml) is utilized, then each (Ml) may independently have the same or different oxidation states.

[0006] The polyheterosiloxane composition may include one (B) second metal

(M2), two second metals (M2), or a plurality of second metals (M2). The second metal (M2) is not limited. In one embodiment, at least one of (Ml) and (M2) is or includes a lanthanide metal. (M2) may be one or more of those metals described above or may be any other metal in the periodic table. (M2) may be a lanthanide metal or a non-lanthanide metal. For example, (Ml) and (M2) may be one of the following:

Each of (Ml) and/or (M2) may independently include one or more lanthanide and/or non-lanthanide metals, singly or in combination. More than one lanthanide metal may be utilized. A mixture of non-lanthanide metals may be utilized alone or along with one or more lanthanide metals. (Ml) and/or (M2) may each independently be any described above and/or include or be a combination of Eu and Y, Eu and La, Eu and Ce, Eu and Gd, Eu and Tb, Eu and Dy, Eu and Sm, Ce and Tb, Tb and Yb, Er and Yb, Pr and Yb, Tm and Yb, and/or combinations thereof. One or more of Ml and M2 may be Eu³⁺. For example, the polyheterosiloxane composition may include Eu³⁺ and exhibit excitation and emission transitions between the ⁵D and ⁷F energy levels in the 4f orbital. A principal excitation line may be observed at approximately 395 nm and principal emission line may be observed at approximately 615 nm. Alternatively, (M2) may be chosen from Ce, Eu, Nd, Er, Sm, Dy, Tb, and/or combinations thereof, or chosen from Eu, Er, Tb, Nd, and combinations thereof.

[0007] The polyheterosiloxane composition also includes (C) siloxy units having the formula (R² ₃SiOi ₂), (R^SiOm), (R¹Si0_{3 2}), and/or (S1O4/2). 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. "M" and "D" units, "M" and "T" units, "M" and "Q" units, "D" and "T" units, "D" and "Q" units, or "T" and "Q" units, and/or combinations thereof.

[0008] Each R¹ 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 R¹ may be the same or different from any other R¹. 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 R¹ 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.

[0009] Each R² is independently a hydrocarbyl group having from 1 to 20, carbon atoms or an organosiloxane having at least one disiloxy unit. Each R² may include 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, or 20, carbon atoms, or any value or range of values therebetween. Typically, R² is different from R¹. Non- limiting examples of R² are those described above for R¹. Non- limiting examples of organosiloxanes having at least one disiloxy unit, as R², are Me₃SiO(SiMe₂0)_nMe, wherein n is from 3 to 100, Me₃SiO(SiMe₂0)_n_ i, wherein n is 3 to 100 and the other two R² are Me, CH₂CH₂[(CH₃)₂SiO]_nOSi(CH3)₂(CH₂)3CH3,-CH₂CH₂Si(CH3)(OSi(CH₃)3)₂,

0(CH₃)₂Si[(CH₃)₂SiO]_mOSi(CH₃)₂(CHCH₂), -OSi(CH₃)₂CH₂CH₂ Si(CH₃)(OSi(CH₃)₃)₂, and combinations thereof.

[0010] At least one or two, e.g. one, two, or three, of R² is a Ci to C₁₀ hydrocarbyl group, e.g. each having 1, 2, 3, 4, 5, 6, 7, 8, 9, and/or 10 carbon atoms. Alternatively, at least one or two, e.g. one, two, or three, of R² is phenyl. In another embodiment, at least one or two, e.g. one, two, or three, of R² is - CH₂CH₂[(CH₃)₂SiO]_nOSi(CH₃)₂(CH₂)₄CH₃, wherein n is from 10 to 20, from 11 to

19, from 12 to 18, from 13 to 17, from 14 to 16, or 15. In further embodiment, at least one or two, e.g. one, two, or three, R² is -CH₂CH₂Si(CH₃) (OSi(CH₃)₃)₂. Alternatively, one or two of R² may methyl and one or two of R² may be phenyl. Furthermore, one, two, or three of R² may be vinyl. In a further embodiment, two or three of R² are -CH₂CH₂Si(CH₃)(OSi(CH₃)₃)₂. Moreover, the [R² ₃Si0_1/2] unit may have the formula Si(C₆H₅)₂ {CH₂CH₂[(CH₃)₂SiO]_nOSi(CH₃)₂(CH₂)₃CH₃}Oi/₂, wherein n is from 1 to 500, from 1 to 100, or from 1 to 50. Alternatively, the unit [R² ₃Si0_1/2] may have the formula Si(C₆H₅)₂ {CH₂CH₂Si(CH₃)(OSi(CH₃)₃)₂}0_1/2

[0011] The (C) siloxy units may include greater than 50 mole or weight percent of R¹Si0_{3 2} siloxy units where R¹ is phenyl; R^SiO^ siloxy units where one R¹ substituent is phenyl, and the other R¹ substituent is methyl; or R^SiO^ and R¹Si0_{3 2} siloxy units where one R¹ substituent in the R^SiO^ siloxy unit is phenyl, and the other R¹ substituent is methyl, and where R¹ is phenyl in the R¹Si0_{3 2} siloxy unit. One or more siloxy units may have the formula [(C6Hs)SiC>₃/₂]d, [(C₆H5)₂Si0_2/2]_d[(C₆H5)Si03/₂]t, or [(CH3)(C₆H₅)Si0_2/2]_d [(C₆H₅)Si03/₂]t.

[0012] 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 (A), (B), and (C) based on a total weight of the polyheterosiloxane composition. Alternatively, the polyheterosiloxane composition may include approximately 100% of (A), (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.

[0013] The varied amounts of each of (A), (B), and (C) are typically described relative to mole fractions of each to a total number of moles of (A), (B), and (C). For example, the mole fractions of (A), (B), and (C) in the polyheterosiloxane composition relative to each other is of the formula [(Ml)]_a[(M2)]_b[R²3Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si03/2]t[Si0₄/2]_q. The subscript m denotes the mole fraction of the optional "M" unit (R² ₃SiOi ₂). The subscript d denotes the mole fraction of the optional "D" unit (R^SiO^). The subscript t denotes the mole fraction of the optional "T" unit (R¹Si0_3/2). The subscript q denotes the mole fraction of the optional "Q" unit (Si0_4/2).

[0014] 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. Alternatively, 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. For example, when (Ml) is a non-lanthanide metal and (M2) is a lanthanide metal, 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, i.e., the sum of a+b, 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.

[0015] m is typically from 0.001 to 0.9, 0.1 to 0.6, or 0.2 to 0.5 or any value or range of values therebetween, m cannot be zero, 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. Each of t and q is typically independently from zero to 0.9, 0.010 to 0.9, 0.001 to 0.7, 0.1 to 0.7, 0.1 to 0.6, or 0.2 to 0.5 or any value or range of values therebetween. Moreover, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1. The terminology "~" describes that the sum of a, b, m, d, t, and q is approximately equal to 1. The sum may be 0.99, 0.98, 0.97, 0.96, 0.95, etc, or any value or range of values therebetween. If the sum does not equal 1, then 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. [0016] 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. Alternatively, 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.

[0017] 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 ²⁹Si and ¹³C 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).

[0018] One or more atoms of (Ml) and (M2) 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). For example, 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.

[0019] 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.

[0020] 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. Typically, 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.

[0021] The polyheterosiloxane composition may have "metal-rich" domains and "siloxane-rich" domains. As used herein the terminology "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). As used herein, the terminology "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. In one embodiment, Ti and/or Al can act as a bridge to Ml to bridge siloxy units with lanthanide-oxygen units. Use of ¹⁷0 NMR, ⁴⁸Ti NMR and/or ²⁷ Al NMR may increase resolution or ability to quantify Si-0 and Lanthanide-0 bonds.

