WO2014152392A1

WO2014152392A1 - Composition including a polyheterosiloxane and an organosiloxane block copolymer

Info

Publication number: WO2014152392A1
Application number: PCT/US2014/027290
Authority: WO
Inventors: David Deshazer; Martin Grasmann; John B. Horstman; Lizhi Liu; Nanguo Liu; Elizabeth Mcquiston; Shawn MEALEY; Randall Schmidt; Kwan SKINNER; Steven Swier
Original assignee: Dow Corning Corporation
Priority date: 2013-03-14
Filing date: 2014-03-14
Publication date: 2014-09-25
Also published as: TW201500473A; WO2014152824A1

Abstract

A composition includes a combination of a (I) polyheterosiloxane composition and a (II) organosiloxane block copolymer. The (I) polyheterosiloxane composition includes at least one lanthanide metal and siloxy units having the formula (R¹ ₃SiO_1/2), (R¹ ₂SiO_2/2), (R¹SiO_3/2), and/or (SiO_4/2). Each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms. The (II) organosiloxane block copolymer includes 40 to 90 mole percent dlsiloxy units of the formula [R^a ₂SiO_2/2] arranged in linear blocks each having an average of from 10 to 400 disiloxy units [R^a ₂SiO_2/2] per linear block. The (II) organosiloxane block copolymer also includes 10 to 60 mole percent siloxy units arranged in non-linear blocks each having a weight average molecular weight of at least 500 g/mol wherein at least one siloxy unit is a trisiloxy unit of die formula [R^bSiO_3/2]. R^a is independently a C₁ to C₃₀ hydrocarbyl and R^b is independently a C₁ to C₂₀ hydrocarbyl.

Description

jjOOOl] Various metals luminesce due to their electronic structures. However, the use of these metals in luminescent materials is typically limited by standard energetic high temperature synthesis and blending and also by quenching of luminescence at high metal concentration. Quenching can occur above a threshold metal concentration where metal ions are allowed to aggregate and subsequent coordinate changes in the electronic structure can lead to non-radiative routes to ground including cross relaxation. In some cases, excited state absorption can lead to quenching. Undetermined mechanisms, typically described as concentration quenching, may also occur. The threshold concentration for quenching can be as low as 1%, limiting the brightness of luminescent materials. Accordingly, there remains an opportunity to develop improved materials.

SUMMARY OF THE DISCLOSURE

[0002] This disclosure provides a composition that includes a combination of a (I) poivheterosiloxane composition and a (II) organosiloxane block copolymer. The (I) poivheterosiloxane composition includes at least one lanthanide metal and siloxy units having the formula (R^SiG^), (R^SiO^), (R³Si(>v2), and/or (SiO^). In these formulae, each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms, In addition, the mole fractions of the at least one lanthanide metal and the siloxy units relative to each other is of the formula [at least. one lanthanide rnetal]a[ ⁱ SiOi 2]_m[R-ⁱ ₂Si0₂ 2]_d[RⁱSi0₃/2]t[Sii)4/2]q, wherein a is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9, and wherein m, d, t, and q cannot all be zero arid the sum of a+m+d+t+q « 1. The (II) organosiloxane block copolymer includes 40 to 90 mole percent disiloxy units of the formula [R^a ₂SiC½] arranged in linear blocks each having an average of from 10 to 400 disiloxy units [R^SiO^] per linear block. The (II) organosi loxane block copolymer also includes 10 to 60 mole percent siloxy units arranged in non-linear blocks each having a weight average molecular weight, of at least 500 g/rnol wherein at least one siloxy unit is a trisiloxy unit of the formula [R^bSiO:v2]. hi these formulae, R^s is independently a Ci to C30 hydrocarbyl and R is independently a Ct to C>o hydrocarbyl. Moreover, each linear block is linked to at least one non-linear block.

I BRIEF D ES PTIOM OF THE FIGURES

[0003] Figure 1 shows the excitation and emission spectrum for a Si+Ti+Eu resin as described in Example 1 with a 10 percent weight loading in Ph~T 120 dp PhMe Resin-Linear Copolymer.

[0004] Figure 2 shows the emission spectra for a Ph-T dp PhMe Resin-Linear copolymer with the Tio_.sEuo.iZno_.i resin described in Example 1 at varying weight percent loadings in a Ph-T 120 dp PhMe Resin-Linear Copolymer.

[0005] Figure 3 shows the excitation spectra of the same material described in Example 1 at varying weight percentage loadings in a Ph-T 120 dp PhMe Resin-Linear Copolymer.

DETAILED 1>ESC IPTIQN OF THE DISCLOSURE.

[0006J This disclosure provides a composition that includes a combination of a (I) poiyheterosiloxane composition and a (11) organosiloxane block copolymer. The combination is a physical combination or mixture of (I) and (11). Each of (Ϊ) and (ΙΪ) can he mixed or combined in any way. For example, (I) and (II) may be combined in a mixer, extruder, reactor, etc. The composition may be, include, consist essentially of, or consist of (I) and (II). In one embodiment, the terminology "consist essentially of^* describes that the composition is free of any polymer, silicone and/or organic, that is not (I) and/or (II), However, it is contemplated that the composition may consist essentially of (1) and (II) and be free of or include one or more photosensitizers. compaiibilizers, and/or curable or non-curable silicones, as described below. Each of (I) and (II) Is described below, it is contemplated that, in some non-limiting embodiments, the terminology "composition" and "poiyheterosiloxane composition" may be used interchangeably below, e.g. relative to amounts of components, physical properties, etc. (I) P lyhetez sHoxaB¾ Comp sif ion.

[0007] The poiyheterosiloxane composition includes at least one lanthanide metal which may be any known in the periodic table. In one embodiment, the poiyheterosiloxane composition includes two or more lanthanide metals.

[0008] In another embodiment, the poiyheterosiloxane composition includes (A) a first metal (M1 ), (B) a second metal (M2), and (C) siloxy units having the formula (R^SiC^),

(R^fSi0₃ 2), and/or (8ί(½), wherein at least one of (Ml.) and (M2) is a lanthanide metal [Θ009] The poiyheterosiloxane composition may include one (A) first metal (Ml ), two first metals (Ml), or a plurality of first metals (Ml), In various embodiments, the first metal (Ml) is not particularly limited and may be a lanthanide metal or a non-ianthanide metal, so long as at least one of (Ml) and (M2) is a lanthanide metal (Ml) may be chosen from Ti, Zr, Al, and Zn, or Ti, Zr, and Al, or Ti, Al, W, Ge, Zr, H£ 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, Trn, 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. Any one or more of the aforementioned metals may be used singly or in combination with themselves or any one or more metals described below. Similarly, any one or more of any metals described below may be used single or in combination with themselves or any one or more of the aforementioned metals.

[0010] in other embodiments, (Ml) may be a non-Ianthanide metal, so long as at least one of (Ml) and (M2) is a lanthanide metal For example, (Ml) may be chosen from Al, Zr, and combinations thereof, in one embodiment, (Ml) is Al. In another embodiment, (Ml) is Zr. in still another embodiment, (Ml) is a combination of Al and Zr.

[0011] The oxidation state of ( l) 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 ( l) may independently have the same or different oxidation states.

[0012] The polyheterosiloxane composition may include one (B) second metal (M2), two second metals (M2), or a plurality of second metals (M2). In various embodiments, the second metal (M2) Is not limited, so long as at least one of (Ml) and (M2) is a lanthanide metal In one embodiment, each of (M i ) and (M2) are independently lanthanide metals and are different from each other. In another embodiment, one of (MI) and (M2) is a lanthanide metal and the other of (Ml) and (M2) is a non-lanthanide metal.

[Θ0.13] In other embodiments, one of (Ml) and (M2) is non-lanthanide metal, e.g. chosen from aluminum (Al), zirconium (Zr), and combinations thereof, and the other of the two is a lanthanide metal

[0014] In various embodiments, (M2) may be one or more of those metals described above or may be any other metal in the periodic table, so long as at least one of (Ml) and (M2) is a lanthanide metal. (M2) may be a lanthanide metal or a non-lanthanide metal. For example, (M l ) and (M2) may be one of the following: First Metal (Ml)

Lanthanide Metal Non-Lanthanide Metal

One or more Lanthanide Metals and one or

Noii-Lanthanide Metal

more Non-Lanthanide Metals

Non-Lanthanide Metal Lanthanide Metal

One or more Lanthanide Metals and one or

Non-Lanthanide Metal

more Non-Lanthanide Metals

One or more Lanthanide Metals and one or One or more Lanthanide Metals and one or more Non-Lanthanide Metals more Non-Lanthanide Metals

Lanthanide Metal Lanthanide Metal

Aluminum Lanthanide Metal

Zirconium Lanthanide Metal

Combination of Aluminum and Zirconium Lanthanide Metal

Lanthanide Metal Aluminum

Lanthanide Metal Zirconium

Lanthanide Metal Combination of Aluminum and Zirconium

Typically, each of (Ml) and/or (M2) may independently include one or more lanthanide and/or non-lanihanide metals, singly or in combination, so long as at least one of (Ml) and (M2) is a lanthanide metal. In one embodiment, more than one lanthanide metal may be utilized. A mixture of non-lanthanide metals may be utilized 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, so long as at least one of (Ml) and (M2) is a lanthanide metal One or more of (Ml) and (M2) may be Eu ^÷. For example, the polyheterosiloxane composition may include Eu^J+ and exhibit excitation and emission transitions between the ^SD and 'F energy levels in the 4f orbital. A principal excitation line may be observed at approximately 395 nm and principal emissio 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.

[0015] The polyheterosiloxane composition also includes (C) siloxy units having the formula

and/or (S1O4 2). These units may be alternatively described as organopolvsiloxane 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 ¹⁴T" units, "M" and "Q" units, "D" and "T" units, "D" and "Q" units, or "T" and "Q" units, and/or combinations thereof In any of the embodiments described herein above or below, it is contemplated that (Ml) and/or (M2) may describe the at least one lanthanide metal introduced above. However, the invention, of course, is not limited to any such embodiment.

[00161 Each R^s 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, 1 1 , 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 R⁵ may be the same or different from any other R¹. Non- limiting examples include methyl, ethyl, propyl, butyl, pentyl, hex l, heptyl, octyl, undecyL octadeeyl, cyclob.ex.yl, aryl, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl, halogenated hydrocarbon, 3,3,3-trifiuoropropyl, 3-chloropropyl, and dichlorophenyl, groups. At least one of R^l 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.

[0017] The (C) siloxy units may include greater than 50 mole or weight percent of R'SiC^ siloxy units where R^f is phenyl; R^SiO^ siloxy units where one R¹ substituent is phenyl, and the other * substituent is methyl; or R^SiG?_/?. and R^!Si0.v2 siloxy units where one R¹ substituent in the R^SiO^ siloxy unit, is phenyl, and the other R¹ substituent is methyl, and where R⁵ is phenyl in the R^iC siloxy unit. One or more siloxy units may have the formula [iQ¾)SiC½]d, [(C₆H5)₂SiO_ml_d[(C₆H₅)Si03/₂ ^"Jt, or [(Ce₃)(C₆H₅)Si0_2¾]_d

[0018] 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, naphtoaies, and acetates, and/or one or more components used to form the polyheterosiloxane composition.

[0019] The varied amounts of each of the at least one lanthanide metal and/or (A), (B), and (C) are typically described relative to mole fractions of each to a total number of moles, e.g. of (A), (B), and (C). For example, the mole fractions of the at least one lanthanide metal, and the siloxy units in the poiyheterosiloxane composition relative to each other may be of the formula [At least one Lanthanide Metai]_a [R^l3Si()i 2]_m[ ¹2Si0₂/2]d[RⁱSi03/2]t[Si0₄/2]_q. In another embodiment, (A), (B). and (C) in the poiyheterosiloxane composition relative to each other is of the formula [(Ml)]_a[(M2)]_b[R^!3SiOi./2]_m[Rⁱ2Si02/2]d[R³SiC:)3_/2]_t[Si0₄/2]q. The subscript m denotes the mole fraction of the optional "M" unit (R^SiOi^). The subscript d denotes the mole fraction of the optional "D" unit

The subscript t denotes the mole fraction of the optional "T" unit (R³SiO;v₂). The subscript q denotes the mole fraction of the optional "Q" unit (SiO^).

[0020] 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 he from 0.1 to 0.9 and b may be from 0.001 to 0,5. The total metal content of the poiyheterosiloxane composition,

1. 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.

[ΘΘ21] m is typically from zero to 0.9, 0,1 to 0.6, or 0.2 to 0,5 or any value or range of values therebetween, d is typically from zero to 0.9, 0.1 to 0,5, or 0,1 to 0.3 or any value or range of values therebetween. Each o 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, m, d, t, and q cannot all be zero and the sum of a+b+m+d+t-i-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 poiyheterosiloxane composition may include residual amounts of groups that, are not described by the aforementioned formula. The poiyheterosiloxane composition may include up to about 5 mole percent of other units, such as those that include Si~OH bonds.

[0022] The poiyheterosiloxane composition may have a formula [(Ml)]_a[(M2)]_b[Rⁱ ₃SiOi/2]_m[R¹2Si0₂/2]d [R^lSi0₃/2]i[Si0.₁/₂]_q, wherein Ml is a combination of metals, e.g. Ti and Zn, a is 0.12, b is 0.08, m is zero, d is 0.6, t is 0.2, and q is zero, . Alternatively, Ml may be a single metal, e.g. Ti, wherein a is 0.6, b is 0,05, m is zero, d is

0.2675, and T is 0.0825, or, e.g. Ti, wherein a is 0.5, b is 0.2, m is zero, d is 0,225, t is 0.075, and q is zero, e.g. so long as at least one of (Ml) and (M2) is a lanthanide metal. The polyheterosiloxane composition may have one of the following formulas,

Tio, j Zrio.osEuo.osDo.e^'f 0.2; i0.6Eu0.0sD0.2675 0.0825; Ti0.5Eu0.2D .22sT0.075; or Tio.4Euo.4Do.15To.05-

Therein, a may be from 0.1 to 0.8, b may be from 0.05 to 0.5, e may be from zero to 0.8, d may be from zero to 0.8, with the provisos thai c and d both cannot be zero and the sum of a+b+c+d ~

1, and wherein at least one of (Ml) and (M2) is a lanthanide metal.

[0023] 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 ²⁹Si liquid or solid state NMR, ⁸Ti NMR, ²⁷ Ai NMR, FT-!R, 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.

ΘΘ24] The polyheterosiloxane composition may also include from ί 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, aikoxy groups. Residual aikoxide (-OR) groups may also be present in polyheterosiloxane structures and may be bonded to (Ml) and Si, as determined using ²⁹Si and ^I3C NMR, e.g, in an organic solvent. Residual counter ions from metal salts may also be present and may be bonded or chelated to (MI) and (M2).

[002SJ One or more atoms of the at least one lanthanide metal, e.g. (Ml) and/or (M2), may^¬ be bonded to the same or different silicon atoms, e.g. through an oxygen bond. Typically, 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 (M l ) 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 substituenis bonded thereto such as residual or un-reaeted substituents used to form the polyheterosiloxane composition. [0026] 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-OM1 or M2-0-ML Atoms of (M2) may also have a one or more substituents bonded thereto such as residual or un-reacied substituents used to form the polyheterosiloxane composition,

[0027] 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-Q-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.