[0022] Alternatively, the metal rich domains may not be of sufficient size to be observed using high resolution transmission electron micrographs (TEM). Thus, the (Ml) and (M2) metals may be sufficiently distributed in the polyheterosiloxane composition and have a domain size smaller than 10 nanometers, alternatively smaller than 5 nanometers, or alternatively smaller than 2 nanometers (detection limits for the TEM). Alternatively, NMR, FT-IR, and/or X-Ray PDF techniques may be utilized throughout this disclosure to determine bonding, polyheterosiloxane composition, etc.

[0023] 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. As used herein, "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.

[0024] 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. For example, 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).

[0025] The polyheterosiloxane composition may be photoluminescent and may emit visible or ultraviolet light when exposed to, or excited by, visible or ultraviolet light. The polyheterosiloxane composition may exhibit a quantum yield of at least 0.05%, as determined using the formula described in greater detail below. In various embodiments, 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. It is contemplated that 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. In various polyheterosiloxane compositions, e.g. EuTiZnSi, quantum yields may be from 35 to 55% measured, for example, using an integrating sphere attached to a Flurolog- 3 fluorescence spectrometer. In other polyheterosiloxane compositions, e.g. ZrTbSi, 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, %.

[0026] A limited size of the metal rich domains may lead to enhanced photoluminescence. For example, concentrations of 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. A representative spectrofluorometer is the Fluorolog-2 or -3 spectrofluorometer (FL2 or FL3) (HORIBA Jobin-Yvon Inc. Edison, NJ, USA).

[0027] The efficiency in which a photoluminescent material converts light from one wavelength to another can be described as quantum yield (QY). Alternatively, 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). Alternatively, equipment such as Fluorolog-2 or -3 spectrofluorometers (FL2 or FL3) (HORIBA Jobin-Yvon Inc. Edison, NJ, USA) may be utilized with appropriate accessories. For example, a combination of a UV-Vis spectrum and a PL/PLE spectra may be utilized.

[0028] In various embodiments, 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. [0029] 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 1000 nm, where the emitted light is a longer wavelength than the excitation wavelength, with a photon quantum yield efficiency of at least 0.1%, where photon quantum yield is determined using the equation described above. Alternatively, 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. Alternatively, 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%.

[0030] 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. Alternatively, 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. Typically, 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.

[0031] 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. Narrow band red emission at approximately 615 nm balances strong red emission for suitable color rendering with visually bright emission. For example, polyheterosiloxane compositions that include Si+Eu ⁺ resin phosphors tend to exhibit a CIE color value of x=0.66, y=0.34, a nearly saturated red, while the emitting in a visually bright range. However, for a similar color value, the peak tends to be approximately 650 nm because much of the broadband emission is over 700 nm, and lost, reducing brightness and system efficacy. The CIE color values of the emitted light may be as follows: x from 0.62 to 0.68, from 0.64 to 0.67, or from 0.65 to 0.66, and y from -.31 to 0.37, from 0.32 to 0.36, or from 0.33 to 0.34.

[0032] 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:

X = \ ΐ {λ )χ' {λ )άλ

o

Y = \ ι{λ )γ {λ )άλ

o

Z = ΐ (λ )ζ' (λ )άλ

0

wherein χ'(λ), y' and z'(X) are color matching functions with peaks at approximately 450 nm, 550 nm and 600 nm respectively, and Ι(λ) is the spectra power distribution. The reported color or chromaticity coordinates x, y and z are calculated x=X/(X+Y+Z), y=Y/(X+Y+Z), and z=Z/(X+Y+Z) and by inspection x+y+z=l .

[0033] 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 Si+Ln 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). Then the excitation/emission spectra are typically reference corrected for both variations in intensities in the excitation source and variations in the photomultiplier tube detector by utilizing the ratio of PMT spectral response to Rc and Rs. 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.

[0034] Absorption spectra are typically determined by monitoring the strongest absorption peak of the polyheterosiloxane composition, e.g. Si+Eu³⁺ luminescent silicones via population of the ⁵L₆ level at 393.5 nm, 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. However, the concentrations may be from 1.5 to 8.0 wt %, depending on the total metal content of the polyheterosiloxane composition.

[0035] In one method, combined absorption and fluorescence data are used to calculate quantum yields relative to a standard reference. Because the optical densities can be kept below < 0.1, quantum yields could be determined via the following equation: QY= [Λ_Γ(λ_Γ)/Λ_χ(λ_χ)][/(λ_Γ)//(λ_χ)][η_χν][Ο_χ/ ] 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 λ, 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. For example, 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 fluroescein (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.

[0036] The polyheterosiloxane composition may also have an asymmetry ratio, typically in an embodiment utilizing Eu³⁺, of from 3.0 to 6.0, from 3.1 to 5.9, from 3.2 to 5.8, from 3.3 to 5.7, from 3.4 to 5.6, from 3.5 to 5.5, from 3.6 to 5.4, from 3.7 to 5.3, from 3.8 to 5.2, from 3.9 to 5.1, from 4.0 to 5.0, from 4.1 to 4.9, from 4.2 to 4.8, from 4.3 to 4.7, from 4.4 to 4.6, or 4.5, or any value or range of values therebetween, as determined using a Flurolog3 (Horiba Scientific) spectrofluorometer by measuring the ratio of the peak emission value of the ⁵Do→ ⁷F₂ transition at 614 nm to the ⁵Do→ ⁷Fi transition at 590 nm. The asymmetry ratio can be calculated according to the method described below. In addition, the asymmetry ratio may change based on selection of lanthanide metal, as can be calculated by those known in the art.

[0037] Asymmetry ratios can be calculated by measuring a ratio of a peak emission value of the polyheterosiloxane composition, e.g. of the ⁵Do→ ⁷F₂ transition at 614 nm to the ⁵D₀→ ⁷Fi transition at 590 nm, which correspond to electric and magnetic dipoles, respectively. In one embodiment, the ⁵Do→ ⁷F₂ transition is a "hypersensitive" electric dipole, and is very sensitive to the local electric field surrounding a lanthanide ion, e.g. Eu³⁺ ion. The ⁵D₀→ ⁷Fi transition is a magnetic dipole, however, and tends to not be sensitive to the local Eu³⁺ environment. Asymmetry ratios close to or less than 1 tend to indicate that only a small amount of distortion takes place near the lanthanide ion, e.g. Eu³⁺, center and that the ion is near an inversion center/resides in a high symmetry environment, while values greater than 1 denote Eu³⁺ in a low symmetry environment. This rationale and explanation may also apply to other lanthanide metals as well.

[0038] The polyheterosiloxane composition may also have a radiative lifetime calculated using emission spectra generated using a fluorescence spectrometer and a 393.5nm excitation wavelength. The terminology "radiative lifetime" describes the lifetime of a material in the absence of any non-radiative processes involved in the conversion of light. Radiative lifetime values for the polyheterosiloxane composition, e.g. a EuTiZnSi polyheterosiloxane composition, may be from 2.43 to 2.73 using a Flurolog-3 fluorescence spectrometer and a photo-multiplier tube detector. Radiative lifetime measurements may be calculated according to the method described below.

[0039] Radiative lifetimes can be calculated from a corrected emission spectrum of a polyheterosiloxane composition in lieu of using Judd-Ofelt theory, known in the art, because the corrected emission spectrum from a spectrofluorometer is representative of relative photon flow vs. wavelength. For example, the ⁵Do→ ⁷Fi transition can be considered to be chemically insensitive to changes in surrounding environment. Under the assumption that the relative magnetic dipole strength is both wavelength independent and proportional to the dipole strength of, e.g. the ⁵Do→ ⁷Fi transition, the shape of the emission spectrum of an lanthanide ions, e.g. Eu³⁺, center can be related to its radiative lifetime via:

wherein ¾ is the radiative lifetime, (known in the art as approximately 14.65 s^"1) is the spontaneous emission probability of the ⁵Do→ ⁷Fi transition for an Eu³⁺ center in vacuum, n is the refractive index of the medium, and IMD is the ratio of the corrected emission spectrum of the material to the emission of just the magnetic dipole transition. Just as above, the same or similar calculations can be made for other lanthanide metals.

[0040] The polyheterosiloxane composition may have an experimental lifetime measurement of from 0.4 to 1.6, from 0.5 to 1.5, from 0.6 to 1.4, from 0.7 to 1.3, from 0.8 to 1.2, from 0.9 to 1.1, or 1.0, milliseconds, or any value or range of values therebetween, as determined using a Flurolog3 (Horiba Scientific) spectrofluorometer according to the method described below.

[0041] Experimental lifetimes can be collected using a Horiba Jobin-Yvon

Fluorolog 3 spectrofluorometer equipped with a 3 slit double grating emission monochromator (2.1 nm/mm, 1200 grooves/mm) and adapted for time-correlated single photon counting, using a 395 nm SpectraLED light emitting diode with a 100 us pulse width. The experimentally collected decay curves are typically analyzed the commercially available DAS6 decay analysis software package, using a 1 parameter exponential fit. Goodness of fit can be determined by minimizing the reduced Chi- squared function and inspection of the weighted residuals. Each decay curve can count at least 10,000 points and data reported tends to be from three independent measurements. Typical sample concentrations typically include 5% wt solids in solvents including toluene and optionally 1-butanol to improve solubility. Measurements can be performed in 1 cm square quartz cuvettes, or equivalents.

[0042] 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.

[0043] 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. The silicone fluid is typically PDMS but is not limited in this way. In various embodiments, 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.

[0044] 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.

[0045] Additional non-limiting examples of 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 Me₃SiO[(OSiMe₃)2SiO]SiMe3 and Me₃SiO[(OSiMe₃)MeSiO]SiMe₃.

Method of Formin2 the Polyheterosiloxane Composition:

[0046] This disclosure also provides a method of forming the polyheterosiloxane composition. The method includes the step of reacting (Α') a metal (M3) alkoxide, (Ε ) an optional hydrolyzable metal (M4) salt, (C) a silicon- containing material having silicon-bonded hydroxy groups, (D) a compatibilizing organosiloxane having at least one [R² ₃SiOi_/2] unit and having a weight average molecular weight (M_w) of less than 10,000 g/mol, and (E) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β'), to form the polyheterosiloxane composition. The method may also include one or more steps as described in WO2011/002826, which is expressly incorporated herein by reference.

[0047] It is to be understood that (Α'), optionally (Β'), (C), (D), and (E) may react together in any order. For example, (Α'), optionally (Β'), (C')_> (D) and (E) may react individually or with more of each other batch wise (e.g. simultaneously) and/or sequentially. One or more portions of (Α'), optionally (Β'), (C')_> (D) and (E) may react individually or with more of portions of each other batch wise (e.g. simultaneously) and/or sequentially. (Β') may not be utilized and alkoxides may be utilized in the absence of a hydrolyzable metal. In another embodiment, (Β') is utilized, e.g. with an alkoxide. [0048] The (Α') 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. 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.

[0049] The metal (M3) is not particularly limited but is typically is the same as (Ml), e.g. a lanthanide metal or a non-lanthanide metal. The metal (M3) of the metal alkoxide may be independently selected and may be the same as (Ml) or (M2) or may be different.

[0050] The metal (M3) alkoxide may have the general formula (I) RlkM30_n

X_D(OR2) vl-k-p-2n. Iⁿ Formula (I), subscript vl is the oxidation state of metal (M3), typically from 1 to 7, 1 to 5, or 2 to 4, 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.

[0051] 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.

[0052] 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) -(R3o)jR4, 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 3 to 4, carbon atoms.

Each R4 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 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and hexyl groups. Non-limiting examples of the aryl groups of 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 R^ are as described above for R2. Non-limiting examples of the polyether group of Formula (VI) include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, me thoxyethoxy ethyl, and ethoxyethoxyethyl groups. Alternatively, R^ 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.

[0053] X is typically chosen from carboxylate ligands, organosulfonate ligands, organophosphate ligands, β-diketonate ligands, and chloride ligands, alternatively carboxylate ligands and β-diketonate ligands. The carboxylate ligands for X typically have a formula RI ^COO^" where R!5 is chosen from hydrogen, alkyl groups, alkenyl groups, and aryl groups. Non-limiting examples of 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 R!5 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 R!5 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and benzyl groups.

Alternatively, R!5 is methyl, 2-propenyl, allyl, and phenyl, β-diketonate ligands for X can have the following structures:

where R16, 18_{? an(}j R21 _are typically chosen from monovalent alkyl and aryl groups. Non-limiting examples of alkyl groups for R16, 18_{? an(}j R21 i_nci_ud_e 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 Rl6, R18₅ and R21 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups. R!9 is typically chosen from alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups for R!9 include CI to C18 alkyl groups, alternatively CI to C8 alkyl groups such as methyl, ethyl, propyl, hexyl and octyl groups. Non-limiting examples of 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. Non- limiting examples of 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!7 and R²⁰ are typically hydrogen or alkyl, alkenyl, and aryl groups. Non-limiting examples of alkyl groups for R!7 and R20 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.

Non- limiting examples of alkenyl groups for 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. Non-limiting examples of aryl groups for R!7 and R20 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups. R16₎ R17₎ R18_j R19₎ R20_{5 an(}j R21 _{are eacn} 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.

[0054] 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, hafnium ethoxide, hafnium 2-ethylhexoxide, hafnium 2- methoxymethyl-2-propoxide, indium methoxyethoxide, iron (III) ethoxide, magnesium ethoxide, magnesium methoxyethoxide, magnesium n-propoxide, molybdenum (V) ethoxide, niobium (V) n-butoxide, niobium (V) ethoxide, cerium

(IV) t-butoxide, cerium (IV) isopropoxide, cerium (IV) ethylthioethoxide, cerium (IV) methoxyethoxide, strontium isopropoxide, strontium methoxypropoxide, tantalum

(V) ethoxide, tantalum (V) methoxide, tantalum (V) isopropoxide, tantalum tetraethoxide diemthylaminoethoxide, di-n-butyldi-n-butoxytin, di-n- butyldimethoxytin, tetra-t-butoxytin, tri-n-butylethoxytin, titanium ethoxide, titanium 2-ethylhexoxide, titanium methoxide, titanium methoxypropoxide, titanium n- nonyloxide, tungsten (V) ethoxide, tungsten (VI) ethoxide, vanadium triisobutoxide oxide, vanadium triisopropoxide oxide, vanadium tri-n-propoxide oxide, vanadium oxide tris(methoxyethoxide), zinc methoxyethoxide, zirconium ethoxide, zirconium 2- ethylhexoxide, zirconium 2-methyl-2-butoxide, and zirconium 2-methoxymethyl-2- propoxide, aluminum s-butoxide bis(ethylacetoacetate), aluminum di-s-butoxide ethylacetoacetate, aluminum diisopropoxide ethylacetoacetate, aluminum 9- octdecenylacetoacetate diisopropoxide, tantalum (V) tetraethoxide pentanedionate, titanium allylacetoacetate triisopropoxide, titanium bis(triethanolamine) diisopropoxide, titanium chloride triisopropoxide, titanium dichloride diethoxide, titanium diisopropoxy bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, titanium trimethacrylate methoxyethoxyethoxide, titanium tris(dioctylphosphato)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, zirconium (bis-2,2' -(alloxymethyl)- butoxide)tris(dioctylphosphate), zirconium diisopropoxide bis(2,2,6,6-tetramethyl- 3,5-heptanedionate), zirconium dimethacrylate dibutoxide, zirconium methacryloxyethylacetoacetate tri-n-propoxide, and combinations thereof. (Α') may be chosen from titanium tetraisopropoxide, titanium butoxide, titanium tetrabutoxide, zirconium tetrabutoxide, or aluminum sec-butoxide.

[0055] The optional (IT) hydrolyzable metal (M4) salt 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, two different salts of the same metal (M4), two salts of different metals (M4), or a plurality of salts of one or more metals (M4), may be utilized.