[0028] The polyheterosiloxane composition may have "metal-rich" domains and "siloxatie- 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-S1). As used herein, the terminology "siloxane-rich" describes structural segments wherein a plurality of bonds are siloxane (Si-O-Si) bonds. The "meta!-rieh" 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-O-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 ^{, 7}0 NMR,^4STi NMR and/or ²'A1 NMR may increase resolution or ability to quantify Si-O and Lanihanide-O bonds.

[0029] 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,

[ΘΘ30] 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,

[0031] 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 (F1.PA).

[0032] The polyheterosiloxane composition is typically photoluniinescent and may emit visible or ultraviolet light when exposed to, or excited by, visible or ultraviolet light. The polyheterosiloxane composition typically exhibits a quantum yield of at least 0.05%, as determined using the formula described in greater detail below, In various embodiments, the polyheterosiloxane composition exhibits a quantu 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, 1 5, 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, %.

[0033] A limited size of the metal rich domains may lead to enhanced photolumineseence. For example, concentrations of lanthanide ions may exceed conventional concentration quenching thresholds without reduction in quantum yield. Photolumineseence may be assessed by measuring the absorption specimm, the photoluminescent emission (PL) spectrum, or the photoluminescent excitation (PLE) spectrum of the polyheterosiloxane composition. The absorption spectrum may be measured with standard spectrometers such as a Varian Carry 5000 spectrophotometer (Agilent Technologies, Palo Alto, CA, USA). The PL excitation and emission spectra may be measured using a spectrofluorometer. Any spectrofluorometer recognized in the art. e.g. the Fluorolog-2 or -3 spectrofluorometer (FL2 or FL3) (HORIBA Jobin-Yvon inc. Edison, NJ, USA), or any one or more described below may be utilized to determine any one or more physical properties described herein.

[0034] 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 fiher-optically coupled to an approximately 4 cm integration sphere, illuminated by a light emitting diode (LEO) and rim by Ocean Optics' Spectra Suite software (Ocean Optics, Dunedin, FL, USA). Alternatively, equipment such as Fluorolog- 2 or -3 spectrofiuorometers (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.

[0035] in various embodiments, the absorption and emission of a sample are measured under the illumination of an LED with a center wavelength of 395 am. 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.

[0036] The polyheierosiloxane 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 polyheierosiloxane 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%.

[0037] 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 1 100 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.

[0038] 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 tenets to be reduced. Narrow band red emission at approximately 615 nra balances strong red emission for suitable color rendering with visually bright emission. For example, polyheterosiloxane compositions that include SREir^rr resin phosphors tend to exhibit a CLE 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.

0039J The 1931 CIE (International Commission on illumination) color space is defined by tristimulus values, X, V 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 = j l (A)x^< (A)d,i

0

Υ = \ ΐ(λ)? (λ)άλ

0

wherein x '(A), y '(λ) and z '{λ) are color matching functions with peaks at approximately 450 nm, 550 nm and 600 nm. respectively, and 1(1) 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+ ¥+Z), and

Z/(X+Y+Z) and b inspection x i y - z 1 .

[Θ040] Steady state emission and excitation measurements are typically collected using a Boriba 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 Ivlems 'Accuracy in Spectrophotometry and Luminescence Measurements', NBS Special Publications p. 378 (1 73), 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 (Re). An intensity standard reference material (2940-C from NIST) is used to monitor variations in the photomultiplier tube detector (P T) signal (Rs). Then the excitation/emission spectra are typically reference corrected for both variations in intensities in the excitation source and variations in the phoiomuitiplier 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 nrn, 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.

[0041] Absorption spectra are typically determined by monitoring the strongest absorption peak of the polyheterosi (oxane composition, e.g. Si+Eu^J' luminescent silicones via population of the ³L₆ 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 conten of the polyheterosiloxane composition.

[ )042] 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:

wherein QY is the quantum yield of the sample, QY_f is the quantum yield of the reference, A is the absorbance at the excitation wavelength λ. n is the retractive 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 LO N sulfuric acid can be used as a reference with an excitation at 340 nm and will produce emission between 370 am and 660 nm. This solution has an established quantum yield of 0.546. Other references include fluorescein (470 nm excitation, 480-700 nm emission, QY 0.91) and rhodamine (535 nm excitation, 550 - 750 nm emission, QY 1 ,00), These reference materials are all commonly used and referenced in the literature, e.g. in Eaton, D., International Union of Pure and Applied Chemistry Organic Chemistry Division Commission on Photochemistry; and/or the Journal of photochemistry and photobiology. B, Biology, 1988. 2(4); p. 523, each of which are expressly incorporated herein by reference relative to these particular materials.

[0043] The polyheterosiloxane composition may also have an asymmetry ratio, typically in an embodiment utilizing Eir⁺, 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, froni 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) speetroftuorometer by measuring the ratio of the peak emission value of the ¾o→ ¾ transition at 614 nm to the ^'Do → ⁷F_f 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.

[0044] Asymmetry ratios can be calculated by measuring a ratio of a peak emission value of the polyheterosiloxane composition, e.g. of the ⁵Do→ ¾ transition at 614 nm to the ¾o→ ⁷F| transition at 590 nm, which correspond to electric and magnetic dipoles, respectively, in one embodiment, the ⁵Do→ 'F₂ transition is a "hypersensitive'^' electric dipole, and is very sensitive to the local electric field surrounding a lanthanide ion. e.g. Eu^'+ ion. The ⁵Do→ 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 thai 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 Ianthanide metals as well.

[0045] The polyheterosi ioxane 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 polyheterosiioxane composition, e.g. a EuTiZnSi polyheterosi!oxane composition, may be from 2.43 to 2.73 using a FhiroIog-3 fluorescence spectrometer and a photo-multiplier tube detector. Radiative lifetime measurements may be calculated according to the method described below.

[0046] Radiative lifetimes can be calculated from a corrected emission spectrum of a polyheterosiioxane composition in lieu of using Judd-Ofelt theory, known in the art, because the corrected emission spectrum from a spectrofluorometer is representative of relati e photon flow vs. wavelength. For example, the ¾ο → ⁷F{ 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 ¾o→ ⁷F-_; transition, the shape of the emission spectrum of an Ianthanide ions, e.g. Eu³⁺, center can be related to its radi

wherein ¾ is the radiative lifetime

art as approximately 14.65 s^" ) is the spontaneous emission probability of the ¾>→ 'Fi transition for an Eu³⁺ center in vacuum, n is the refractive index of the medium, and I_MD is the ratio of the corrected emission spectrum of the material to the emission of just the magnetic dipole transition. Just as abo ve, the same or similar calculations can be made for other Ianthanide metals.

[0047] The polyheterosiioxane 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.

[0048] 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 ixrn 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 lends to be from three independent measurements. Typical sample concentrations typically include 5% wt solids in solvents containing toluene and optionally 1 -butanol to improve solubility. Measurements can be performed in 1 cm square quartz cuvettes, or equivalents.

[Θ049] 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 R spectrometer. The spectra can be collected by directly measuring powder samples via attenuated total reflection (ATR) using a ZnSe or diamond cell.

[Θ05Θ] The polyheterosiloxane composition, and/or the composition as a whole, may include a silicone fluid, e.g. a non-curable silicone fluid, as appreciated in the art. The silicone fluid is typically EDMS 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.

[0051] Non-limiting examples of linear silicone fluids suitable for use herein include irirnethylsiloxy-terrninaied dimeihylsiloxane 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 trimethyisiloxy-terminated polydimethylsiloxane having a viscosity of about 0.1 Pa s at 25 °C. |0052] Additional non-limiting examples of suitable cyclic silicone fluids include the cyclic polydimethylsiloxanes sold by Dow Corning Corporation under the trade names "Dow Corning¹* 244, 245, 344, and 345 Fluids", depending on the relative proportions of octamethyleyclotetrasiioxane and deeamethylcyelopeniasiloxane. 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 (GSiMe₃)MeSiO]SiMe₃.

[0053] The polyheterosiloxane composition and/or the composition as a whole may include, includes less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 , or 0.5, weight percent of, or be free of, a curable silicone and/or an organic matrix, e.g. a curable organic composition. Curable silicone and/or organic matrices of such embodiments may be as described in one or both of U.S. Ser. Nos. 61 /662,201 and 61/662,192, each of which are expressly incorporated herein by reference in one or more non-limiting embodiments.

(II)_n Qrj*a¾fldioxans Block Co ol¾|$er

[0054] The organosiloxane block copolymer may also be described as a "resin-linear" organosiioxane block copolymer. Qrganopolysiloxanes are polymers typically including siloxy units independently chosen from (R SiOi_/2 ), (RaSiOz^), (RSi0_{3 2}), or (S1O4/2) siloxy units, where R may be any organic group. These siloxy units are commonly described as M, D, T, and Q units respectively. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures vary depending on the number and type of siloxy units in the organopolysiloxane.

[0055J "Linear" organopolysiloxanes typically include mostly D or (¾8Κ>_{2 2}.) siloxy units, which results in polydiorganosiloxanes that are fluids of varying viscosity, depending on the "degree of polymerization" or DP as indicated by the number of D units in the polydiorganosiloxane. "Linear" organopolysiloxanes typically have glass transition temperatures (T_g) that are Sower than 25°C.

[0056] "Resin" organopolysiloxanes include a weight or molar majority of T or Q siloxy units. When T siloxy units are predominately used to prepare an organopolysiloxane, the resulting organosiloxane is often described as a "silsesquioxane resin". Increasing the amounts of T or Q siloxy units in an organopolysiloxane typically results in organopolysiloxane copolymers having increasing hardness and/or glass like properties. "Resin" organopolysiioxanes typically have higher T_g values than linear organopolysiioxanes. For example, organopolysiloxane resins often have T_g values greater than 50°C.

[00S7J As described above, the orgaiiosiloxane block copolymer may also be described as a "resin-linear" orgaiiosiloxane block copolymer. The terminology "resin-linear'¹ typically describes orgaiiosiloxane block copolymer including "linear" D siloxy units in combination with "resin" T siloxy units. The present orgaiiosiloxane copolymers are "block" copolymers, as opposed to "random'⁵ copolymers. As such, the present orgaiiosiloxane block copolymer describes an organopolysiloxane including D and T siloxy units, where the D units are primarily bonded together to form polymeric chains having 10 to 400 D units, which are described herein as "linear blocks". The T units are primarily bonded to each other to form branched polymeric chains, which are described as "non-linear blocks^'". One or more non-linear blocks may further aggregate to form "nano dornains" in the orgaiiosiloxane block copolymer.

[0058] The organosiloxane block copolymer is not particularly limited but typically has a weight average molecular weight (M_w) of at least 20,000 g/mole. In various embodiments, the organosiloxane block copolymer has a weight average molecular weight of at least 40,000, 50,000, 60,000, 70,000, or 80,000, g/moie. Alternatively, the organosiloxane block copolymer may have a weight average molecular weight of from 40,000 to 100,000, from 50,000 to 90,000, from 60,000 to 80,000, from 60,000 to 70,000, of from 100,000 to 500,000, of from 150,000 to 450,000, of from 200,000 to 400,000, of from 250,000 to 350,000, or from 250,000 to 300,000, g/mol. In still other embodiments, the organosiloxane block copolymer has a weight average molecular weight of from 40,000 to 60,000, from 45,000 to 55,000, or about 50,000, g/mol. The weight average molecular weight may be determined using Gel Permeation Chromatography (GPC) techniques, such as those described in the Examples.

[00S9] The organosiloxane block copolymer of this disclosure includes:

(A) 40 to 90 mole percent di siloxy units of the formula [KSSi j arranged in linear blocks each having an average of from 10 to 400 disiloxy uni ts [R^SiO^] pe linear block; and

(B) 10 to 60 mole percent trisiloxy units of the formula

arranged in non-linear blocks each having a molecular weight of at least 500 g/mol , in one embodiment, the organosiloxane block copolymer also includes (C) 0.5 to 25 mole percent silanol groups [≡SiOH]. For example, the linear blocks may have an average of from 20 to 390, 30 to 380, 40 to 370, 50 to 360, 60 to 350, 70 to 340, 80 to 330, 90 to 320, 100 to 310, 110 to 300, 120 to 290, 130 to 280, 140 to 270, 150 to 260, 160 to 250, 170 to 240, 180 to 230, 190 to 220, or 200 to 210, or any range or combination thereof, disiloxy units per linear block.

[0060] In other embodiments, at least 30% of the non-linear blocks are crosslinked with another non-linear block and aggregated in nano-domains. Alternatively, alternatively at least at 40% of the non-linear blocks are crosslinked with another non-Linear block, and aitematively at least at 50% of the non-linear blocks are crosslinked with another non-linear block. Furthermore, each linear block is linked to at least one non-linear block.

[0061] T he aforementioned formulas may be alternatively described as [R^l2Si02/2]a "Si0₃/2] where the subscripts a and b represent the mole fractions of the siloxy units in the organosiloxane block copolymer, in these formulas, a may vary from 0.4 to 0.9, alternatively from 0.5 to 0.9, and aliernatively from 0.6 to 0.9. Also in these formulas, b can vary from 0.1 to 0.6, alternatively from 0.1 to 0.5 and alternatively from 0.1 to 0.4. Moreover, in these formulas, R¹ may be independently a Ct to C30 hydrocarbyl. The hydrocarbyl may independently be an alkyl, aryl, or alkylaryl group. As used herein, hydrocarbyl also includes halogen substituted hydrocarbyls. Alternatively, R¹ may be a Cj to Cjg or a C\ to ( ,, alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl group. Alternatively R^! may be methyl. R¹ may be an aryl group, such, as phenyl, naphthyl, or an anthryl group. Alternatively, R¹ may be any combination of the aforementioned alkyl or aryl groups. Aitematively, R¹ is phenyl, methyl, or a combination of both.

[0062] Relative to R', each may independently be a Ci to C20 hydrocarbyl. As used herein, hydrocarbyl also includes halogen substituted hydrocarbyls. R may aitematively be an aryl group, such as a phenyl, naphthyl, or anthryl group. Alternatively, R¹ may be an alkyl group, such as methyl, ethyl, propyl, or butyl. Alternatively, R^A may be any combination of the aforementioned alkyl or aryl groups. Alternatively, ^A is phenyl or methyl.

[0063] The organosiloxane block copolymer may include additional siloxy units, such as M siloxy units, Q siloxy units, other unique D or T siloxy units (e.g. having a organic groups other than R^! or R²), so long as the organosiloxane block copolymer includes the mole fractions of the disiloxy and trisiloxy units as described above. In other words, the sum of the mole fractions as designated by subscripts a and b, do not necessarily have to sum to one, The sum of a + b may be less than one to account for amounts of other siloxy units that may be present in the organosiloxane block copolymer. For example, the sum of a + b may be greater than 0.6, greater than 0.7, greater than 0,8, greater than 0.9, greater than 0.95, or greater than 0.98 or 0.99.

[ΘΘ64| In one embodiment, the organosiloxane block copolymer consists essentially of the disiloxy units of the formula [R 2SJO2/2] and trisiloxy units of the formula [1¾ ^'8ϊί¾/2], in the aforementioned weight percentages, while also including 0.5 _{0 25 mole percent silanol groups [≡SiOH], wherein R¹ and R - are as described above. Thus, in this embodiment, the sum of a+b (when using mote fractions to represent the amount of disiloxy and trisiloxy units in the copolymer) is greater than 0.95, alternatively greater than 0.98. Moreover, in this embodiment, the terminology "consisting essentially of describes that the organosiloxane block copolymer is free of other siloxane units not described immediately above.

[0065] In one embodiment, the organosiloxane block copolymer includes at least. 30 weight percent of disiloxy units, altemaiively at least 50 weight percent, alternatively at least 60 weight percent, or alternatively at least 70 weight percent of disiloxy units. The amount of disiloxy and trisiloxy units in the organosiloxane block copolymer may be described according to the weight percent of each in the organosiloxane block copolymer. In one embodiment, the disiloxy units have the formula [(CM^SIOM]. in a further embodiment, the disiloxy units have the formula

[0066] The formula R^S^^^R'SiO?_/?]^ and related formulae using mole fractions, as described herein, do not limit the structural ordering of the disiloxy [ ^SiOaa] and trisiloxy [R^SiOsa] units in the organosiloxane block copolymer. Rather, these formulae provide a non- limiting notation to describe the relative amounts of the two units in the organosiloxane block copolymer, as per the mole fractions described above via the subscripts a and b. The mole fractions of the various siloxy units in the organosiloxane block copolymer, as well as the silanol content, may be determined by ²⁹Si NMR techniques.

[0067J Referring back to the optional silanol groups (^: SiOI i), the amount of silanol groups present in the organosiloxane block copolymer typically varies from 0.5 to 35 mole percent silanol groups [=SiOH], alternatively from 2 to 32 mole percent silanol groups [≡SiOH], and alternatively from 8 to 22 mole percent silanol groups [^SiOH]. The silanol groups may be present in any siloxy units within the organosiloxane block copolymer. The amounts described above represent the total amount of silanol groups in the organosiloxane block copolymer, in one embodiment, a molar majority of the silanol groups are bonded to trisi!oxy units, i.e., the resin component of the block copolymer.

[0068] The silanol groups that may be present on the resin component of the organosiloxane block copolymer, or any other functional groups, as recognized in the art that may be present, may allow the organosiloxane block copolymer to further react or cure at elevated temperatures or to cross-link. The crosslinking of the non-linear blocks may be accomplished via a variety of chemical mechanisms and or moieties. For example, crosslinking of non-linear blocks within the organosiloxane block copolymer may result from the condensation of residual silanol groups present in the non-linear- blocks of the organosiloxane block copolymer. Alternatively, crosslinking may result from hydrosi!ylation, free-radical reaction, and/or any other mechanism known in the ait.

[0069] Crosslinking of the non-linear blocks within the organosil xane block copolymer may also occur between "free resin" components and the non-linear blocks. "Free resin" components may be present in the organosiloxane block copolymer as a result of using an excess amount of an organosiloxane resin during the preparation of the organosiloxane block copolymer. The free resin components may crosslink with the non-linear blocks by condensation of the residual silanol groups present in the non-blocks and in the free resin components. The free resin components may alternatively provide crosslinking by reacting with lower molecular weight compounds such as those utilized as erosslinkers, as described in greater detail below.

[0070] Alternatively, certain compounds can be added during preparation of the organosiloxane block copolymer to crosslink non-resin blocks. These crosslinking compounds may include an organosilane having the formula R⁵ _qSiX₄-_q which may be utilized during the formation of the organosiloxane block copolymer (see, for example, step II of the method as described below). In the aforementioned formula, R^s is typically a Ci to Cg hydrocarbyl or a Q to Cg halogen-substituted hydrocarbyl, X is typically a hydrolysable group, and q is typically 0, 1, or 2. R⁵ may alternatively be a Cj to Cg halogen-substituted hydrocarbyl, a C\ to Cg alkyl group, a phenyl group, or a methyl group, an ethyl group, or a combination of methyl and ethyl groups. X may be any hydrolyzable group, an oximo, aeetoxy, halogen atom, hydroxy! (OH), or an alkoxy group. In one embodiment, the organosilane is an alkyltriacetoxysilane, such as methyltriacetoxysilane, ethyltriacetoxysilane, or a combination of both, Commercially available representative alkyltriacetoxysilanes include ETS-900 (Dow Coming Corp., Midland, MI). Other suitable, non-limiting organosilanes useful as erosslinkers include rneihyl- tris(meihylethylketoxime)silane (MTO), methyl triacetoxys lane, ethyl triacetoxysilane, tetraaeetoxysilarie, tetraoximesilane, dimethyl diaeetoxysilane, dimethyl dioximesilane, methyl tFls(methylmethylketoxime)silane. Typically, crosslinks within the organosiloxane block copolymer are siloxane bonds≡Si-0-Si≡, resulting from the condensation of silanol groups. |ΘΘ71| The amount of crossl inking in the organosiloxane block copolymer may be estimated by determining an average molecular weight of the organosiloxane block copolymer, such as with GPC techniques, Typically, eross!inkmg the organosiloxane block copolymer increases average molecular weight. Thus, an estimation of the extent of erossiinking may be made, given the average molecular weight of the organosiloxane block copolymer, the selection of the linear siloxy component (i.e., chain length as indicated by degree of polymerization), and the molecular weight of the non-Hnear block (which may be primarily controlled by the selection of the organosiloxane resin used to prepare the organosiloxane block copolymer).

[0072] The organosiloxane block copolymer may be isolated in a solid form, for example by casting films of a solution of the organosiloxane block copolymer in an organic solvent and allowing the solvent to evaporate. Upon drying or forming a solid, the non-linear blocks of the organosiloxane block copolymer typically aggregate together to form "nano-domains". As used herein, "predominately aggregated" describes that a majority of non-linear blocks of the organosiloxane block copolymer are typically found in certain regions of the organosiloxane block copolymer, described herein as the "nano-don ains". As used herein, "nano-domains" describes phase regions within the organosiloxane block copolymer that are phase separated and possess at least one dimension, e.g. length, width, depth, or height, sized from 1 to 100 nanometers. The nano-domains may vary in shape, providing at least one dimension of the nano-domain is sized from 1 to 100 nanometers. Thus, the nano-domains may be regular or irregularly shaped. The nano-domains may be spherically shaped, tubular shaped, and in some instances lamellar shaped.

[0073] The organosiloxane block copolymer may include a first phase and an incompatible second phase, the first phase including predominately the disiloxy units [R^SiG^] and the second phase including predominately the trisiloxy units [I^SiO;^], wherein the non-linear blocks are aggregated into nano-domains which are incompatible with the first phase,

72 [0074 J The structural ordering of the distloxy and trisiloxy units, and characterization of the nano-domains, may be determined using analytical techniques such as Transmission Electron Microscopic (TEM) techniques, Atomic Force Microscopy (AFM), Small Angle Neutron Scattering, Small Angle X-Ray Scattering, and Scanning Electron Microscopy.

[0075] Alternatively, the structural ordering of the disiloxy and trisiloxy units in the block copolymer, and formation of nano-domains, may be inferred by detenmning certain physical properties of the organosiloxane block copolymer, e.g. when the organosiloxane block copolymer is used as a coating, in one embodiment, a coating formed from the organosiloxane block copolymer and/or organosiloxane block copolymer has an optical transrnittance of visible light greater than 95%. Such optical clarity is typically only possible when visible light is able to pass through a medium and not. be diffracted by particles (or domains as used herein) having a size greater than 150 nanometers. As the particle size (domains) decreases, optical clarity may increase.

[0076] The organosiloxane block copolymer of this disclosure may include phase separated "soft" and "hard" segments resulting from blocks of linear D units and aggregates of blocks of non-linear T units, respectively. These respective soft and hard segments may be determined or inferred by differing glass transition temperatures (T_g). Thus a linear segment may be described as a "soft" segment typically having a low T_? for example less than 25°C, alternatively less than 0°C, or alternatively even less than -2G°C. The linear segments typically maintain "fluid" like behavior in a variety of conditions. Conversely, non-linear blocks may be described as "hard segments" having higher T_gs values, for example greater than 30°C, alternatively greater than 40°C , or alternatively even greater than 50°C.

[0077] In various embodiments, the organosiloxane block copolymer can he processed several times if a processing temperature (T_ptocessing) s less than a temperature required to cure ( cure), i.e., if Tprocessmg < T«,_re , In various embodiments, the organosiloxane block copolymer will cure and achieve high temperature stability when T_process_t!¾ ^>T_ettre. Thus, the organopolysiloxane block copolymer may offer the advantage of being "re~proeessable" in conjunction with the benefits typically associated with silicones, such as hydrophobicity, high temperature stability, and moisture UV resistance.

?3 [0078] The organosiloxane block copolymer Is not particularly limited to any physical properties. Typically, the organosiloxane block copolyxner has a viscosity greater than 100 or 1 ,000 CSt at 120°C and may have an infinite viscosity. The organosiloxane block copolymer has a refractive index greater than 1.4 and may have a refractive index greater than 1.44, 1.5, 1 ,54. or alternatively greater than 1.55, as determined using ASTM D542. In other embodiments, the organosiloxane block copolymer has greater than 50, 55, 60, 65, 70, 75. 80, 90, 95, 96, 97, 98, or 99, or about 100, % light transmittance. The light transmittance is typically determined using ASTM E-903-96 or a modified version of ASTM D1003 which specifies how to measure light transmittance using a class C light source, in the modified version, the class€ light source is replaced with a light source that produces the solar spectrum (i.e., the AM 1.5G spectrum). Spectral transmittance values are also independent of reflective losses in the modified method in contrast to ASTM D1003. Measurements are acquired using a Varian Gary 5000 between 200- 1700 nni.

[0079] Typically, the organosiloxane block copolymer resists yellowing, resists light absorption losses, has increased toughness, has excellent thermal stability, exhibits excellent flexibility in processing (e.g. B-staged films can be pre-cured but can be reilown and post- cured), and/or exhibits adhesion to numerous types of surfaces typically without a need for adhesion promoters, and/or combinations thereof. In addition, the organosiloxane block copolymer typically can maintain similar refractive indices e.g. RI (PliMe) ^' 1 ,55 and Ri (Ph-T) = 1.56) but simultaneously allow for many different mechanical properties to be manipulated and customized. Moreover, PDMS resin-linears may be utilized wherein refractive indices are dissimilar. In addition, the organosiloxane block copolymer can. provide adhesion and dissipation of stresses in the solid state light reducing chance of failure. Furthermore, the organosiloxane block copolymer can be tailored to have a (high) refractive index which may be matched or similar to a refractive index of a superstate such as front glass, which increases efficiency. Moreover, the organosiloxane block copolymer typically offers excellent melt flowability simultaneously with shelf stability,

[0080] The organosiloxane block copolymer may also have an initial tensile strength greater than 1.0 MPa, alternatively greater than 1.5 MPa, or alternatively greater than 2 MPa. The organosiloxane block copolymer may alternatively have an initial % elongation at break (or rupture) greater than 40%, alternatively greater than 50%, or alternatively greater than 75%. As used herein, tensile strength and % elongation at break are measured according to ASTM D4I2.

[0081] The organosiloxane block copolymer may retain certain physical properties such as tensile strength and % elongation at break, upon heat aging, in one embodiment, the tensile strength of the organosiloxane block copolymer remains within 20%, alternatively within 10%, or alternatively within 5% of its original value upon heat aging at 200°C for 1000 hours. In other embodiments, the % elongation at break is at least 10%, alternatively 50%, or alternatively 75% upon heat aging at 200°C for 1000 hours.

[0082] In one embodiment, the organosiloxane block copolymer may be described as "melt processahle." In this embodiment, the organosiloxane block copolymer may exhibit fluid behavior at elevated temperatures, e.g. upon "melting". The melt flow temperature may be determined by measuring the storage modulus (CP), loss modulus (( ") and tan delta as a function of temperature storage using commercially available instruments. For example, a commercial rheometer (such as TA Instruments' ARES-RDA -with 2KSTD standard flexular pivot spring transducer, with forced convection oven) may be used to measure the storage modulus (G')_} loss modulus (G") and tan delta as a function of temperature. Test specimens (typically 8 mm wide, 1 mm thick) may be loaded in between parallel plates and measured using small strain oscillatory rheology while ramping the temperature in a range from 25°C to 300°C at 2°C/min (frequency 1 1 1/.}. The flow onset may be calculated as the inflection temperature in the G' drop (e.g. flow), the viscosity at 120°C is reported as a measure for melt processabiliiy and the cure onset is calculated as the onset temperature in the G' rise (e.g. cure). Typically, the FLOW of the organosiloxane block copolymer will also correlate to the glass transition temperature of the non-linear segments (i.e. the resin component) in the organosiloxane block copolymer, Alternatively, the "melt processabiliiy" and/or cure of the organosiloxane block copolymer may be determined by rheological measurements at various temperatures, In a further embodiment, the organosiloxane block copolymer may have a melt flow temperature of from 25°C to 200°C, alternatively from 25^CC to 160°C, or alternatively from 50°C to I60°C.

I0OB3J In various embodiments, the organosiloxane block copolymer has a storage modulus (G') at 25°C of from 0.01 MPa to 500 MPa and a loss modulus (G") of from 0.001 MPa to 250 MPa, alternatively a storage modulus (G') at 25°C of from 0.1 MPa to 250 MPa and a loss modulus (G") of from 0.01 MPa to 125 MPa, alternatively a storage modulus (CF) at 25°C of from 0.1 MPa to 200 MPa and a loss modulus (G") of from 0.01 MPa to 100 MPa. In other embodiments, the organosiloxane block copolymer has a storage modulus (G') at 120°C of from 10 Pa to 500,000 Pa and a loss modulus (G") of from 10 Pa to 500,000 Pa, alternatively a storage modulus (G') at 120°C of from 20 Pa to 250,000 Pa and a loss modulus (G") of from 20 Pa to 250,000 Pa, alternatively a storage modulus (G') a t 120°C of from 30 Pa to 200,000 Pa and a loss modulus (G") of from 30 Pa to 200,000 Pa. In still other embodiments, the organosiloxane block copolymer has a storage modulus (G') at 200°C of from 10 Pa to 100,000 Pa and a loss modulus (G") of from 5 Pa to 80,000 Pa, alternatively a storage modulus (G') at 200°C of from 20 Pa to 75,000 Pa and a loss modulus (G") of from 10 Pa to 65,000 Pa, alternatively a storage modulus (G') at 200^C'C of from 30 Pa to 50,000 Pa and a loss modulus (G") of from 15 Pa to 40,000 Pa. Melt proeessability may enable reflow of the organosiloxane block copolymer around various device architecture, e.g. after an initial coating or after the organosiloxane block copolymer is disposed on the device. This feature may be beneficial to various encapsulated electronic devices.

[0084] In one embodiment, the organosiloxane block copolymer is "curable". In this embodiment, the organosiloxane block copolymer may undergo further physical property changes through curing the organosiloxane block copolymer. As described above, the organosiloxane block copolymer includes a certain amount of silanol groups. The presence of these silanol groups may allow for further reactivity, i.e. a cure mechanism. Upon curing, the physical properties of organosiloxane block copolymer may be further altered.