[0056] Typically, the hydrolyzable metal (M4) is the same as the (M2). The hydrolyzable metal (M4) may be a lanthanide metal or a non-lanthanide metal. The hydrolyzable metal (M4) may be the same as (Ml) or (M2) or metal (M3) or may be different. In addition, hydrolyzable metal (M4) may be independently selected and may any one of the aforementioned options for (Ml) and/or (M2) and/or metal (M3). However, at least one of metal (M3) and hydrolyzable metal (M4) is typically a lanthanide metal.

[0057] The optional (Ε ) hydrolyzable metal (M4) salt may be further described as (B' l) a non-hydrated metal salt having a general formula (IV)

R^_eM4(Z)(_v2_e)/_w or (Ε 2) a hydrated metal salt having a general formula (V) M4(Z)_v2/_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, β-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 ¾() 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.

[0058] In Formulas (IV) and (V), 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). Typically, each Z is independently chosen from carboxylate ligands, β-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 β-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.

[0059] The carboxylate ligands may also be chosen from acrylate, methacrylate, butylenate, ethylhexanoate, undecanoate, undecylenate, dodecanoate, tridecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, cis-9- octadecylenate (C 18), cis- 13-docoylsenoate (C22). The carboxylate ligand may be undecylenate or ethylhexanoate. Alternatively, the organic sulfonate ligands for Z may have a formula R22SC>3^~, where R22 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of alkyl groups, alkenyl groups and aryl groups are as described above for R.15. Alternatively R22 is tolyl, phenyl, or methyl.

[0060] The organic phosphate ligands for Z typically have a formula (R23())2

PC>2^" or R23O- PO32-, where R23 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups, alkenyl groups and aryl groups are as described above for R!5. Alternatively R23 may be phenyl, butyl, or octyl.

[0061] Organic phosphite ligands for Z may have a formula (R24())2 PO^~ or

R24Q_ P02^^", where R24 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups, alkenyl groups and aryl groups are as described above for R!5. Alternatively R24 may be phenyl, butyl, or octyl. Alternatively, Z in Formulas (IV) and (V) may be independently chosen from carboxylate ligands, β-diketonate ligands, nitrate ligands, sulphate ligands, and chloride ligands. Alternatively, Z may include carboxylate ligands and β-diketonate ligands.

[0062] In Formulas (IV) and (V), subscript e is typically a value from 0 to 3, alternatively from 0 to 2, and alternatively 0. In Formula (IV), 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 R5. In Formula (V), x 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.

[0063] Examples of (Β') hydrolyzable metal salts described by Formula (IV) include but are not limited to lanthanum acetate, cerium acetate, praseodymium acetate, neodymium acetate, promethium acetate, samarium acetate, europium acetate, gadolinium acetate, terbium acetate, dysprosium acetate, holmium acetate, erbium acetate, thulium acetate, ytterbium acetate, lutetium acetate, lanthanum acetylacetonate, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, promethium acetylacetonate, samarium acetylacetonate, europium acetylacetonate, gadolinium acetylacetonate, terbium acetylacetonate, dysprosium acetylacetonate, holmium acetylacetonate, erbium acetylacetonate, thulium acetylacetonate, ytterbium acetylacetonate, lutetium acetylacetonate, and combinations thereof. Non- limiting examples of hydrated metal salts (BΊ) described by Formula (VI) include the hydrated versions of any of the metal salts as described above for (B'l).

[0064] In one embodiment, (Β') is chosen from (B'l) a non-hydrated metal salt having a general formula (IV) R^_eM4(Z)(_v2__e)/_w and (B^'2) a hydrated metal salt having a general formula (V) M4(Z)_v2/_w-xH20, wherein (M4) is a lanthanide metal, v2 is the oxidation state of M4, w is the oxidation state of Z, Z is independently chosen from alkoxides, carboxylates, β-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.

[0065] In another embodiment, (Α') and (Β') 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 (Α'), and optionally (Β'). The percent may be further described as mole or weight percent as a theoretical calculated stoichiometric amount.

[0066] Referring now to (C), it is a silicon-containing material having silicon-bonded hydroxy groups. 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.

[0067] The (C 1) siloxane can be a disiloxane, trisiloxane, or polysiloxane, or combinations thereof. Similarly, 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.

[0068] 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.

[0069] 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.

[0070] In one embodiment, (C) is further defined a hydrolysis product of at least one of: (C'i) a organosiloxane, (C'ii) a silane, and combinations thereof. In this embodiment, 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. In other words, (C'i) may have a hydrolyzable group, (C'ii) may have a hydrolyzable group, or 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.

[0071] The (C) hydrolysis product, i.e., the product formed from reaction with water, may include R⁵ _g(R⁶0)f(HO)_jSiO(4-₍f₊g_+j))/2 and/or hydrolyzed silane R⁵ _h(HO)_kSiZ'i, wherein, for example, R⁵ is hydrogen or a hydrocarbyl group. A hydrolyzed organosiloxane R⁵ _g(R⁶0)f(HO)_jSiO(4-₍f₊g_+j))/2 or hydrolyzed silane R⁵ _h(HO)_kSiZ'; can be used directly or diluted with aromatic solvents (toluene) and alcohol before added to a mixture of (Α') and optionally (Β').

[0072] One or both of (C'i) and/or (C'ii) may be treated with stoichiometric amounts of water including catalytic amounts of a strong acid, e.g. HC1 or any "strong acid", or any highly diluted aqueous acid to initiate or promote hydrolysis. Formation of 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. For example, a silane (C'ii), e.g. having a general formula (III) R⁵ _hSiZ'i (wherein Z' = CI and i = 1 , 2), may be treated with stoichiometric amounts of water in the presence of a base, typically an amine such as triethylamine or pyridine, to capture resulting HC1 as a hydrochloride salt. After removal of the hydrochloride salt, a hydrolyzed silane, e.g. R⁵ _hSi(OH)i, can be isolated or used directly in solution when added to the reaction mixture of A' and B' .

[0073] In other embodiments, organosiloxane (C'i) (e.g. R⁵g(R⁶0)_fSiO(4_

_(f+g))/2) and/or silane (C'ii) (e.g. R⁵ _hSiZ';) are treated with diluted aqueous acid, such as 0.1 N HC1, to form a mixture. The aqueous acid may be used in stoichiometric amounts relative to hydrolysable groups OR⁶ or Z' (e.g. wherein Z' = OR⁶). 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' .

[0074] In other embodiments, a solution of silane R⁵ _hSiZ'i (wherein Z' = CI and i = 1, 2), in diethyl ether (1 :5) is added dropwise to a stirred cooled solution of stoichiometric amounts of triethylamine or pyridine and water in a diethyl ether- acetone mixture (e.g. 7: 1). 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. An excess of 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/diethyl ether. The product may be isolated as white solid. [0075] (C'i), which may be reacted to form the hydrolysis product, may be an organosiloxane having an average siloxane unit formula (II)

(f+g))/2_> ^and/or (C'ii) may be a silane having a general formula (III) R^SiZ'j. In these formulas, each R⁵ 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) -(R3o)jR4, where j is a value from 1 to 4, each R3 is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R^ 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.

[0076] In Formula (II), subscript f may be a value from 0.1 to 3 and alternatively from 1 to 3. In Formula (II), subscript g may be a value from 0.5 to 3 and alternatively from 1.5 to 2.5. In Formula (II), subscripts (f+g) may have a value from 0.6 to 3.9 and alternatively from 1.5 to 3. For example, 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.

[0077] Alternatively, Z' may be a hydrolysable group such as acetoxy, oxime, silazane, CI or OR⁶ and/or each R5 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. In one embodiment, at least one R5 groups of (C'i) and/or (C'ii) silane is an R group, as described above. Alternatively, at least one R5 = R may be as described by formula (II) or (III). Additionally, h is typically a value from 0 to 3,

1 is typically a value from 1 to 4 and (h+i) equals 4. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0078] 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 R^ in Formulas (II) and (III) may be, for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, or octenyl groups. Alternatively, 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 in formulas (II) and (III) may be phenyl, naphthyl, benzyl, tolyl, xylyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups. Alternatively, 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.