[0085] The structural ordering of the disiloxy and trisiloxy units in the organosiloxane block copolymer as described above may provide the organosiloxane block copolymer with certain unique physical property characteristics when the organosiloxane block copolymer are formed. For example, the structural ordering of the disiloxy and trisilox units in the copolymer may provide organosiloxane block copolymer tha allow for a high optical transmittance of visible light. The structural ordering may also allow the organosiloxane block copolymer to flow and cure upon heating, yet remain stable at room temperature. The siloxy units may also be processed using lamination techniques. These properties may be useful to provide coatings for various electronic articles to improve weather resistance and durability, while providing low cost and eas procedures that are energy efficient. [0086] In various embodiments, the organosiloxane block copolymer is thermoplastic, i.e., not functionalized or functionalized but not cured/curable. For example, the organosiloxane block copolymer may be utilized in an uneured state. Alternatively, the organosiloxane block copolymer may be functionalized. For example, the organosiloxane block copolymer may be vinyl functional or aerylate functional In one embodiment, the organosiloxane block copolymer is Si-H functional or SiOH functional.

[0087] In other embodiments, at least one of the R^b groups is phenyl. Alternatively, at least one of the R^b groups may be aryl, naphthyl, or a Q to C₆ alkyl group. In another embodiment, at least one of the R groups is methyl. Still further, at least one of the R groups may be methyl or phenyl. In still other embodiments, the disiloxy units of the organosiloxane block copolymer have the formula [(CHaXCetySiOa/a]. Alternatively, the disiloxy units of the organosiloxane block copolymer may have the formula [(G¾)2SiQ2_/2j.

[0088] Any one or more of the aforementioned physical properties including, but not limited to, emission, lifetimes, etc. may describe the properties of (I) and/or (II) and/or the composition as a whole, in various non-limiting embodiments. For example, (1) may have a particular peak emission that may be the same or different from the peak emission of the composition as a whole,

[0089] The composition may also include a (D) photosensitizer. The (D) photosensitizer may be added to (I) and/or (Π) or may be added to the composition independently of (I) and/or (II), In one embodiment, the (D) photosensitizer is a part of (I). The photosensitizer may impart a larger peak emission intensity to the composition/(i) polyheterosiloxane composition at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 to 470, 340 to 460, 350 to 450, 360 to 440, 370 to 430, 380 to 420, 390 to 410, or about 400, nm, as compared to a control composition/control (I) polyheterosiloxane composition free of the photosensitizer, i.e., an identical composition but for the (D) photosensitizer.

[ΘΘ90] The photosensitizer may be present in the composition (I) polyheterosiloxane composition in an amount of less than 3 moles of photosensitizer per one mole of the at least one lanthanide metal, e.g. one or more metals (Ml) and/or (M2). In other words, the (D) photosensitizer may present in an amount greater than zero but less than 3 moles of the photosensitizer per one mole of the least one lanthanide metal, e.g. one or more metals (Ml) and/or (M2), typically a lanthanide metal, in various embodiments, the (D) photosensitizer is present in amounts of less than 2.5, less than 2, less than 1.5, less than 1, less than 0,75, less than 0.5, less than 0.25, less than 0.1, less than 0.05, less than 0.01 , less than 0.005, less than 0.001, less than 0,0005, less than 0.0004, etc. moles of photosensitizer per one mole of the at least one lanthanide metal. In other embodiments, the (D) photosensitizer is present in amounts of from 0.0001 to 0.0002, 0.0001 to 0,0003, 0.0001 to 0.0004, 0.0001 to 0.0005, 0.0001 to 0.0006, 0.0001 to 0.0007, 0.0008 to 0.0009, 0.0001 to 0.001, 0.0004 to 0.004, 0.001 to 0.1, 0.001 to 0.009, 0.001 to 0,008, 0.001 to 0,007, 0,001 to 0.006, 0.001 to 0.005, 0.001 to 0.004,0.001 to 0.003, 0.001 to 0.002, 0.01 to 0.09, 0.01 to 0.08, 0.01 to 0.07, 0.01 to 0.06, 0,01 to 0.05, 0.01 to 0.04, 0.01 to 0.03, 0.01 to 0.02, 0.1 to 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.4, 0.1 to 0.3, or 0.1 to 0,2, moles of photosensitizer per one mole of the at least one lanthanide metal,

[0091] The (D) photosensitizer is not particularly limited. In one embodiment, the (D) photosensitizer is chosen from (1) a β-diketone, (ii) a β-diketonate, (D) a salicylic acid, (iv) an aromatic carboxylic acid, (v) an aromatic earboxylate, (vi) a polyaminoearhoxylic acid, (vii) a polyaminocarboxylate, (viii) a N-heterocycIic aromatic compound, (ix) a Sehiff base, (x) a phenol, (xi) an aryloxide, and combinations thereof. In various other embodiments, the (D) photosensitizer is (i) a β-diketone, or (ii) a β-diketonate, or (D) a salicylic acid, or (iv) an aromatic carboxylic acid, or (v) an aromatic earboxylate, or (vi) a polyaminocarboxylic acid, or (vii) a polyaminocarboxylate, or (viii) a N-heterocyclic aromatic compound, or (ix) a Schiff base, or (x) a phenol, or (xi) an aryloxide, or a combination of one or more of the aforementioned compounds, in still other embodiments, the photosensitizer is a β-diketone or a β-diketonate. In additional embodiments, the (D) photosensitizer is an aromatic carboxylic acid or aromatic earboxylate. Alternatively, the (D) photosensitizer may be a salicylic acid or a salicylate. The photosensitizer may be any one of the aforementioned types of compounds and/or may be further defined as a mixture of two or more of any of the aforementioned types of compounds.

[0092] Non-limiting examples of suitable (D) photosensitizers include 1,3- diphenylpropandione; 2-thenoyltrifluoroacetone, 2-dithenoylpropandione, 1 ~phenyl~3-(2- fluoryi)propandione; l-(4-biphenyl)-3-(2-fluoiyl)propandione; l -(2-naphtyI)~3-(2- fluoryl)propandione; 1 -(1 -naphtyl)-3-(2-fiuoryl)propandione; i ~(2,3,4,5-tetrafluorophenyf)~3-(2- iluoryl)propan.dione; 1 l -(2-fluoryI)-4,4,4 rifluorob taiie-l,3-dione; 1 -(2,3,4,5- ietrafluorophenyl)-3~(2~fluoryl)propaiidione; l.~(2,4,6-trifIuorophenyl)-3-(2-fluoryl)propandione; 1 ~(3_;4.5 rifluorophenyl)~3-(2-fiuoryl)propandione; 1 ~(5~bromothiophen-2-yl)~4,4,4- trif3uorobutane-1 ,3-dione; l-(4'~methoxy~4-biphenyl)-4₉4₅4-trichlorobutaiie-l,3-dione; 9- hydroxyphenaien~I-one, iropolone, diethyl 2~hydroxyazu3ene-l ,3-dicarboxylates; benzoic acid, 4-(octyloxy)benzoic acid, 4-(i-butyI)benzoic acid, 2-etfaoxybezoic acid, 3 -eihoxybezoic acid, 4- ethoxybezoic acid, 2-methoxybenzoie acid, 3 -me thox benzoic acid, 4-inethoxybenzoic acid, 4- butoxybenzoic acid. 1 -naphthoic acid, 2-naphthoic acid, biphenyl-2-carboxylic acid, biphenyl~4~ carboxylic acid, 9-fluorenone-l-carboxylic acid, fluorene-9-carboxylic acid, fluorobenzoic acid, chlorobenzoic acid, 2-hydroxybenzoic acid, 2-methyj. benzoic acid, 3-methyIbeiizoic acid, 4- meihylbenzoic acid, 3 ,5-dimeth !benzoic acid, 4-cyanobenzoic acid; 2,2'-bipyridines, 4,4'- bipyridines, 2,2'₅2"-bipyri dines, 1 , 10-phenantrolines, 1 ,8-naphthylridmes, benzimidazole- pyridines, bis(benzimidazoi)pyridines, porphyrines, macrocyclic irnines, ¾Salen, 8- hydroxyquinolines; 5,7-dihalo-8-hydroxyquinolines; benzimidazole substituted 8~ hydroxyquinolines, EDTA, DPTA, DOT A, and combinations thereof.

[0093] Additional non-limiting examples of suitable (D) pliotosensiiizers may ha ve one or more of the structures below:

Wherein Rl ^::: 2-fluor l, R2 - 4-biphenyl; l-naphthyl; 2-naphthyl; phenyl; trifluoromethyl;

2,3,4,54etrafluorophenyl; 2,4.6~trifluorophenyl; 3,4,5-trifl.uorophenyl; and R3 = H;

Wherein RI^:::: trifluoromethyl; 2 = 5-bromo-2-thiophene; and R3 = H; Wherein Rl = trichloromethyl; R2 = 4'-methoxy-4-biphenyl; and R3 ^:::: H; or Wherein RL R2 = phenyl, naphthyi, biphenyl, fluory!, or perfiuoroalky!, and R3=H; or

Wherein X = OH, F, CI, Br, CN, N<¼, OR¹ (R¹ - CI - CI 8), 2 (CI - CIS), R3 (branched); or any one or more of:

R ^::: alkyl or aryl

, ORl (Rl : alkyl, aryl), N02, aryl, alkyl NRL OH, COO! L COORl

X: H, alkyl, aryl, COOB, COORl

R: F, CI, Br, I, OR! (Rl : alkyl, aryl), N02, aryl, aikyL NR1 OH, COOH, COOR1

R: F, CI, Br, I, OR I (Rl : alkyl, aryl), N02, aryl, alkyl, NR1 , OH, COOH, COOR1

. CI

This disclosure also provides a method of forming the polyheterosiloxane composition, The method includes the step of reacting (Α') a rneial (M3) aikoxide, (B ) an optional hydrolyzable metal (M4) salt, (C) a silicon-containing material having silicon-bonded hydroxy groups, and (F) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β'), so long as at least one of (Α') and (Β') is a lantbanide metal. This step forms a poiyheterosiSoxane composition (i.e., a polyheterosiloxane composition that is not "sensitized" because the (D) photosensiiizer is not yet added/present). The method may also include one or more steps as described in WO201 1/002826, which is expressly incorporated herein by reference.

[0095] It is to be understood that (Α'), optionally (Β'), (C), and (F) may react together in any order to form the polyheterosiloxane composition. For example, (A')_> optionally (Β'), (C), and (F) may react individually or with more of each other batch wise (e.g. simultaneously) and/or sequentially. One or more portions of (Α'), optionally (B'j, (C), and (F) 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, (B⁵) is utilized, e.g. with an alkoxide.

[0096] 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, so long as at least one of (Α') and (Β') is a lanthanide metal. 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,

[0097] The metal (M3) is not particularly limited but is typically is the same as (Ml ), e.g. a lanthanide metal or a non-ianthanide metal, so long as at least one of (Α') and (Β') is a lanthanide metal. The metal (M3) of the metal alkoxide may he independently selected and may^¬ be the same as (Ml) or (M2) or may be different so long as at least one of (Α') and (Β') is a lanthanide metal.

[0098] The metal (M3) alkoxide may have the general formula (1) R^ 30_n Xp(OR.2)_v„ k-p-2n. ^ⁿ 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 therebe tween the aforementioned values and ranges are hereby expressly contemplated.

[0099] R} 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 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyL octyl, decyl, dodecy!, hexadecyl, and octadecyl groups. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00100] Each 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) ~(R3Q)-R4_? whe e j is a value from 1 to 4 and alternatively 1 to 2. Bach R3 IS typically an independently selected divalent alkyiene group having from 2 to

6, 3 to 5, or 3 to 4, carbon atoms. Each is typically an independently selected hydrogen atom or monovalent alkyi 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 R^ include phenyl and benzyl. Non- limiting examples of the divalent alkyiene group include ^~CH2CH2~ and -( ^"I ^ I UCK;; }·· . Non- limiting examples of the alkyl groups having from 1 to 6 carbon atoms of ll^ are as described above for R^, Non-limiting examples of the polyether group of Formula (VI) include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, methoxyethoxyethyl, and ethoxyethoxyethyl groups. Alternatively, 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.

[001Θ1] 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

R^COO" where is chosen from hydrogen, alkyl groups, alkenyl groups, and aryl groups.

Non-limiting examples of alkyl groups for include alkyl groups having from 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms as described above for . Non-limiting examples of alkenyl groups for R^ include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, 2-propenyl, ally!, hexenyL and octenyl groups. Non-limiting examples of aryl groups for R ^ include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and benzyl groups. Alternatively, is methyl, 2-propenyl, allyl, and phenyl, β-diketonate ligands for X can have the following structures:

or where RJ ^, R} $, and R2 are typically chosen from monovalent alkyl and aryl groups. Non- limiting examples of alkyl groups for R}&, ^, and R-2 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 4 carbon atoms such as methyl, ethyl, trifluoromethyL and t- buiyl groups. Non-limiting examples of aryl groups for RJ ⁶, R^, and ^ ^ include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyi groups. _s typically chosen from alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups for 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^ include alkenyl groups having from 2 to 18 carbon atoms, alternatively C2 to C8 carbon atoms such as allyl, hexenyi, and octenyl groups. Non-limiting examples of aryl groups for 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 ^) are typically hydrogen or alkyl, alkenyl, and aryl groups. Non-limiting examples of alkyl groups for R*? and R^O include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.

Non-limiting examples of alkenyl groups for R^? and R^ include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, allyl, hexenyi, and octenyl groups. Non-limiting examples of aryl groups for R ^ and R^O include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups. R^, R , ^_S R^₅ R 0_{? am}| R2I _are 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.

[00102] 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 (ill) ethoxide, barium isopropoxide, cadmium ethoxide, cadmium methoxide, cadmium methoxyethoxide, chromium (ill) isopropoxide, copper (II) ethoxide, copper (Π) methoxyethoxyemoxide, gallium ethoxide, gallium isopropoxide, diethyidiethoxygermane. ethyltriethoxyge mane, methyltriethoxy germane, tetra-n- butoxygermane, hafnium ethoxide, hafnium 2-ethylhexoxide, hafnium 2-methoxymethyl-2- propoxide, indium methoxyethoxide, iron (ill) ethoxide, magnesium ethoxide, magnesium methoxyethoxide, magnesium n-propoxide, molybdenum (V) ethoxide, niobium (V) n-butoxide, niobium (V) ethoxide, cerium (IV) t~butoxi.de, 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 tri sopropoxide oxide, vanadium tri-n-propoxide oxide, vanadium oxide tris(niethoxyethoxide), zinc methoxyethoxide, zirconium ethoxide, zirconium 2-ethylhexoxide, zirconium 2-methyl-2- butoxide, and zirconium 2-methoxymethyl-2-propoxide, aluminum s-butoxide bis(ethylacetoaeetate), aluminum di-s-butoxide ethylacetoacetate, aluminum diisopropoxide ethylacetoacetate, aluminum 9-octdecenylacetoacetate diisopropoxide, tantalum (V) tetraethoxide pentanedionate, titanium allylacetoaeetate triisopropoxide, titanium bis(triethanolaniine) diisopropoxide, titanium chloride triisopropoxide, tiianium dichloride diethoxide, titanium diisopropoxy bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethy1acetoacetate)₅ titanium methacryiate triisopropoxide, tiianium methacryloxy ethylacetoacetate triisopropoxide, titanium trimethacrylate methoxyethoxyethoxide, titanium tris(dioctyiphosphato)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, zirconium (bis-2,2 ' -(al loxymethyl)- butoxide)tris(dioctylphosphate), zirconium diisopropoxide bis(2,2,6,6~tetramethyl-3 ,5- heptanedionate), zirconium dimethacrylate dibutoxide, zirconium methacryioxyethylacetoacetate tri-n-propoxide, and combinations thereof. (A ) may be chosen from titanium tetraisopropoxide, titanium butoxide, titanium tetrabutoxide, zirconium tetrabutoxide, or aluminum sec-butoxide.