[0079] In Formula (III), each Z' may be a chloro atom (CI) or OR , where R6 is as described above. Alternatively, Z' may be OR . In Formula (III), subscript h may be a value from 0 to 3, from 1 to 3, or from 2 to 3. In Formula (III), subscript i is a value from 1 to 4, from 1 to 3, or from 1 to 2. In Formula (III), subscripts (h+i) may equal 4. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0080] 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.

[0081] Referring to the (D) compatibilizing organosiloxane, this organosiloxane has at least one [R² ₃SiOi_/2] unit. However, the compatibilizing organosiloxane may have more than one [R² ₃SiOi 2] unit. The compatibilizing organosiloxane also has a weight average molecular weight (M_w) of less than 10,000 g/mol. In various embodiments, the 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. Alternatively, the M_w may be any value or range of values described immediately above or between those values described immediately above.

[0082] In one embodiment, the (D) compatibilizing organosiloxane has an average formula chosen from:

DI) (RO)(C6H5)2SiCH2CH₂[(CH₃)2SiO]nOSi(CH₃)2(CH2)3CH₃ ;

DII) (R'0)(C6H5)2SiCH₂CH2 Si(CH₃)(OSi(CH₃)₃)2; Dili) (RO)3SiO(CH₃)2Si[(CH₃)2SiO]_mOSi(CH₃)2 (CHCH₂); or

DIV) (R' 0)(C₆H5)2SiOSi(CH3)2CH₂CH₂Si(CH3)(OSi(CH3)₃)2, wherein each n is independently from 3 to 100, alternatively from 10 to 12, each m is independently from 3 to 100, alternatively from 20 to 30, and R' is a Ci to C₄ alkyl group. Alternatively, the (D) compatibilizing organosiloxane may have the average formula:

wherein n is from 3 to 100, 3 to 50, or 3 to 15.

Alternatively, the (D) compatibilizin organosiloxane may have the average formula:

Even further, the (D) compatibilizing organosiloxane may have the average formula:

wherein n is from 3 to 100, alternatively from 20 to 30.

[0083] In other embodiments, the (D) compatibilizing organosiloxane has the formula: (MegSiO^MeSiCHzCHzSiCCHg^OSiCCeHsMOMe). Even further, the (D) compatibilizing organosiloxane may have the formula (R⁸ ₃SiO)_n(R⁸)(3-_n)Si-R⁹-Si(R⁸)₂

OSi(R 1^l0^u)₂X, wherein n is 1 or 2. Each R 8 may be independently a monovalent Ci to C₂o hydrocarbyl. The hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group, including halogen substituted hydrocarbyls. Each R⁸ may independently be a Ci to C₂o alkyl group, a Ci to Cis alkyl group, a Ci to C₆ alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. R⁸ may be an aryl group, such as phenyl, naphthyl, or an anthryl group, or any combination thereof. Alternatively, each R⁸ may independently be phenyl, methyl, or a combination of both. Each R⁹ 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 R¹⁰ may independently be a monovalent Ci to C30 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 (C₆H₅). X may be a hydrolyzable group chosen from -OR¹¹, CI, -OC(0)R⁹, -N(R⁹)₂, or

wherein each R¹¹ is independently hydrogen or a Ci to C₆ alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, pentyl, or hexyl group. Alternatively, X may be an alkoxy, hydroxyl, carboxy, amine, chloride, or oxime group, e.g. -OCH₃, -OCH2CH₃, -OH, -CI, or -OC(=0)CH₃. In one embodiment, the organosiloxane has the following formula: (Me₃SiO)2(Me)SiCH₂CH₂Si (CH₃)₂OSi(C₆H₅)2(OMe), wherein Me is a methyl group. Alternatively, the organosiloxane has the formula (R⁸3SiO)_n(R⁸)₍3__n)Si-G-Si(R⁸)₂OSi(R¹⁰)₂X, wherein n is 1 or 2, R⁸ is independently a monovalent Ci to C2₀ hydrocarbyl, G is a siloxane or polysiloxane bridging group comprising at least one siloxy unit selected from a (R¹² ₂Si0₂2), (R¹²Si032), or (S1O4_/2) siloxy units, wherein R¹² may be any organic group, R¹⁰ is independently a monovalent Ci to C₃₀ hydrocarbyl including at least one aryl group, X is a hydrolyzable group chosen from -OR⁹, CI, -OC(0)R⁹, -N(R⁹)2, or - and R¹¹ is hydro gen or a Ci to C₆ alkyl group. G may also be a combination of hydrocarbyl bridging groups, such as the divalent C2 to C12 hydrocarbyl groups described above, and a siloxane or polysiloxane. In various embodiments, G is a polydimethylsiloxane of the formula -0(Me₂Si0₂2)_q- where the subscript q is from 1 to 20, alternatively from 1 to 10, or alternatively from 1 to 5. When the polysiloxane bridging group includes a (R¹²Si032), or (S1O42) siloxy unit(s), the group may further include additional M siloxy units to provide endcapping groups. Alternatively, one or more T or Q units may be silanol terminated.

[0084] Typically, an amount of (E) water is utilized (and/or reacted) with (Α') and optionally (Β') so that polyheterosiloxanes having at least two non-Si metal elements can be formed. Since water can also be incorporated via hydrated metal salts (Ε 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. Alternatively, 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.

[0085] Typically, the water is added slowly to (Α') and optionally (Β') in an attempt to ensure that the metal alkoxide does not react quickly with the water so as to form a precipitate. Alternatively, the water may be diluted with one or more solvents, such as those described above. Depending on the solvents used and when they are added, 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.

[0086] Each of the components (Α'), optionally (Β'), (C), and/or (D) may be liquid or solid and it is typical that they are pre-mixed or dispersed. Stirring one or more of the components (Α'), optionally (Β'), (C) and/or (D) in a solvent may provide a homogenous dispersion. As used herein, the terminology "dispersion" describes that the molecules of the various components (Α'), ((Β'), (C) and/or (D) are homogenously distributed. A solvent may not be needed if one or more components (Α'), ((Β'), (C) and/or (D) 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. Non- limiting examples of 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.

[0087] Typically, reaction of (Α') and optionally (Β') with (E) 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.

[0088] 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.

[0089] This disclosure also provides a polyheterosiloxane composition that is the reaction product of: the (Α') metal (M3) alkoxide, the (Ε ) optional hydrolyzable metal (M4) salt, the (C) silicon-containing material having silicon-bonded hydroxy groups, the (D) compatibilizing organosiloxane having at least one [R² ₃SiOi_/2] unit and having a weight average molecular weight (M_w) of less than 10,000 g/mol, and an (E) amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β'), wherein each R² is independently a hydrocarbyl group having from 1 to 20 carbon atoms or an organosiloxane having at least one disiloxy unit.

[0090] The (D) compatibilizing organosiloxane allows the polyheterosiloxane composition (e.g. through one or more M units) to be "compatible" with external, i.e., independent, silicones, e.g. organopolysiloxanes. The terminology "compatible," typically describes that the polyheterosiloxane composition can form a stable homogeneous clear mixture, as visually evaluated, when combined with a silicone. Those of skill in the art appreciate when a mixture is homogeneous, stable, and/or clear. Typically, the mixture is clear in that light passes through it.

[0091] The polyheterosiloxane composition may be compatible with, for example, polydimethylsiloxanes (350 cSt DOW CORNING^® 200 fluid), vinyl- terminated polydimethylsiloxanes (DOW CORNING^® SFD 119 Fluid), OH- terminated polydimethylsiloxanes (having a viscosity of 40 mm²/sec at 25 °C), vinyl- terminated polyphenylmethylsiloxanes (M^VlD^PhMe25M^Vl), and OH-terminated polypheny lmethylsiloxanes (having a viscosity of 500 mm²/sec at 25 °C). [0092] In various embodiments, the polyheterosiloxane composition may be compatible with 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. 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 multipart component system. For example, 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.