[00103] The optional (Β ^') hydrol zable 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 metal s ( 4), or a plurality of salts of one or more metals (M4), may be utilized.

[00104] 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 ( 4) 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.

[00105] The optional (Β') 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 (B^'2) a hydrated metal salt having a general formula (V) M4(Z)_v2/_w*xl¾0. v2 is the oxidation state of hydrolyzable metal (M4) and w is the oxidation siate of ligand Z where Z is typically independently chosen from earboxylates, 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 h ving 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 1¾0 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.

[00106] 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, p~diketonaie 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.

[00107] The carboxylate ligands may also be chosen from aerylate, methacrylate, hutylenate, ethylhexanoate, undecanoate, undecylenate, dodecanoate, trideeanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, ci s-9-octadecyienate (CI 8), cis-13- docoylsenoate (C22). The carboxylate ligand may be undecylenate or ethylhexanoate. Alternatively, the organic sulfonate ligands for Z may have a formula Ε-^ΒΟ ", where R" 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^, Alternatively R^2 is tolyL phenyl, or methyl.

[00108] The organic phosphate Hgands for Z typically have a formula (R23())2 PO2^" or R.23Q~ TQy^", where 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^ ³. Alternatively R^3 may be phenyl, butyl, or octyl,

[Θ0Ι09] Organic phosphite Hgands for Z may have a formula (R24Q)2 PQ^~ or R24Q- P02^^~, where R^4 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 R^4 ma be phenyl, butyl, or octyl. Alternatively, Z in Formulas (IV) and (V) may be independently chosen from carboxylate Hgands, β-diketonate Hgands, nitrate Hgands, sulphate ligands, and chloride Hgands, Alternatively, Z may include carboxylate ligands and β~ diketonate ligands.

[OOliO] 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 are as described above for

R-^"5. 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.

[00111] Examples of (Β') hydrolyzable metal salts described by Formula (IV) include but are not limited to lanthanum acetate, cerium acetate, praseodymium acetate, neodymium acetate, promethiu 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 aceiylacetonaie, ytterbium acetylacetonate, lutetium acetylacetonate, and combinations thereof. Non-limiting examples of hydrated metal salts (B'2) described by Formul (VI) include the hydrated versions of any of the metal salts as described above for (B' l).

[00112] Additional non-limiting examples of (Β') include but are not limited to lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, scandium acetate, yttrium acetate, lutetium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, chromium acetate, molybdenum acetate, tungsten acetate, manganese acetate, technetium acetate, rhenium acetate, iron acetate, ruthenium acetate, osmium acetate, cobalt acetate, rhodium acetate, iridium acetate, nickel acetate, palladium acetate, platinum acetate, copper acetate, silver acetate, zinc acetate, cadmium acetate, mercury acetate, aluminum acetate, gallium acetate, indium acetate, thallium acetate, tin, lead acetate, antimony acetate, bismuth acetate, 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, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, rubidium acetylacetonate, cesium acetylacetonate, beryllium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, strontium acetylacetonate. barium acetylacetonate, scandium acetylacetonate, yttrium acetylacetonate, lutetium acetylacetonate, titanium acetylacetonate, zirconium acetylacetonate, hafnium acetylacetonate, vanadium acetylacetonate, niobium acetylacetonate, tantalum acetylacetonate, chromium acetylacetonate, molybdenum acetylacetonate, tungsten acetylacetonate, manganese acetylacetonate, technetium acetylacetonate, rhenium acetylacetonate, iron acetylacetonate, ruthenium acetylacetonate, osmium acetylacetonate, cobalt acetylacetonate, rhodium acetylacetonate, iridium acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, copper acetylacetonate, si l ver acetylacetonate, zinc acetylacetonate, cadmium acetylacetonate, mercury acetylacetonate, aluminum acetylacetonate, gallium acetylacetonate, indium acetylacetonate, thallium acetylacetonate, tin acetylacetonate, lead acetylacetonate, antimony acetylacetonate, lanthanum acetylacetonaie, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, promethium acetylacetonate, samarium acetylacetonate, europium acetylacetonate, gadolinium aceiylacetonaie, terbium acetvlaceionate, dysprosium aceiylacetonaie. holmium aceiylacetonaie, erbium acetvlaceionate, thulium aceiylacetonaie, ytterbium aceiylacetonaie, aluminum acrylate, aluminum methacrylate, aluminum stearate, barium methacrylate, barium acrylate, bismuth 2- eihylhexaiioate, calcium methacrylate, calcium acrylate, calcium undecylenate, copper (Π) methacrylate, copper (II) 2-ethylhexanoate, hafnium 2-ethylhexanoate, iron methacrylate, iron acrylate, lead methacrylate, lead acrylate, lead 2-ethylhexanoate, lithium methacrylate, lithium acrylate, magnesium methacrylate, magnesium acrylate, potassium methacrylate, potassium acrylate, potassium sulfopropylmeihacry!ate, potassium sulfopropylacrylaie, cerium (ΠΪ) 2- ethylhexanoate, europium (ill) acrylate, europium (ill) methacrylate, neodymiiim methacrylate, neodymium neodecanoate, yttrium methacrylate, silver acrylate, silver methacrylate, silver neodecanoate, sodium acrylate, sodium methacrylate, sodium allylsulfonate, strontium acrylate, strontium methacrylate, bis(2-ethylhexanoate)tin, bis(neodecanoate)tin, n-butyltris(2~ethylhexar!oa:te)tiri_? di-n-butylhis(2-ethylhexanoaie)tin, zinc acrylate, zinc methacrylate, zinc neodecanoate, zinc undecanoate, zinc 2-ethylhexanoate, zirconium methacrylate, copper sulphate, zinc chloride, silver nitrate, iron nitrate, nickel nitrate, zinc nitrate, acryloxytri-n~butyltin, acryioxytriphenyltin, di-n-butylbis(2,4- pentanedionate)tin, di~n~ butyldiacetoxytin, di-n-butyldiacrylatetin, di-n-bu.tyidilauryltin, di-n-buty!dimethacrylatetin, di-n- butyidmeodecanoatetin, dimethy!bis(2,4-pentanedionate)tin, dimethyldineodecanoatetin, dioctyldilauryitin, methacryloxytti-n-butyltin, tri-n-butylacetoxytin, and tri-n- butylbcnzoyloxytin. zinc acetate dibydrate, nickel aceiate tetrahydrate, magnesium acetate tetrahydraie, zinc nitrate hexahydrate, and copper sulphate pentahydraie, benzoates thereof, alkylbenzoates thereof, alkyloxybenzoates thereof, triphenyl acetates thereof, and/or combinations thereof,

[00113] in one embodiment, (Β') is chosen from (BM) a non-hydrated metal salt having a general formula (IV) R?_eM4(Z) _v2__e)/w ^an^ (B^'2) a hydrated metal salt having a general formula (V) M4(Z _v2/_w- H20, 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 R? 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.

[00114] In another embodiment, (Α^') and (B") are reacted with water to form a mixed metal oxide solution including metal (M3)-()~(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 (B^')„ The percent may be farther described as mole or weight percent as a theoretical calculated stoichiometric amount.

OOilSj Referring now to (C), it is a silicon-containing material having silicon-bonded hydroxy groups. The silicon-containing material can be (C' l) a siioxane having silicon-bonded hydroxy groups, (C'2) a silane having si I icon -bonded hydroxy groups, or combinations thereof.

[00116] The (C' l ) siioxane can be a disiloxane, trisiloxane, or polysiloxane, or combinations thereof. Similarly, the (C'2) silane can be a monosilane, disilane, tr silane, or polysilane or combinations thereof. The structure of the (C' l ) siioxane 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 polysi!oxanes, the silicon-bonded hydroxy groups can be located at terminal, pendant, or at both terminal and pendant positions.

[00117] Non-lirniting examples of (C'l) siloxanes having silicon-bonded hydroxy groups include MQ resins, OH-functional polydialkylsiloxanes, poiydimethylsiloxane, polyalkylphenylsiloxanes polyphenylmethyldisiloxanes, polyarylalky siloxanes, polydiphenylsiloxanes, polydiarylsiloxanes, polytrifluorumethylsiloxanes, polydiphenylsiloxane dimethylsiloxane copolymers, polyaryl siloxanes, polytrifluoropropylmethylsiloxane, and combinations thereof.

[00118] Non-limiting examples of (C'2) silanes having silicon-bonded hydroxyl groups include phenylsilanetriol, diphenyisilanediol, phenylmethylsilanediol, dimethylsilanediol, trimethylsilanolj, triphenylsilanol, phenyldimethoxysi !anol, phenylmethoxysilanediol, methyldimethoxysilanol, methylmethoxysilanediol, phenyldiethoxysilanol, phenylethoxysilanediol, methyldiethoxysilanoh and methylethoxysilanediol, and combinations thereof. [ΘΘΙ19] 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.

[00120] The (C) hydrolysis product, i.e., the product formed from reaction with water, may include R⁵ _g(R^t,0);(HO)_!SiO(4-(_f+g+j)) 2 and/or hydrolyzed silane R⁵ _h(HO)kSiZ wherein, for example, R⁵ is hydrogen or a hydrocarbyl group. A hydrolyzed organosiloxane R⁵g( °0)_t(HO)_jSiO(4._(f;-g÷j))_/2 or hydrolyzed silane

can he used directly or diluted with aromatic solvents (toluene) and alcohol before added to a mixture of (Α') and optionally (Β').

[0Θ121] One or both of (C'i) and/or (C'ii) may be treated with stoichiometric amounts of water containing catalytic amounts of a strong acid, e.g. HC1 or any "strong acid", or any highly diluted aqueous acid to initiate or promote hydrolysis. Formation of a hydrolysis product may be accelerated by mixing hydrol sable (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 (111) R hSi 'j (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 triethyiarnine or pyridine, to capture resulting 1 (CI as a hydrochloride salt. After removal of the hydrochloride salt, a hydrolyzed silane, e.g.

can be isolated or used directly in solution when added to the reaction mixture of A' and B\

[00122] in other embodiments, organosiloxane (C'i) (e.g. ⁵g(R⁶0)_fSiO(4.(i÷_g)) 2) and/or silane (C'ii) (e.g. R⁵ _hSiZ<j are treated with diluted aqueous acid, such as 0.1 N HQ, 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\ ΘΘ123] In other embodiments, a solution of silane (wherein Z' ^:::: CI and i ^~ 1 , 2), in diethvlether (1 :5) is added dropwise to a stirred cooled solution of stoichiometric amounts of triethylamine or pyridine and water in a diethylether-acetone mixture (e.g. 7: 1). The mixture may then be stirred for additional time and precipitated amine or pyridine hydrochloride may he filtered off and the filtrate reduced to 1 /10 volume, e.g. using a rotary evaporator at S0°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 he collected via filtration and washed with cold pentane or hydrocarbon and re-crystaliized from pentane/diethylether. The product may be isolated as white solid.

[00124] (C'i), which may he reacted to form the hydrolysis product, may be an organosiloxane having an average siloxane unit formula (II)

and/or

(C'ii) may be a silane having a general formula (III) R^SiZ']. In these formulas, each R⁵ is hydrogen or a hydrocarbyl group, each is typically an independently selected hydrogen atom or alkyl group having from I to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) -(R^C j R^ 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, 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.

[00125] 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 he from 0.1 to 3 and g may be from 0.5 to 3. Examples of (C'i) described by Formula (II) include oligonieric and polymeric organosiloxanes. such as MQ resins.

[00126] Alternatively, Z' may he a hydrolysable group such as acetoxy, oxime, silazane, CI or QR6 and/or each Rp 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 R¹ group, as described above. Alternatively, at least one = R^x may be as described by formula (II) or (III). Additionally, h is typically a value from 0 to 3, i 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 ar hereby expressly contemplated.

[00127] The alky! groups having 1 to 18 carbon atoms of in Formulas (II) and (ill) are typically as described above for RJ - Alternatively, the alky! group may include 1 to 6 carbon atoms and be, for example, a methyl, ethyl, propyl, butyl, or hexyl group. The alkeny! groups having from 2 to 18 carbon atoms of in Formulas (II) and (I II) may be, for example, vinyl, propenyl, buteny!, pentenyl, hexenyl, or octeny! 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 (ill) 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.

[ )0128] In Formula (ill), each Z' may be a chloro atom (CI) or OR⁶, where R⁶ is as described above. Alternatively, Z' may be OR^. In Formula (111), subscript h may be a value from 0 io 3, from 1 to 3, or from 2 to 3. In Formula (HI), subscript i is a value from 1 to 4, from 1 to 3, or from 1 to 2. in Formula (ill), subscripts (h+i) may equal 4. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00129] Examples of the silanes (C'ii), which may be reacted to form the hydrolysis product, described by Formula (III) include methyl trichlorosi!ane, phenyltriehiorosiiane, dimethyldichlorosilane, phenylmethyldichlorosilane, methyltrimethoxysifane, phenyltrimeihoxysilane, dimethyldimethoxysilane, pheny!methyldimethoxysilane, and combinations thereof.

[00130] Typically, an amount of (F) 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 hvdrated metal salts (B^'2), hydrated metal salts may be utilized such that no liquid water may be utilized and the water originates from the hydrated metal salts. 0.5 mole of water may be used for hydrolysis and condensation of 1 mole of alkoxy and other hydroiyzable 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, 1 10 ΐο 140, or 120 ίο 130, %, of the theoretical amount of water necessary for complete hydrolysis and condensation of aikoxy and other hydrolyzable groups, as first described above. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contempl ated.

[00131] 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 ma he present and need to be hydrolyzed and condensed are any found on the components used, including, but not limited to, chioro.

[00132] Each of the components (Α'), optionally (Β'), and/or (C) may be liquid or solid and it is typical that they are pre-mixed or dispersed. Stirring one or more of the components (A⁵), optionally (Β'), and/or (€') in a solvent may provide a homogenous dispersion. As used herein, the temiinology "dispersion" describes that the molecules of the various components (Α'), (Β'), and/or (C) are homogenously distributed, A solvent may not be needed if one or more components (Α'), (Β'), and/or (C) can be dispersed in one or more of each other. Such solvents may be as described and may be polar solvents, non-polar solvents, hydrocarbon solvents including aromatic and saturated hydrocarbons, alcohols, etc. Non-limiting exainpl.es of suitable solvents include hydrocarbonethariol, 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,

[00133] Typically, reaction of (A⁵) and optionally (Β') with (F) water proceeds at room temperature (e.g. 20-30°C) but if desired, elevated temperatures up to about 140°C may be used. Alternatively, the temperature can range from 20°C to 120°C. Typically, the reaction may proceed from 30 minutes to 24 hours and alternatively from 10 minutes to 4 hours.

[00134] An optional method step includes removing the solvent to form the polyheierosiloxane composition. The solvent can be removed by any conventional manner such as heating to elevated temperatures or using reduced pressure. The polyheierosiloxane composition can then be redispersed in a solvent of choice such as toluene, THF, butyl acetate, chloroform, dioxane, 1 -butanoi, and pyridine. Since the Si~G-M may be susceptible to hydrolytie cleavage in the presence of water, to maximize shelf life it is typical to minimize the exposure of the polyheierosiioxane composition to moisture.

[00135! ^ ^^e method of forming the sensitized polyheierosiioxane composition may also include the step of (Π) introducing a (D) photosensitizer to one or more of (Α'), (Β'), (C), (E) as described below, and/or (F), prior to the step of reacting and/or introducing (D) to the polyheierosiioxane composition, to form the sensitized polyheierosiioxane composition. Said differently, until this step is completed, the polyheierosiioxane composition formed by reaction of (Α'), optionally (Β'), (€'), (E) and/or (F), is not yet "sensitized." Only after introduction of the (D) photosensitizer to the "polyheierosiioxane composition" is that polyheierosiioxane composition then described as sensitized, i.e., described as the "sensitized polyheierosiioxane composition."

[00136] The (D) photosensitizer may be present in the sensitized polyheierosiioxane composition in an amount, of less than 3 moles of (D) photosensitizer per one mole of the lanthanide metal. The step of introducing is not particularly limited and may include introducing by any method such as pouring, spraying, etc. ^'The step of introducing may occur before, during, or after combination of one or more of (Α'), (Β'), (C), (E) and/or (F), and/or before, during, or after reaction of one or more of (A')» (Β'), (C), (E) and/or (F). The step of introducing may- occur more than once. For example, amounts of the (D) photosensitizer may be introduced at various points in the method, in one embodiment, the (D) photosensitizer is added to the polyheierosiioxane composition after (Α^' ), optionally (Β'), (C')_s (E) and/or (F) react. Alternatively, the (D) photosensitizer can be added to a vessel in conjunction with (Α') and one or more solvents. Further, the (D) photosensitizer can be added to a vessel in conjunction with (Β') and/or (C) and one or more solvents. Even further, the (D) photosensitizer can he added to a vessel in conjunction with (E) and/or (F), As described above, the (D) photosensitizer may impart a larger peak emission intensity to the sensitized polyheierosiioxane composition at an excitation wavelength of from 200 io 1 ,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 io 470, 340 to 460, 350 to 450, 360 to 440, 370 io 430, 380 to 420, 390 to 410. or about 400, nm, as compared to a control polyheierosiioxane composition free of the (D) photosensitizer. The method may also include one or more steps as described in PCT application No. PCT/US 10/40510, which is expressl incorporated herein by reference. [00137] The method may altematively include the step of reacting (Α'), (Β'), ( ), and (E) a eompatibillzing organosiloxane having at least one [R ₃810₁ 2] unit and having a weight average molecular weight (M_w) of less than 10,000 g/'mol.

[00138] Referring to the (E) eompatibillzing organosiloxane, this organosiloxane has at least one [R² ₃SiOj/2] unit. However, the eompatibillzing organosiloxane may have more than one [R²3SiQi_/2] unit. The eompatibillzing 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,

[00139] In one embodiment, the (E) eompatibillzing organosiloxane has an average formula chosen from:

DI) (R^,O)(C₆H5)2SiCH2CH2 (Ci|₃)₂SiO]„()Si(Cif 2{CH2)₃CH ;

Dli) (RO)(C₆H5)2SiCH₂CH2 Si(CH₃)(OSi(CH₃)3)2;

Dili) ( '0)3SiO(CH3)2Si[(CH3)₂SiO]_rriOSi(CH₃)2 (CHCH₂); or DIV) (RO)(C H5)₂SiOSi(CS¾)2Cl¾CH2Si(C¾)(OSi(CH3)3)2, wherein each n is independently from 3 to 100, altematively from 10 to 12, each m is independently from 3 to 100, altematively from 20 to 30, and R' is a Cj to C4 alky), group. Altematively, the (E) eompatibillzing organosiloxane may have the average formula:

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

Alternatively, the (E) cornpatibilizing or anosiloxane may have the average formula:

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

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

[00140] In other embodiments, the (E) compatibilizing organosiloxane has the formula: (Me₃SiO)2MeSiCH2CH2Si(CH₃>₂0Si(C6H5)2(O e). Even further, the (E) compatibilizing organosiloxane may have the formula CR^S3SiO)n(R¾_3-n)Si~R⁹-S (R⁸)2 OSi(R^{i 0})2X, wherein n is 1 or 2, Each R⁸ may be independently a monovalent C_\ to C₂o hydrocarbyl. The hydroearbyl group may independently be an alkyi, aryl, or alkylaryl group, including halogen substituted hydrocarbyls. Each R may independently be a Q to C?n alkyi group, a C_\ to Qg alkyi group, a

Ci to C₆ alkyi group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. R' may be a aryl group, such as phenyl, naphthyl, or an anihryl group, or any combination thereof Alternatively, each R may independently be phenyl, methyl, or a combination of both, Each R^' may independently be a divalent hydrocarbon group including 2 to 12 carbon atoms or 2 to 6 carbon atoms and may be described as ethylene, propylene, or isobutylene. Each R may independently be a monovalent C_\ to C3.3 hydrocarbyl including at least one aryl group, an aryl group, such as phenyl, naphthyl, or an anihryl group, any combination of the aforementioned alkyi or aryl groups, or phenyl (CsHs). X may be a hydro lyzable group chosen from -OR^{1 1}. CI, -OC(0)R⁹, - N(R⁹)₂, or -ON=CR⁹2 wherein each R^u is independently hydrogen or a Q to alkyi group such as a methyl, ethyl, propyl, isoprop l, butyl, pentyl, or hexyl group. Alternatively, X may be an alkoxy, bydroxyl, carboxy, amine, chloride, or oxime group, e.g. -OCH3, -OCH₂CH₃, -OH, -CI, or

In one embodiment, the organosiloxane has the following formula: (Me₃SiO)2(Me)SiCH2CH₂Si _.(CH₃)20Si(C6H₅)₂(OMe), wherein Me is a methyl group. Alternatively, the organosiloxane has the formula (R⁸ ₃SiQ)_ri(R%-n)Si-G~Si(R⁸)₂QSi(Rⁱ⁰)₂X, wherein n is 1 or 2, R^l is independently a monovalent Q to C₂0 hydrocarbyl, G is siloxane or polysiloxane bridging group comprising at least one siloxy unit selected from a

(R^L¾i0_3/2), or (SK½) siloxy units, wherei R¹² may be any organic group, Rⁱ⁰ is independently a monovalent Ci to C₃₀ hydrocarbyl including at least one aryl group, X is a hydrolyzable group chosen from -OR⁹, CI, -QC(G)R⁹, -N(R⁹)₂, or -ON=CR⁹ ₂ and R^ri is hydrogen or a C_x to C₆ alkyl group. G may also be a combination of hydrocarbyl bridging groups, such as the divalent C₂ to Cj_.2 hydrocarbyl groups described above, and a siloxane or polysiloxane. In various embodiments, G is a polydimethylsiloxane of the formula -0(Me2Si02/₂)_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 (R^LiSi03/₂), or (SiO^) 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.

Method_, of Formmg the Organosiloxane Block Copolymer

[00141] The organosiloxane block copolymer may be formed using a method that includes the step of I) reacting a) a linear organosiloxane and b) an organosiloxane resin comprising at least 60 mol % of [R ^'SiOa,^] siloxy units in its formula, in c) a solvent. In one embodiment, the linear organosiloxane has the formula Rⁱ _q(I¾(3._q)SiO( ⁱ2.Si02/2)i₃Si(E)(3- ) R^! _q, wherein each R¹ is independently a Cj to C30 hydrocarbyl, n is 10 to 400, q is 0, 1 , or 2, E is a hydrolyzable group including at least one carbon atom. In another embodiment, each is independently a C; to C₂o hydrocarbyl, In still another embodiment, the amounts of a) and b) used in step I are selected to provide the organosiloxane block copolymer with 40 to 90 moI% of disiloxy units

and 10 to 60 mol% of trisiloxy units [R'SiOs_/i]. In an even further embodiment, at least 95 weight, percent of the linear organosiloxane added in step I is incorporated into the organosiloxane block copolymer.

[ΘΘΪ42] In still another embodiment, the method includes step of II) reacting the organosiloxane block copolymer from step I), e.g., to crosslink the trisiloxy units of the organosiloxane block copolymer and/or to increase the weight average molecular weight (M_w) of the organosiloxane block copolymer by at least 50%. A further embodiment includes the step of further processing the organosiloxane block copolymer to enhance storage stability and/or optical clarity and/or the optional step of removing the organic solvent.

[00143] The reaction of the first step may be represented generally according to the following schematic:

wherein various OH groups on the organosiioxane resin may he reacted with the hydrolyzable groups (E) on the linear organosiioxane, to form the organosiioxane block copolymer and an H- {)·^*) compound. The reaction in step I may be described as a condensation reaction between the organosiioxane resin and the linear organosiioxane.

[00144] The linear organosiioxane described immediately above typically has the formula R^!q(E)₍3-q SiO(R¹?.Si02 2)nS {B) 3._q) R.^!q, where each R^! may be independently a C¾ to C30 hydrocarbvl, wherein the subscript "n" may be described as the degree of polymerization (dp) of the linear organosiioxane and may vary from 10 to 400, wherein the subscript "q" may be 0, 1, or 2, and wherein E is a hydrolyzable group including at least one carbon atom. An amount of alternative siloxy units, such as "T" (R¹8103,-₂) siloxy units, may also be incorporated into the linear organosiioxane, As such the linear organosiioxane may be described as "predominately" linear by having a weight or molar majority of D (R^SiC ) siloxy units. Furthermore, the linear organosiioxane may be a combination of several linear organosiloxanes.

[00145] R¹ in the above linear- organosiioxane formula may independently be an alkyl, aryl, or alkylaryl group. R^] may be a Q to C30 alkyl group, alternatively R¹ may be a Cj to g alkyl group. Alternatively R¹ may be a Cj to alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Alternatively R¹ may be methyl. II^s may be an aryl group, such as phenyl, naphthyl, or an anthryl group. Alternatively, R¹ may be any combination of the aforementioned alkyl or aryl groups. Alternatively, R¹ is phenyl, methyl, or a combination of both. E may be chosen from any hydrolyzable group including at least one carbon atom, but typically E is chosen from an oximo, epoxy, carboxy, amino, or amido group. Alternatively, E may have the formula R^! C(=0)0- , RSC^N-O- , or R⁴C=N-0- where R¹ is as described above, and R⁴ is hydrocarbylene, In one embodiment, E is ' f-;CC( 0)0- (acetoxy) and q is 1. In one embodiment, E is

(methylethylketoxy) and q is 1. In another embodiment, the linear organosiioxane has the formula (CH₃)_q(E)(3.q)SiO[(CH3)2Si022)]nSi(E) 3- _q)(C¾)_q, where E, n, and q are as described above. In still another embodiment, the linear organosiloxane has the formula (CH )_ιΊ(Ε)(₃^8ΪΟ[(ΟΗ₃)(ϋ₆Η₅)8ϊθ2/2)1.8ί(Ε)₍3-_κ.)(€ΐ;:1₃)_¾, where E, n, and q are as described above.

[00146] Typically, to prepare the linear organosiloxane, a silanol capped polydiorganosiloxane is reacted with an "endblocking" compound such as an alkyltriacetoxysilarte or a dialkylketoxirne. The stoichiometry of this endblocking reaction is typically adjusted such that a sufficient amount of the endblocking compound is added to react with the silanol groups on the silanol capped polydiorganosiloxane. Typically, one mole of the endblocking compound is used per mole of silanol on the silanol capped polydiorganosiloxane, Alternatively, a molar excess such as 1 to 10% molar excess of the endblocking compound may be used. The reaction is typically conducted under anhydrous conditions to minimize condensation reactions of the silanol polydiorganosiloxane. Typically, the silanol capped polydiorganosiloxane and the endblocking compound are dissolved in an organic solvent under anhydrous conditions, and allowed to react at room temperature, or at elevated temperatures (e.g. up to the boiling point of the solvent).

The (b) Organosiloxane Resin:

[00147] The organosiloxane resin described above typically includes at least 60 mol % of [R S1.O3 2] siloxy units in its formula, where each ^4, independently may be a Ci to C¾o hydrocarbyl. in various embodiments, the organosiloxane resin may include any amount and combination of other , D, and Q siloxy units, providing the organosiloxane resin includes at least 70 mol % of [R²SiC½3 siloxy units, e.g., at least 80 mol % of [R²Sii¾/2j siloxy units, at least 90 rnoi % of [R^{^}SiOs^] siloxy units, or at least 95 mol % of [R S1O3/2J siloxy units. Non- limiting organosiloxane resins useful as component b) include those known as "silsesquioxane" resins.

001481 Each R² is typically independently a Q to C₂0 hydrocarbyl. Alternatively, R² may be an aryl group, such as phenyl, naphthyl, anthxyl group. Alternatively, R^* may be an alky! group, such as methyl, ethyl, propyl, or butyl. Alternatively, R" may be any combination of the aforementioned alkyl or aryl groups. Alter atively, W^' is phenyl or methyl. The weight average molecular weight (M_w) of the organosiloxane resin is not limited, but typically ranges from 1000 to 10,000. or alternatively from 1500 to 5000 g/mol. [00149] Organosiloxane resins including high amounts of [R S1O3/₂] siloxy units may have a concentration of Si-OZ, wherein z may be hydrogen (i.e. silanol), an alky! group (e.g. so that OZ is an alkoxy group), or alternatively OZ may also be any of the "E" hydrolyzable groups as described above. The Si-OZ content as a mole percentage of all siloxy groups present on the organosiloxane resin and may be determined by 'Si NMR, The concentration of the OZ groups may vary, as dependent on the mode of preparation, and subsequent treatment of the organosiloxane resin. Typically, the silanol (Si-OH) content of organosiloxane resin suitable for use herein is at least 5 mole %, alternatively at least 10 mole %, alternatively 25 mole %, alternatively 40 mole %, or alternatively 50 mole %. However, higher or lower mole percents may alternatively be utilized.

[00150] Organosiloxane resins may be prepared by hydrolyzing an organosilane having three hydrolyzable groups on a silicon atom, such as a halogen or alkoxy group in an organic solvent, A representative example for the preparation of a silsesquioxane resin may be found in US 5,075,103, which is expressly incorporated herein by reference. Furthermore, many organosiloxane resins are available commercially and sold either as a solid (flake or powder), or dissolved in an organic solvent. Suitable, non-limiting, commercially available organosiloxane resins useful as component b) include; Dow Corning® 217 Flake Resin. 233 Flake, 220 Flake, 249 Flake, 255 Flake, Z-6018 Flake (Dow Coming Corporation, Midland MI).