[0093] The curable silicone can be further described as curing to form a thermoset silicone polymer or a thermoplastic silicone polymer. Typically, as used herein and below, the term "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. Although 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. Also, the term "thermoset polymer" may describe a cured (i.e., cross-linked) silicone polymer that does not convert to a fluid state on heating. As used herein and below, the term "thermoset polymer" typically describes a silicone polymer having the property of becoming permanently rigid (non-flowable) when cured (i.e., cross-linked).

[0094] 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 hydrosilylation catalyst.

[0095] 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. In one embodiment, the cross-linking agent has the formula R^qSiXzi.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.

[0096] 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.

[0097] A peroxide-curable silicone typically includes an organopolysiloxane having silicon-bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.

[0098] An epoxy-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded epoxy-functional organic groups. Typically, before curing, a proton source, such as an amine, SiH, acid generator, or a cationic photo-acid generator, are utilized.

[0099] A hydrosilylation-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 hydrosilylation-curable silicone is generally heated for a length of time sufficient to cure (cross-link).

[0100] A condensation-curable silicone can be cured (i.e., cross-linked) by heating, e.g. at a temperature of from 50 to 250 °C, for a period of from 1 to 50 h. If a condensation catalyst is included, the condensation-curable silicone can typically be cured at a lower temperature, e.g., from room temperature (-23 ± 2 °C) to 150 °C.

[0101] Alternatively, the condensation-curable silicone can be cured by exposure to moisture or oxygen at a temperature of from 100 to 450 °C for a period of from 0.1 to 20 h. When the (II) 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.

[0102] Further, the condensation-curable silicone can be cured by exposure 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 and, for example, 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.

[0103] A radiation-curable silicone can be cured by exposure to an electron beam. Typically, 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, and 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^. Depending on the voltage, the time of exposure is typically from about 10 seconds to 1 hour.

[0104] Radiation-curable silicones that include a cationic or free radical photoinitiator can be cured by exposure to radiation having a wavelength of from 150 to 800 nm, alternatively from 200 to 400 nm, at a dosage sufficient to cure (crosslink). 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^. Moreover, the Radiation-curable silicone can be externally heated during or after exposure to radiation to enhance the rate and/or extent of cure.

[0105] Peroxide-curable silicones can be cured by exposure to a temperature of from room temperature (-23 ± 2 °C) to 180 °C, for a period of from 0.05 to 1 h. Epoxy-curable silicones can be cured by exposure it to a temperature of from room temperature (-23 ± 2 °C) to 180 °C, for a period of from 0.05 to 1 h.

[0106] A curable and/or non-curable silicone may be present with the polyheterosiloxane composition in a compatibilized silicone composition, wherein the terminology "compatibilized" describes that the polyheterosiloxane composition is "compatible" with the curable silicone, as described above. In one embodiment, the curable and/or non-curable silicone is present in an amount of at least about 50 weight percent based on a total weight of the compatibilized silicone composition. In various embodiments, the curable and/or non-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 compatibilized silicone composition. In other embodiments, the curable and/or non-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 compatibilized silicone composition. Similarly, the polyheterosiloxane composition may be present in the compatibilized silicone composition in amounts set forth above or in amounts of from 1 to 20, 2 to 19, 3 to 18, 4 to 17, 5 to 16, 6 to 15, 7 to 14, 8 to 13, 9 to 12, or 10 to 11, weight percent based on a total weight of the compatibilized 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.

[0107] This disclosure also provides a cured or uncured or partially cured compatibilized silicone composition. In one embodiment, the cured compatibilized silicone composition is the cured product of the aforementioned polyheterosiloxane composition including the polyheterosiloxane composition and the curable silicone described above. The cured or uncured or partially cured compatibilized silicone composition is not particularly limited and 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 or uncured or partially cured compatibilized silicone composition may be predetermined by selecting and customizing the polyheterosiloxane composition and the a curable or non-curable silicone, as well as the methodology and conditions used for preparation.

[0108] This disclosure also provides an article which is not particularly limited and may be any three dimensional article. 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. In various embodiments, the substrate, in whole or in part, includes or is paper, plastic, a polymer, metal, wood, glass, or combinations thereof.

[0109] In one embodiment, 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. In a non- limiting example, a mold having the shape of a hemi-spherical bowl may be utilized to produce an article having a shape of a spherical dome. Additionally, 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 μιη, or greater than 10 um.

[0110] 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 or uncured or partially cured compatibilized silicone composition, e.g. the cured product of the polyheterosiloxane composition including the curable silicone described above. In various embodiments, the coating has an average thickness of from 1 to 10, 2 to 9, 3 to 8, 4 to 7, or 5 to 6, μιη or cm. In other embodiments, the coating has an average thickness of from 10 to 100, 15 to 95, 20 to 90, 25 to 85, 30 to 80, 35 to 75, 40 to 70, 45 to 65, 50 to 60, or about 65, μιη. In still other embodiments, 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, μιη. In additional embodiments, 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, μιη. In further embodiments, 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, μιη. However, the coating is not limited to this thickness.

[0111] 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. EXAMPLES

[0112] The following examples are included to demonstrate various embodiments of the disclosure and are not limiting. All percentages are in weight % unless indicated otherwise. All measurements are conducted at 23°C unless indicated otherwise.

Test Methods:

2 Si Nuclear Magnetic Resonance Spectroscopy (NMR)

[0113] Samples for NMR analysis are prepared by introducing approximately

2 grams of sample into a vial and diluting with approximately 6 grams of 0.04M Cr(acac)3 solution in CDCI₃. Samples are mixed and transferred into a silicon-free NMR tube. Spectra are acquired using a 400 MHz NMR.

Example 1

[0114] 9.68g ZnAc₂.2H₂0, 61.3g butyl titanate polymer (BTP, DuPont

Tyzor^®), 52g toluene are charged to a 1 liter flask. A clear solution is obtained after the mixture is stirred at RT for lhour. Then, a prehydrolyzed siloxane is added. This solution is prepared by mixing 18.76g PhMeSi(OMe)₂, 8.09g 0.1M HCl (10% in 1- BuOH), and 15g toluene and sonicating the mixture for 30 minutes. After stirring at RT for 2.5 hours, the solution is heated to 85°C for 30 minutes and turns translucent. Then, the solution is cooled to RT and solvent are removed using a rotary evaporator. A white solid polyheterosiloxane composition (Tio_.64Zn_anD^Ph2o.₂5 (as determined using ²⁹Si NMR)) is produced and then dissolved in toluene at 45wt%. Subsequently, 20.2g of the polyheterosiloxane in toluene solution is mixed with lOg additional toluene, 2.12g OH-terminated polydimethylsiloxane (DMS12, Gelest, MW 400-700), and 7.00g OH-terminated polydimethylsiloxane (DMS21, Gelest, MW 4200) in a 100ml flask and stirred at 90°C for 1 hour. The solution is casted on glass slides. After solvent evaporation at RT for 2 hours, clear coatings including 50% Tio.6₄Zno.iiD^PhMeo.₂5 and 50% polydimethylsiloxane are obtained.