[Q015IJ Organosiloxane resins including amounts of

siloxy units and silanol contents may also retain water molecules, especially in high humidity conditions. Thus, it may be beneficial to remove excess water present by "drying" the linear- organosiloxane prior to reacting in step I. This may be achieved by dissolving the linear organosiloxane in an organic solvent, heating to reflux, and removing water by separation tech iques (for example Dean Stark trap or equivalent method).

[001.52] The amounts of a) and b) used in the reaction of step I are typically selected to provide the organosiloxane block copolymer with 40 to 90 mol% of disiloxy units R^ iO?^] and .10 to 60 mol% of trisiloxy units [R²SiQ3_/2j. The mol % of disiloxy and trisiloxy units present in components a) and b) may be determined using Si NMR techniques. The starting mol % then typically determines the mass amounts of components a) and b) used in step I.

[00153] The amount of components (a) and (b) also typically provides a molar excess of silanol groups on the organosiloxane resin versus an amount of linear organosiloxane. Typical ly, a sufficient amount of the organosiloxane resin is added to potentially react with (all) the Linear organosiloxane added in step I). As such, a molar excess of the organosiloxane resin may be used. The amounts used may be determined by accounting for the moles of the organosiloxane resin used per mole of the linear organosiloxane.

[00154] As described above, the reaction of step Ϊ is typically a condensation reaction between the hydrolyzahle groups of the linear organosiloxane with the silanol groups of the organosiloxane resin. A sufficient amount of silanol groups typically remains on the resin component of the formed organosiloxane block copolymer to further react in step II. Typically, at least 10 mole %, alternatively at least 20 mole %, or alternatively at least 30 mole % silanol remains o the trisiloxy units of the organosiloxane block copolymer as produced in step I.

[0Θ155] The reaction conditions for reacting the aforementioned (a) linear organosiloxane with the (b) organosiloxane resin are not particularly limited. Typically, reaction conditions are selected to affect a condensation type reaction between the a) linear organosiloxane and b) organosiloxane resin, Various non-limiting embodiments and reaction conditions are described in the Examples below^r. In some embodiments, the (a) linear organosiloxane and the (b) organosiloxane resin are reacted at room temperature. In other embodiments, (a) and (b) are reacted at temperatures that exceed room temperature and that range up to about 50, about 75, about 100, or even up to about 150°C. Alternatively, (a) and (b) can he reacted together at reflux of the solvent. In still other embodiments, (a) and (b) are reacted at temperatures that are below room temperature by 5, 10, or even more than 10°C. In still other embodiments (a) and (b) react for times of L 5, 10, 30, 60, 120, or 180 minutes, or even longer. Typically, (a) and (b) are reacted under an inert atmosphere, such as nitrogen or a noble gas. Alternatively, (a) and (b) may be reacted under an atmosphere that includes some water vapor and/or oxygen, Moreover, (a) and (b) may be reacted in any size vessel and using any equipment including mixers, vortexers, stirrers, heaters, etc. In other embodiments, (a) and (b) are reacted in one or more organic solvents which may be polar or non-polar. Typically, aromatic solvents such as toluene, x lene, benzene, and the like are utilized. The amount of the organosiloxane resin dissolved in the organic solvent may vary, but typically the amount is selected to minimize the chain extension of the linear organosiloxane or pre-mature condensation of the organosiloxane resin.

[00156] The order of addition of components (a) and (b) may vary, but typically the linear organosiloxane is added to a solution of the organosiloxane resin dissolved in the organic solvent. This order of addition may enhance the condensation of the hydrolyzable groups on the linear organosiloxane with the silanol groups on organosiloxane resin, while minimizing chain extension of the linear organosi loxane or pre-mature condensation of the organosiloxane resin.

[00Ϊ57] The progress of the reaction in step I, and the formation of the organosiloxane block copolymer may be monitored by various analytical techniques, such as GPC, IR, or ² Si NMR, Typically, the reaction in step I is allowed to continue until at least. 95 weight percent of the linear organosiloxane added in step I is incorporated into the organosiloxane block copolymer.

[00158] The second step may further include reacting the organosiloxane block copolymer from step I) to crosslink the trisiloxy units of the organosiloxane block copolymer to increase the molecular weight of the organosiloxane block copolymer by at least 50%, alternati ely by at least 60%, alternatively by 70%, alternatively by at least 80%, alternatively by at least 90%, or alternatively by at least 100%. The reaction of the second step of the method ma be represented generally according to the following schematic;

[00159] The reaction of step ΪΪ may crosslink the trisiloxy blocks of the organosiloxane block copolymer fomied in step I, which typically increases the weight average molecular weight of the organosiloxane block copolymer. The crosslinking of the trisiloxy blocks may also provide the organosiloxane block copolymer with an aggregated concentration of trisiloxy blocks, which ultimatel may form the aforementioned "nano-domains" in the solid composition. In other words, the aggregated concentration of trisiloxy blocks may phase separate when the organosiloxane block copolymer is isolated as a solid such as a film or (cured) coating. The aggregated concentration of trisiloxy block within the organosiloxane block copolymer and subsequent formation of "nano-domains" in the solid composition including the organosiloxane block copolymer may provide enhanced optical clarity of the solid composition as well as the other physical property benefits associated therewith. [00160] The crosslinking reaction in Step ΪΪ may be accomplished via a variety of chemical mechanisms and/or moieties. For example, crosslinking of non-linear blocks within the organosiloxane block copolymer may result from the condensation of residual silanol groups present in the non-linear blocks of the organosiloxane block copolymer. Crosslinking of the non-linear blocks within the organosiloxane block copolymer may also occur between "free resin" components and the non-linear blocks. "Free resin" components may be present in the organosiloxane block copolymer as a result of using an excess amount of an organosiloxane resin in step I of the preparation of the organosiloxane block copolymer. The free resin component may crosslink with the non-linear blocks by condensation of the residual silanol groups present on the non-linear blocks and on the free resin. The free resin may provide crosslinking by reacting with lower molecular weight compounds added as crosslinkers, as described below.

[00161] Step II may occur simultaneously upon formation of the organosiloxane block copolymer of step I, or involve a separate reaction in which conditions have been modified to affect the step II reaction, The step II reaction may occur in the same conditions as step I. In this embodiment, the step II reaction proceeds as the organosiloxane block copolymer is formed. Alternatively, the reaction conditions used for step I) may be extended to promote the step II reaction. Alternatively, the reaction conditions may be changed, or additional ingredients added to affect the step II reaction.

[00162] The step Π reaction conditions may depend on the selection of the hydrolyzable group (E) used in the starting linear organosiloxane. When (E) in the linear organosiloxane is an oxime group, the step II reaction may to occur under the same reaction conditions as step I. That is, as the organosiloxane block copolymer is formed in step I, it may continue to react via condensation of the silanol groups present on the resin component to further increase the molecular weight of the organosiloxane block copolymer. Not wishing to be bound by any theory, when (E) is an oximo group, the hydrolyzed oximo group (for example methyl ethylketoxime) resulting from the reaction in step I may act as a condensation catalyst for the step II reaction. As such, the step II reaction may proceed simultaneously under the same conditions for step I. In other words, as the organosiloxane block copolymer is formed in step I, the organosiloxane block copolymer may further react under the same reaction conditions to further increase molecular weight via a condensation reaction of the silanol groups present on the resin component of the organosiloxane block copolymer. However, when (E) on the linear organosiloxatie is an acetoxy group, the resulting hydrolyzed group (acetic acid), may not sufficiently catalyze the step Π reaction. Thus, in one embodiment, the step II reaction may be enhanced with a further component to affect condensation of the resin components of the organosiloxane block copolymer, as described in an embodiment below.

[00163] In one embodiment, an organosilane having the formula R⁵ _qSiX4_-q is added during step ΙΪ), where R⁵ is a Cj to Cg hydrocarbyl or a Ci to C_¾ halogen-substituted hydrocarbyl, X is a hydroiysabfe group, and q is 0, L or 2. In other embodiments, ⁵ is a Q to Cg hydrocarbyl or a Ci to Cg halogen-substituted hydrocarbyl, or alternatively R³ is a Ci to Cg alkyl group, or alternatively a phenyl group, or alternatively R⁵ is methyl, ethyl, or a combination of methyl and ethyl. In one embodiment, X may be any hydrolyzable group, alternatively X may be E, as described above, a halogen atom, hydroxy! (OH), or an alkoxy group. In another embodiment, the organosilane is an alkyltriacetoxysilane, such as methyltriacetoxysilane, ethyltriacetoxysilane, or a combination of both. Commercially available representative alkyltriacetoxysilanes include ETS-900 (Dow Corning Corp., Midland, MI). Other suitable, non- limiting organosi lanes include methyl- tris(rnethylethylketoxime)silane (MTQ), methyl triacetoxysilane, ethyl triacetoxysilane, tetraacetoxysilane, tetraoximesilane, dimethyl diaeetoxysilane, dimethyl dioximesilane, methyl tris(methyIrnethylketoxirne)silane.

[00164] The amount of organosilane having the formula ⁵ _qSiX4._q when added during step Π) may vary, but may be based on the amount of organosiloxane resin used in the method. The amount of silane used typically provides a molar stoichiometry of 2 to 15 mol% of organosiiane/mols of Si on the organosiloxane _resi_n. Furthermore, the amount of the organosilane having the formula R⁵ ₍ SiX4_-q added during step II) may be controlled to ensure a stoichiometry that does not consume all the siianol groups on the organosiloxane block copolymer. In one embodiment, the amount of the organosilane added in step II is sele _ted _to provide an organosiloxane block copolymer including 0.5 to 35 mole percent of siianol groups [≡SiOH].

[00165] Step III in the present method is optional, and includes further processing the organosiloxane block copolymer formed using the aforementioned method steps to enhance storage stability and/or optical clarity. As used herein the phrase "further processing" describes any further reaction or treatment of the organosiloxane block copolymer to enhance storage stability and/or optical clarity, The organosiloxane block copolymer as produced in step II may Include an amount of reactive "OZ" groups (e.g. ≡SiOZ groups, where Z is as described above), and/or X groups (where X is introduced into the organosiloxane block copolymer when the organosilane having the formula R⁵ _qSiX4__q is used in step Π). The OZ groups present on the organosiloxane block copolymer at this stage may be silanol groups that were originally present on the resin component, or alternatively may result from the reaction of the organosilane having the formula R^_qSiX^_q with silanol groups, when the organosilane is used in step II. Alternatively, further reaction of residual silanol groups may further enhance the formation of the resin domains and improve the optical clarity of the organosiloxane block copolymer, Thus, optional step ! S i may be performed to further react OZ or X present on the organosiloxane block copolymer produced in Step ΙΪ to improve storage stability and/or optical clarity. The conditions for step III may vary, depending on the selection of the linear and resin components, their amounts, and the endcapping compounds used,

[00166J In one embodiment of the method, step III is performed by reacting the organosiloxane block copolymer from step II with water and removing any small molecular compounds formed in the method such as acetic acid. In this embodiment, the organosiloxane block copolymer is typically produced from a linear organosiloxane where E is an acetoxy group, and/or an acetoxy silane is used in step II. Although not wishing to be bound by any theory, the organosiloxane block copolymer formed in step II may include a quantity of hydrolyzable 8ΐ-ϋ-€(0)Ο¾ groups, which may limit, the storage stability of the organosiloxane block copolymer. Thus, water may be added to the organosiloxane block copolymer formed from step II, which may hydrolyze Si-0-C(0)C¾ groups to further link the trisiloxy units, and eliminate acetic acid. The formed acetic acid, and any excess water, may be removed by known separation techniques. The amount of water added in this embodiment may vary, but typically is 10 weight. %, or alternatively 5 weight % is added per total solids (as based on organosiloxane block copolymer in the reaction medium).

[00167] In another embodiment of the method, step 111 is performed by reacting the organosiloxane block copolymer from step II with an endcapping compound chosen from an alcohol, oxime, or trialkyisiloxy compound. In this embodiment, the organosiloxane block copolymer is typically produced from a linear organosiloxane where E is an oxime group. The endcapping compound may be a C C2o alcohol such as methanol, ethane L propanol, butanol, or others in the series. Alternatively, die alcohol is n- butanol. The endcapping compound may also he a trialkyisiloxy compound, such as trimethyimethoxysilane or trimethylethoxysiiane. The amount of endcapping compound may vary but typically is between 3 and 15 t % with respect to the organosiloxane block copolymer.

[00168] Step IV of the present method is also optional, and includes removing the organic solvent used in the reactions of steps ί and IL The organic solvent may be removed by any known techniques, but typically includes heating the organosiloxane block copolymer compositions at elevated temperature, either at atmospheric conditions or under reduced pressures,

[00169] In additional non-limiting embodiments, this disclosure includes one or more elements, components, method steps, test methods, etc. as described in one or more of PCTYUS 11/052615, PCT/US 11/52513, PCT/USi 1/52518, PCT/US 11/52747, PCT/US 11/52751, each of which is expressly incorporated herein by reference.

[00170] The composition as a whole, i.e., including (I) and (II) described above, may be formed using any steps of the art. For example, the method may include the steps of physically combining (I) and (ΪΙ) in a mixer, extruder, reactor, etc. In various embodiments, (I) and (II) can be combined or blended by any method known in the art., e.g. using a co-solvent, melt mixing, high energy planetary mixing, sonic horn, extruder, etc. Once the mixture is formed, the mixture can be further converted into a color conversion layer by extrusion into a film, coating onto a release liner, spray drying into a powder, etc,

Additional Embodimeatsf

[0017.11 T is disclosure also provides a cured silicone composition. Said differently, the cured silicone composition is the cured product of (I) and (II). The product may be cured by any mechanism of the art, e.g. condensation, free-radical polymerization, hydrosiiylaiion, and/or any other mechanism known in the silicone arts. For example, if the (II) organosiloxane block copolymer is functionalized, e.g. ihermoset, the cured product may include the polymerization/reaction/cured product of molecules of (11) reacting with themselves via condensation, free-radical polymerization, hydrosiiylaiion, and/or any other mechanisms known in the silicone ait,

[00172J The cured silicone composition is not particularly limited and may be partially cured or completely cured. The cured silicone composition may be in any three dimensional fonn including a film, sheet, as a gel, as a molded form, as a cast form, etc. The level of clarity of the cured silicone composition may be predetermined by selecting and customizing the polyheterosiloxane composition and the curable silicone, as well, as the methodology and conditions used to prepare the cured silicone composition.

[00173] 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,

[00174] 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 heml-sphericai 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 suc 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 ran, greater than 100 nm. greater than 1 μηι, or greater than 10 um.

[00175] The coating may be disposed on and in direct contact with the substrate or disposed on and separated in space with the substrate. The coating may be disposed on one or more portions of the substrate or on the entire substrate. The coating includes the cured silicone composition. 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, μΐΏ, 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, μηι, 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, μηι. 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, pm. However, the coating is not limited to this thickness. [Θ0176] 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 em 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.

[00177] This disclosure also provides a method of forming the cured product. This method includes the step of curing the (II) organosiloxane block copolymer. As described above, the step of curing may be accomplished via any curing mechanism known in the silicone arts, e.g. condensation, free-radical reaction, hydrosiiy!ation, etc.

[ΘΘΙ78] This disclosure further provides a product including the (I) polyheterosiloxane composition and the cured product of the (II) organosiloxane block copolymer. In this embodiment, (I) and the cured product of (II) may be combined by any method known in the art including physical mixing, e.g. as described above. (I) may be present in, or combined with, (II) and then (II) may be cured to form such a product.