Example 2

[0115] 14.50g ZnAc₂.2H₂0, 61.1 lg BTP, 20g 1-BuOH, and 60g toluene are charged to a 1 liter flask. A clear solution is obtained after the mixture is stirred at RT for 2 hours. 34.45g Ph₂Si(OMe)₂ is added into the flask. Under stirring, a solution including 8.80g 0.1M HCl and 79.2g 1-BuOH is added into the flask slowly. After stirring at RT for 50 minutes, the solution is heated to 90°C for 15 minutes and turns translucent. Then, the solution is cooled to ~40°C. A solution including 0.79g 0.1M HCl and 7.1 g 1-BuOH is added to the flask quickly. The total amount of H₂0 is 145% of that which is needed for hydrolysis and condensation. The combined solution is then heated to 90°C again for 28 minutes. Subsequently, -69 g solvent is distilled off and the solution becomes translucent after cooling to RT. Finally, a remainder of solvent is removed using a rotary evaporator. A white solid polyheterosiloxane composition (Tio.56Zno.i4D^Ph2o.3o (as determined using ²⁹Si NMR) is produced and then dissolved in butyl acetate at 45wt%. Subsequently, 4.0 g of the above polyheterosiloxane solution is mixed with 1.8 g OH-terminated polyphenylmethylsiloxane (having a viscosity of 500 mm²/sec at 25°C)) and 2.2 g toluene in a vial. The clear solution is casted on glass slides. The coatings are dried at RT overnight and heated at 100°C for 30 minutes and then at 140°C for 1 hour. Clear coatings including 50% Tio.56Zno.i4D^Ph2o.₂5 and 50% polyphenylmethylsiloxane are obtained.

Example 3

[0116] 29.9g 10% Europium 2-ethylhexanoate toluene/ 1-butanol (ratio 7/1) solution is charged to a 250ml flask, along with O. lg 0.1M HCl and stirred 30 minutes. 4.38g tetraisopropyltitanate is then added and stirred at RT for 15 minutes and then 100°C for 20 minutes. Subsequently, a prehydrolyzed siloxanes solution is added. This solution is prepared by mixing 11.23g (A) as set forth below, wherein n is 10-12, 0.55g 0.1M HCl, 5.0g toluene, and 8.0g IPA and sonicating the mixture for 15 minutes. The clear solution is stirred at 60°C for 30 minutes and solvents are removed using a rotary evaporator at 60°C and 5 mmHg. The product is a clear light yellow viscous liquid, compatible with polydimethylsiloxanes, vinyl-terminated polydimethylsiloxanes, and OH-terminated polydimethylsiloxanes.

[0117] The terminology "compatible," as used in at least the Examples, describes that the polyheterosiloxane composition forms a stable homogeneous clear mixture, as visually evaluated, when combined with polysiloxanes after mixing.

(A) , n~10-12

Example 4

[0118] 29.9g 10% Europium 2-ethylhexanoate toluene/ 1-butanol (ratio 7/1) solution is charged to a 250ml flask, along with 0.09g 0.1M HC1, and stirred 30minutes. 4.38g tetraisopropyltitanate is then added and stirred at RT for 15 minutes, then heated to 100°C for 20 minutes and stirred. Subsequently, a prehydrolyzed siloxanes solution is added. This solution is prepared by mixing 11.37g (B) as shown below, 0.57g 0.1M HC1, 5.0g toluene, and 8.0g IPA and sonicating the mixture for 15 minutes. The clear solution is stirred at 60°C for 30 minutes and solvents are removed using a rotary evaporator at 60°C and 5 mmHg. The product is a clear yellow viscous liquid, compatible with phenylmethyl cyclic siloxanes, vinyl-terminated polypheny lmethylsiloxanes, and OH-terminated polyphenylmethylsiloxanes.

Example 5

[0119] 10.80g 10% Cerium 2-ethylhexanoate toluene solution is charged to a

250ml flask, along with 3.67g aluminum sec-butoxide/sec-butanol solution (2.5mmol Al g). A clear yellow solution is obtained after stirring at 90°C for 30 minutes. A prehydrolyzed siloxanes solution is then added. This solution is prepared by mixing 20. lg (C) as shown below, lO.Og octyltrimethoxysilane, 2.0g 0.1M HC1, 16.5g IPA, and 5.2g toluene and sonicating the mixture for 15 minutes. The clear solution is stirred at 90°C for 2.5 hours and solvents are removed using a rotary evaporator at 90°C and 8 mmHg. The product is a clear brown viscous liquid, compatible with polydimethylsiloxanes, vinyl-terminated polydimethylsiloxanes, and OH-terminated polydimethylsiloxanes .

Example 6

[0120] 6.05g Europium 2-ethylhexanoate, 50g toluene, and 20g IPA are charged to a 250ml flask along with 0.36g 0.1M HCl and stirred 30 minutes. 8.35g tetraisopropyltitanate is then added and stirred at 85°C for 30 minutes. A prehydrolyzed siloxanes solution is then added. This solution is prepared by mixing 30.0g (C), 15.0g octyltrimethoxysilane, 2.34g 0.1M HCl, 18.0g IPA, and 6.5g toluene and sonicating the mixture for 20 minutes. The solution is then heated to reflux for 30 minutes, 60g solvents are distilled, and the solution is cooled to RT. The solution is then filtered through 0.45 μιη filter and remaining solvents are removed using a rotary evaporator. A hazy liquid is obtained, compatible with polydimethylsiloxanes, vinyl- terminated polydimethylsiloxanes, and OH-terminated polydimethylsiloxanes.

Example 7

[0121] l.Og of the polyheterosiloxane product from Example 5 is mixed with

8.1g 165DP polydimethylsiloxane, 0.19g 65DP methylhydrogensiloxane, and 1 drop of 6000 ppm Pt catalyst in a dental cup. After complete mixing the mixture is cured in a glass dish at 120°C for 10 minutes. A clear elastomeric article is formed.

Example 8

[0122] Example 7 is repeated except that the polyheterosiloxane product from

Example 3 is used in place of the polyheterosiloxane product from Example 5. In this example, a clear elastomer article is also formed

Example 9 - Synthesis of (Me^SiO)_?MeSiCH_?CH_?Si(CH _?OSi(C_fi¾)_?(OMe)

[0123] In a typical synthesis of ViMe₂SiOSiPh₂(OMe), 151.8g divinyltetramethyldisiloxane, 100.3g Ph₂Si(OMe)₂ and 0.40g triflic acid (FC-24 )are mixed in a 1 liter flask and stirred for 1 hour at 50°C and 5 hours at RT. 2.0g CaC0₃ is added to the flask and stirred at RT for overnight. Then, the mixture is pressure filtered through a 0.45μιη filter. The recovered material is subjected to rotary evaporation and ViMe₂Si(OMe) and unreacted divinyltetramethyldisiloxane are removed at 50-60°C and 0.3-0.5 mmHg. 117.6 g material is collected in a 3-neck flask. The flask is then heated to 90°C and O.lg 1% Pt is added to the flask. Under stirring, 70.8g (Me₃SiO)₂SiMeH (MD^HM) is slowly added into the flask in approximately 30 minutes. FTIR is used to monitor the SiH content of the mixture after 15 minutes and it is determined that the SiH is approximately completely consumed. 1.6g MD^HM is then added to the flask and stirred at 110°C for 30 minutes. FTIR reveals a weak SiH peak at -2148 cm^"1.

[0124] A thin film evaporator (Pope Scientific) is then used to purify the product. A 1^st run is set at 120°C and 0.4-0.5 mmHg. Unreacted Ph₂Si(OMe)₂ and small amount of MD^HM are removed. A 2^nd run is set at 210°C and 0.4-0.5 mmHg. The product, (Me₃SiO)₂MeSiCH₂CH₂Si(CH₃)₂OSi(C₆H5)₂(OMe) is separated from yellow residue.

Example 10- Synthesis of Polyheterosiloxane Composition using MeaSiO)₇MeSiC¾CH₇Si(C¾)₇.OSi(Cfi¾)₇.(OMe)

[0125] First, 29.9g europium 2-ethylhexanoate (10% in toluene) is transferred to a 100ml flask, then 0.090 g 0.1 M HCl is added to the flask. It turned clear after stirring for 10 minutes. l.Og toluene and 4.40g tetraisopropoxide (TPT) are added to the flask and stirred at 60°C for 40 minutes. Then a prehydrolyzed monofunctional siloxane solution is added. This solution is prepared by mixing 12.40g (Me₃SiO)₂MeSiCH₂CH₂Si(CH₃)₂OSi(C₆H5)₂(OMe), 0.67g 0.1 M HCl, and 9.0g IPA and sonicating for 10 minutes at RT. The solution is clear and stirred at RT for 10 minutes. Volatile components are removed using a rotary evaporator at 60°C and 0.5 mmHg for 30 minutes. A clear yellow photoluminescent liquid is transferred to a glass vial. Eu element content is estimated to be 4.9% based on the weights of raw materials and final product.

[0126] The product is compatible with polydimethylsiloxanes (350 cSt DOW

CORNING^® 200 fluid), vinyl-terminated polydimethylsiloxanes (DOW CORNING^® SFD 119 Fluid), OH-terminated polydimethylsiloxanes (having a viscosity of 40 mm²/sec at 25°C), vinyl-terminated polyphenylmethylsiloxanes (M^VlD^PhMe ₂5M^Vl), and OH-terminated polyphenylmethylsiloxanes (having a viscosity of 500 mm²/sec at 25°C). [0127] The aforementioned examples demonstrate that the compatibilizing organosiloxanes increase the compatibility of polyheterosiloxane compositions with various polysiloxanes and that this compatibility can be maintained even upon curing.

[0128] One or more of the values described above may vary by ± 5%, ± 10%,

± 15%, ± 20%, ± 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. The disclosure is illustrative including words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced otherwise than as specifically described herein.

[0129] In various non-limiting embodiments, 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 U.S. Provisional Patent Application Serial Numbers 61/662,199; 61/662,201 ; 61/662,171 ; 61/662,192; 61/662,180; 61/662,249; 61/662,264; 61/662,276; 61/782,628; 61/782,230; 61/784,581 ; 61/783,036; 61/784,311 ; 61/851 ,990; 61/783,797; 61/781,808; 61/781 ,818; 61/781,827; 61/785,834; 61/786,102; 61/784,741 ; 61/785,352; 61/784,823; and/or 61/785,134, each of which is expressly incorporated herein by reference in its entirety in one or more non- limiting embodiments. Moreover, this application expressly claims priority to each of the immediately aforementioned U.S. Provisional Patent Applications independently.

Claims

CLAIMS What is claimed is:

1. A polyheterosiloxane composition comprising:

(A) a first metal (Ml),

(B) a second metal (M2),

(C) siloxy units having the formula (R² ₃SiOi ₂), (R^SiO^), (R¹Si0_{3 2}), and/or (Si0_4/2),

wherein each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms,

wherein each R² is independently a hydrocarbyl group having from 1 to 20 carbon atoms or an organosiloxane having at least one disiloxy unit,

wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R² ₃Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si0_3/2]_t[Si0_4/2]_q,

wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from 0.001 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,

wherein d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1.

2. The polyheterosiloxane composition of claim 1 wherein at least one of R² is a Ci to do hydrocarbyl group.

3. The polyheterosiloxane composition of claim 1 wherein at least one of R² is phenyl.

4. The polyheterosiloxane composition of claim 1 wherein at least one of

R² is

-CH₂CH₂[(CH₃)₂SiO]_nOSi(CH₃)₂(CH₂)₄CH₃, wherein n is from 3 to 50.

5. The polyheterosiloxane composition of claim 1 wherein at least two of R² is phenyl.

6. The polyheterosiloxane composition of claim 1 wherein [R² ₃SiOi_/2] has the formula

Si (C₆H₅)₂ {CH₂CH₂[(CH₃)₂SiO]_nOSi(CH₃)₂(CH₂)₃CH₃}Oi/₂ wherein n is 3 to 50.

7. The polyheterosiloxane composition of claim 1 wherein at least one R² is

-CH₂CH₂Si(CH₃)(OSi(CH₃)₃)₂.

8. The polyheterosiloxane composition of claim 1 wherein [R² ₃SiOi_/2] has the formula Si(C₆H₅)₂ {CH₂CH₂Si(CH₃)(OSi(CH₃)3)2}0_1/2.

9. The polyheterosiloxane composition of claim 1 wherein one of R² is methyl and another of R² is phenyl.

10. The polyheterosiloxane composition of claim 1 wherein one of R² is vinyl.

11. The polyheterosiloxane composition of claim 1 wherein two of R² are -CH₂CH₂Si(CH₃)(OSi(CH₃)₃)₂.

12. A polyheterosiloxane composition of claim 1 further defined as the reaction product of:

(A') a metal (M3) alkoxide,

(B ') an optional hydrolyzable metal (M4) salt,

(C) silicon-containing material having silicon-bonded hydroxy groups,

(D) a compatibilizing organosiloxane having at least one [R² ₃SiOi_/2] unit and having a weight average molecular weight (M_w) of less than 10,000 g/mol, and

(E) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (AO and optionally (B ,

wherein each R² is independently a hydrocarbyl group having from 1 to 20 carbon atoms or an organosiloxane having at least one disiloxy unit.

13. The polyheterosiloxane composition of claim 12 wherein the compatibilizing organosiloxane has an average formula chosen from:

DI)

(R'0)(C₆H₅)₂SiCH₂CH₂[(CH₃)₂SiO]_nOSi(CH₃)₂(CH₂)₃CH₃,

DII) (R' 0)(C₆H₅)₂SiCH₂CH₂Si(CH₃)(OSi(CH₃)₃)₂,

Dili) (R' 0)₃SiO(CH₃)₂Si[(CH₃)₂SiO]_mOSi(CH₃)₂(CHCH₂), or

DIV)

(R'0)(C₆H₅)₂SiOSi(CH₃)₂CH₂CH₂Si(CH₃)(OSi(CH₃)₃)₂, wherein each n is independently from 10 to 12, each m is independently from 20 to 30, and each R' is a Ci to C₄ alkyl group.

14. The polyheterosiloxane composition of claim 12 wherein the compatibilizing organosiloxane has the average formula:

wherein n is from 3 to 50.

15. The polyheterosiloxane composition of claim 12 wherein compatibilizing organosiloxane la:

16. The polyheterosiloxane composition of claim 12 wherein compatibilizing organosiloxane has the average formula:

wherein n is from 3 to 100.

17. The polyheterosiloxane composition of claim 12 wherein the compatibilizing organosiloxane has the formula: (Me₃SiO)₂MeSiCH₂CH₂Si(CH₃)₂0Si(C₆H₅)₂(OMe).

18. The polyheterosiloxane composition of claim 12 wherein the compatibilizing organosiloxane has the formula: (R⁸ ₃SiO)_n(R³⁸)(3__n) Si-R⁹- Si(R⁸)₂OSi(R¹⁰)₂X

wherein n is 1 or 2, each R⁸ is independently a monovalent Ci to C2₀ hydrocarbyl, each R⁹ is a divalent C2 to C₁₂ hydrocarbyl, each R¹⁰ is independently a monovalent Ci to C30 hydrocarbyl having at least one aryl group, X is a hydrolyzable group chosen from -OR , CI, -OC(0)R , -N(R^U)₂, and -ON=CR¹ and wherein R is hydrogen or a Ci to C₆ alkyl group.

19. A compatibilized silicone composition comprising polyheterosiloxane composition of any preceding claim and a silicone.

20. A method of forming the polyheterosiloxane composition of any preceding claim comprising the step of reacting:

(A') a metal (M3) alkoxide,

(B ') an optional hydrolyzable metal (M4) salt,

(C) silicon-containing material having silicon-bonded hydroxy groups

(D) a compatibilizing organosiloxane having at least one [R² ₃SiOi/₂] unit and having a weight average molecular weight (M_w) of less than 10,000 g/mol, and

21. A method of forming a polyheterosiloxane composition comprising the step of reacting:

(AO a metal (M3) alkoxide,

(B 0 an optional hydrolyzable metal (M4) salt,

(CO silicon-containing material having silicon-bonded hydroxy groups,