EXAMPLES

[00179] 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.

[00180] Photoluminescence of the examples is be measured using a Fiuorolog-2 or Fluorolog-3 spectrofluorometer, manufactured by Jobin Yvon SPEX, and an Ocean Optics USB4000 spectrometer fiber coupled to an integrating sphere and using Ocean Optics' Spectr Suite software. The specific parameters are as described above.

[00181] 350 ml of a 2: 1 ratio of toluene and ethanol is charged to a 3-neck 500 ml round flask equipped with reflux condenser and temperature probe. 28.422 g titanium i-propoxide is charged to the flask followed by 6.120 g zinc benzoate and 20.598 g europium benzoaie salts. A stoichiometric amount of water (1 ,472 g) is added dissolved in 20 mi of a 3: 1 ratio ethanol and toluene at room temperature followed by heating the reaction mixture to 75 °C The reaction mixtures are stirred for 2 hours at 75 °C, then a pre-hydrolyzed siloxane moiety is added. More specifically, this pre-hydrolyzed siloxane moiety is formed by hydro) y zing a mixture of 5.469 g PhSi(OMe)₃ and 1.983 g PhMeSi(OMe)₂ with 1.622 g 0.I N HCL After 15 minutes, the residual amount of water (1 ,793 g ¾0) is added dissolved in 20 ml of a 3: 1 ratio ethanol and toluene. The reaction mixtures are then stirred for further 2 hours at 75 °C, cooled to ambient and then filtered through 0.45 μηι PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at 75°C and 15 nimHg resulting in white solids. The products show orange or red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. The quantum yield of these examples is determined as solids and is approximately 37% QY for each.

[00182] Synthesis of blue sensitizing ligand l-(2~naphmyi)~3-(fluoryl)propanedione (NFPD) is carried out according to the experimental procedure given by V. Divya, .O, Freire, M.L.P. Reddy Dalton Trans., 2011 , 40, 325. 0.005 g of the blue photosensitizer is added to a solution of the 1 g Tio.sEuo.iZno.i^^SiOi^.lmfR^iO. ajd i toluene. The solution is filtered through 0,2 μτα PTFE filter media and evaporated to dryness giving a solid polyheterosiloxane composition of Tio.5Eiio.2Zno.1 2Si OaalmP*-¹

+ NFPD. 0Θ183] 60 ml of a 3: 1 ratio of toluene and ethanol is charged to a ί-neck 250 ml round flask equipped with reflux condenser and temperature probe, 5.684 g of Titanium /-propoxide is charged to the flask followed by 3,435 g europium benzoate, A stoichiometric amount of water (0.120 g) is added in 10 ml of a 3: 1 ratio ethanol and toluene at room temperature followed by heating the reactio mixture to 75 °C. The reaction mixture is stirred for 2 hours at 75 °C then the pre~hydrolyzed siloxane moieties, formed by hydroiyzing 0.330 g PhSi(OMe)3 and 0.91 1 g PhMeSi(OMe)2 with 0.270 g HC! are added. After 15 min the residual amount of water (0,431 g) is added in 10 ml of a 3:1 ratio ethanol and toluene. The reaction mixture is stirred for further 2 hours at 75 °C, cooled to ambient and then filtered through 0.45 μηι PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at 75 °C and 15 mmHg resulting in solid products. The product showed orange or red luminance with near UV excitation, with a peak emission wavelen th around 615 nm and a peak excitation wavelength around 395 nm.

[0 )184] A 500mL 3neck round bottom flask is loaded with toluene (68.0g) and Dow Corning 217 flake (27. Og). The flask is equipped with a thermometer, Teflon stir paddle, and a Dean Stark apparatus, prefiiled with toluene, attached to a water-cooled condenser. A nitrogen blanket is applied. An oil hath is used for heating. The mixture is then heated at reflux for 30 minutes, and subsequently cooled to 108°C (pot temperature). A solution of toluene (22. Og) + siianol terminated PhMe siloxane (33. Og) (endblocked with 50/50 methyl triacetoxysilane / ethyl triacetoxysilane - ΜΤΑ'ΈΤΑ Gelest (1.04g₅ 0.00450mols Si) is prepared in a glove box (same day) under nitrogen by adding the 1VIT A/ETA to the polymer and mixing at room temperature for 2hrs. This solution is added to the Dow Corning 217 flake solution quickly at 108°C, and heated at reflux for 4hrs. The reaction mixture is then cooled to 108°C, and 50/50 MTA/ETA (4.79g, 0.0207mols Si) added. After heating at reflux for 2hrs, the mixture is cooled to a pot temperature of 90°C and DI water (4„54g) then added. The mixture is heated at reflux for Ihr (no removal of water). The mixture is then heated at reflux and water removed via azeotropic distillation, 20min i'--109°C). Heating continues at reflux for an additional 3hrs. Typically, no more water collects in the Dean Stark at this time. The mixture is cooled to 100°C and pre-dried Darco G60 carbon black (0.60g) added. After cooling to room temperature with stirring the mixture is then stirred overnight at room temperature. The reaction mixture is then pressure filtered through a 0,45um filter the following day. [Θ0185] A 1 L 3 neck round bottom flask is loaded with toluene (192.62g) and 217 flake (72. Og, 0.527mols Si) to form a mixture. The flask is equipped with a thermometer, glass stir shaft with a Teflo paddle, and a Dean Stark apparatus attached to a water-cooled condenser and prefilled with toluene. A nitrogen blanket is applied and a heating mantle is used for heating. The mixture is heated at reflux for 30 minutes and 0.12ml water removed, The mixture is then cooled to about 2 degrees below reflux.

[0Θ186] A bottle is then loaded with silanol terminated PDMS (88. Og siloxane, 1.18mols Si) and toluene (47.38g) to form a solution. Subsequently, 50/50 MT A/ETA methyl triacetoxysilane / ethyl triacetoxysilane (5.93g, 0.026 Imols Si) is added in a glove box (same day) under nitrogen and mixed at room temperature for 1 hour. Then, this solution is added to the 217 flake mixture and the combination is heated at reflux (1 13°C) for 2hrs while 1.48ml water is removed. The combination is then cooled to 1 Q8°C and 50/50 MTA/ETA (5.99g, 0.0264mols) is added. This combination is then heated at reflux for Ihr and 0.30ml water is removed.

[00187] A 12L 3 neck round bottom flask is loaded with toluene (1482, 05g) and 217 flake (1800 g, 13.18 niols Si) to form a mixture. The flask is equipped with a thermometer, glass stir shaft with a Teflon paddle, and a Dean Stark apparatus attached to a water-cooled condenser and prefilled with toluene, A nitrogen blanket is applied and a heating mantle is used for heating. The mixture is heated at reflux for 30 minutes and 8.17 g water removed. The mixture is then cooled to about 2 degrees below^r reflux,

[00188] A bottle is then loaded with silanol terminated PDMS (88. Og siloxane, LlSmols Si) + toluene (47.38g). The silanol terminated PDMS is capped with 50/50 MTA/ETA (5.93 g, 0.0261mols Si) in a glove box (same day) under nitrogen by adding the 50/50 MTA/ETA to the PDMS and mixing at room temperature for 1 hour. Subsequently, the PDMS solution is added to the 217 flake solution quickly and heated at reflux (1 13°C) for 2hrs with 1.48ml water removed. Then, the solution is cooled to 108°C and 50/50 MTA/ETA (5.99g. 0.0264 mols) is then added. This combination is then heated at reflux for Ihr and 0.30ml water removed.

[00189J Water treatment (20: 1 molar ratio, water: MTA/ETA) is then necessary to hydrolyze remaining acetoxy groups left from the silane used. More specifically, the following process is repeated three times. The aforementioned combination is cooled to 90°C and 18,92 g of DI water is added. The water is then removed via azeolropic distillation over 45 minutes. Moreover volati!es are distilled off (164,7g) to increase solids content.

The polyheterosiloxane composition (Tio.5Euo.2¾o.i[R¹2Si()2 ]_in[ ⁱSi 3/2]d) + NFPD formed in Example 2 is dissolved in toluene at 25% solids, syringe filtered (0.2 micron), and added at 0, 2.5wt%, 5wt% and 1.0wt% to the 45wt% Ph-T - 120dp PhMe resin linear copolymer of Example 3, 70% in toluene, to form different mixtures,

[00191] Subsequently, 1mm thick films are formed from casting these mixtures and stacking and hot pressing at 120°C for 5min. Samples are uncured, physically gelled films that are optically clear and exhibit no tack. After formation, each film is evaluated to determine haze, light txansmittance, and clarity, pursuant to ASTM Di 003. The results are set forth below.

In addition, each film is evaluated to determine LQE, x and y color according to

CiE 1931, and u' and v' color according to CIE 1976, as set forth below.

[00193] Rlieology evaluations are determined using an AREA RDA from TA Instruments at 5°C/mm using IHz frequency at a 5% strain. These rheology evaluations show almost no impact of 5wt% composition on the flow and cure behavior of the composition.

[00194] The aforementioned data show that cured luminescent compositions were successfully produced, as demonstrated by the LQE and CJE color coordinate data, with sufficient compatibility between the resin-linear host material and the photo luminescent polyheterosiloxane component, as demonstrated by the Haze, Transmi tance and Clarity data.

[00195] 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. In additional non-limiting embodiments, all values and ranges of values within any aforementioned range of numbers are hereby expressly contemplated.

[001 6] 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 PCT Patent Application Numbers PCT/US2013/046813 and PCT/US2013/046784; one or more of U.S. Provisional Patent. Application Numbers 61/782230; 61/782628; 61/851990; 61/783797; and 61/784581 : each of which was previously filed, and is expressly incorporated herein by reference in its entirety relative to these non-limiting embodiments, or PCT application docket number DC11529PCT1/071038.01583 or Taiwanese application docket number DO 1530NP1/071038.01590, each of which is concurrently filed and expressly incorporated herein by reference in its entirety relative to these non-limiting embodiments.

Claims

What is claimed is:

1 , A composition comprising a combination of:

(I) a polyheierosiloxane composition comprising;

at least one lanthanide meiak and

siloxy units having the formula (R^SiOia). (R^SiO-^), (R^iO-y?), and/or (S1O4/2), wherein each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms,

wherein the mole fractions of the at least one lanthanide metal and the siloxy units relative to each other is of the formula

[at least one lanthanide metai]_A[R sSiGialmjj 2Si02/2]d[R SiO;v₂]t[Si04₂]_q, wherein a is from 0.001 to 0.9, m is from zero to 0.9. d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9,

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

(II) an orgarsosiloxane block copolymer comprising:

40 to 90 mole percent disiloxy units of the formula [R^SIOM] arranged in linear blocks each having an average of from 10 to 400 disiloxy units [ ^SiO^] per linear block; and

10 to 60 mole percent siloxy units arranged in non-linear blocks each having a weight average molecular weight of at least 500 g/mol wherein at least one siloxy unit is a trisiloxy unit of the formula [R^bSi0.v2];

wherein R^A is independently a Q to C30 hydrocarbyl and R^B is independently a Q to C20 hydrocarbyl, and

wherein each linear block is linked to at least one non-linear block,

2. The composition of claim 1 wherein said (Ϊ) a polyheierosiloxane composition is further defined as comprising;

(A) a first metal (Ml),

(B) a second metal (M2),

(C) siloxy units having the formula

(R^lSi<¾/2), and/or (S-O4 2), wherein each R is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms,

wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R Si0₁/₂]_m[R¹2SiO_M]_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 zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9,

wherein m, d, t and q cannot all be zero and the suns of a+b+m+d+t+q ~ I, and wherein at least one oxygen atom of said siloxy units is bonded to at least one of (Ml) and/or (M2),

wherein at least one of (Ml) and (M2) is a lanthanide metal,

3. The composition of claim 1 or 2 wherein the organosiloxane block copolymer is thermoplastic or wherein the organosiloxane block copolymer is functional ized.

4. The composition of claim 1 or 2 wherein the organopolysiloxane block copolymer is functionalized, wherein the organosiloxane block copolymer is Si-H functional or SiOH functional, and wherein the organopolysiloxane block copolymer comprises 0.5 to 25 mole percent silanol groups [≡≡Si()H].

5. The composition of any one of the preceding claims wherein at least 30% of the non-linear blocks are crosslinked with another non-linear block and aggregated in nano-domains.

6. The composition of any one of claims 2 to 5 wherein each of (Ml) and (M2) is independently a lanthanide metal different from each other.

7. The composition of any one of the preceding claims exhibiting a quantum yield of at leas! 0.05%.

8. The composition of any one of claims 2 to 7 wherein (Ml) is chosen from Ti, Zr, Al, Zn, Hf, Ta, Y, Nb and combinations thereof and (M2) is chosen from Ce, Eu, Nd, Er, Sm₅ Dy, Tb, and combinations thereof,

9. The composition of any one of claims 2 to 8 wherein one of (Ml) and (M2) is

Eu³⁺.

10. The composition of any one of claims 2 to 5 wherein one of (Ml) and (M2) is a non-lanthanide metal or combinations thereof, and the other of (Mi) and (M2) is a lanthanide metal or combinations thereof.

1 1. The composition of any one of claims 2 to 10 wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Mi)]_a[(M2)]_b R¹2Si02/2]d[RⁱSi0 /2]t wherein a is from 0.1 to 0.8, b is from 0.05 to 0.5, and each of d and t is independently from 0.1 to 0.8.

12. The composition of any one of claims 2 to 1 1 comprising -(Si-0-Ml-0-M2)~ bonds.

13. The composition of any one of claims 2 to 12 that:

(i) emits light having a wavelength of 400 to 1700 mn when excited by a light source having a wavelength of 200 to 1000 nrn; or

(ii) emits light having a wavelength of 450 to 750 nm when excited by a light source having a wavelength of 250 to 520 nm; or

(Hi) emits visible light having a wavelength of 450 to 650 nm when excited by UV light; or

(iv) emits infrared light having a wavelength of 1450 to 1650 nrn when excited by light having a wavelength from 650 to 5,000 nm; or

(v) emits near R light having a wavelength of 1000 to 1 100 nm when excited by light having a wavelength from 650 to 5,000 mn,

with the proviso that the emitted light has a longer wavelength than the excitation light source, or

(vi) emits light having a peak of from 610 to 620 nm.

14. The composition of any one of the preceding claims wherein the (C) siloxy units have the formula [(CH (C6H₅)SiO2aj_d (C6i-i5)SiO3«]t or

[(C₆H₅)Si0₃2lt.

15. The composition of any one of the preceding claims wherein the organosiloxane block copolymer comprises at least 30 weight percent disiloxy units.

16. The composition of any one of the preceding claims wherein the disiloxy units of said organosiloxane block copolymer have the formula (CHsXCeHjjSiCb ?],

17. The composition of any one of claims 1 to 15 wherein the disiloxy units of said organosiloxane block copolymer have the formula (CH^SiGa_/aj.

18. The composition of any one of the preceding claims wherein ill) has a weight average molecular weight of at least 20,000 g/mole.

19. A product comprising (I) and the cured product of (II) of any one of the preceding claims.

20. A method of forming the composition of any one of claims 1 to 18 comprising the siep of combining (I) and (II).