Organosiloxane compositions and uses thereof

Abstract

The present disclosure provides methods of making organosiloxane polymer compositions from hydrosilylation curable compositions comprising at least the components (a) and (b) and at least one of components (c) and (d): (a) an organosiloxane resin material comprising aliphatic unsaturation; and (b) an organosiloxane crosslinker comprising multiple silicon atom-bonded hydrogen atoms (e.g., an SiH siloxane); in combination with at least one of (c) at least one organosiloxane comprising at least two silicon atom-bonded hydrogen atoms; and (d) at least one organosiloxane comprising at least two silicon atom-bonded hydrocarbyl groups comprising aliphatic unsaturation (e.g., a di-vinyl functional siloxane). Such hydrosilylation curable compositions have, in some instances, significantly faster cure speed, relative to their condensation curable counterparts. A faster cure speed can be important for encapsulating electronic devices, such as light-emitting diode (LED) chip devices, including devices having tall structures.

Claims

1. A hydrosilylation curable composition comprising components (a), (b), and (e) and at least one of components (c) and (d): (a) a resin material having the unit formula
[R.sup.1R.sup.2R.sup.3SiO.sub.1/2].sub.a[R.sup.1R.sup.2R.sup.4SiO.sub.1/2].sub.b[R.sup.1R.sup.5SiO.sub.2/2].sub.c[R.sup.1SiO.sub.3/2].sub.d, wherein R.sup.1, R.sup.2, and R.sup.3 are independently a C.sub.1 to C.sub.30 hydrocarbyl group free of aliphatic unsaturation, and R.sup.4 and R.sup.5 are independently a C.sub.1 to C.sub.30 hydrocarbyl group free of aliphatic unsaturation or a C.sub.2 to C.sub.30 hydrocarbyl group comprising aliphatic unsaturation, 0subscript a<0.1, 0<subscript b<0.2, 0subscript c<0.2, subscript d=(1abc), the resin material has a weight average molecular weight of about 1500 grams per mole (g/mole) to about 5000 g/mole, and the resin material has a mole ratio of silicon bonded hydroxy (SiOH) to resin material of about 0.05 to about 0.5; (b) a crosslinker having the unit formula [R.sup.1R.sup.2R.sup.8SiO.sub.1/2].sub.e[R.sup.1R.sup.9SiO.sub.2/2].sub.f[R.sup.1SiO.sub.3/2].sub.g, wherein R.sup.1 and R.sup.2 are independently a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation, R.sup.8 and R.sup.9 are independently a H, a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation or a silane radical of the formula [R.sup.10R.sup.11Si].sub.p[R.sup.10R.sup.11SiH] (wherein R.sup.10, R.sup.11 is independently a H or a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation, subscript p is an integer from 0 to 10), subscript e is an integer from 0 to 10, subscript f is an integer from 0 to 10, subscript g is an integer from 0 to 20, and the number of SiH groups in the crosslinker is2 per crosslinker molecule; and (e) a hydrosilylation catalyst; and at least one of: (c) an SiH siloxane having the formula
[R.sup.1R.sup.2R.sup.6SiO.sub.1/2][R.sup.1R.sup.2SiO.sub.2/2].sub.m[O.sub.1/2SiR.sup.6R.sup.2R.sup.1], wherein R.sup.1 and R.sup.2 is independently a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation, R.sup.6 independently is H or a silane radical of the formula [SiR.sup.1R.sup.2].sub.p[R.sup.1R.sup.2SiH], wherein subscript p is an integer from 0 to 10, and subscript m is an integer from 20 to 200; and (d) an organosiloxane comprising at least two silicon atom-bonded hydrocarbyl groups comprising aliphatic unsaturation having the unit formula
[R.sup.1R.sup.2R.sup.7SiO.sub.1/2][R.sup.1R.sup.2SiO.sub.2/2].sub.n[O.sub.1/2SiR.sup.7R.sup.1R.sup.2], wherein R.sup.1 and R.sup.2 is independently a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation, R.sup.7 is a C.sub.2 to C.sub.30 hydrocarbyl comprising aliphatic unsaturation, and subscript n is an integer from 20 to 200.

2. The hydrosilylation curable composition of claim 1, wherein the curable composition comprises component combinations selected from the group consisting of: components (a), (b), (d), and (e); components (a), (b), (c), and (e); and components (a), (b), (c), (d), and (e).

3. The hydrosilylation curable composition of claim 1, wherein R.sup.4 or R.sup.7 is vinyl.

4. The hydrosilylation curable composition of claim 1, wherein subscript f or g is 0.

5. The hydrosilylation curable composition of claim 1, comprising a crosslinker of the formula [R.sup.1R.sup.2R.sup.8SiO .sub.1/2].sub.e[R.sup.1R.sup.9SiO.sub.2/2].sub.f and a crosslinker of the formula [R.sup.1R.sup.2R.sup.8SiO.sub.1/2].sub.e[R.sup.1SiO.sub.3/2].sub.g in a ratio of about 5:1 to about 3:1 w/w, wherein R.sup.1, R.sup.2, R.sup.8, R.sup.9, subscript e, subscript f, and subscript g independently are as defined therein.

6. The curable composition of claim 1, wherein 0.05<subscript b<0.15 or 0.08<subscript b<0.15; or wherein 0subscript c<0.1; or wherein 0.05<subscript b<0.15 or 0.08<subscript b<0.15 and 0subscript c<0.1.

7. The hydrosilylation curable composition of claim 1, wherein the resin material has a weight average molecular weight of about 2400 g/mole to 3600 g/mole; or wherein the resin material has a mole ratio of silicon bonded hydroxy (SiOH) to resin material of about 0.1 to about 0.3; or wherein the resin material has a weight average molecular weight of about 2400 g/mole to 3600 g/mole and the resin material has a mole ratio of silicon bonded hydroxy (SiOH) to resin material of about 0.1 to about 0.3.

8. The hydrosilylation curable composition of claim 1, wherein subscript m is an integer from 50 to 150; or wherein subscript n is an integer from 50 to 150; or wherein m is an integer from 50 to 150 and n is an integer from 50 to 150.

9. The hydrosilylation curable composition of claim 1, wherein the curable composition further comprises a condensation catalyst; or wherein the curable composition further comprises a phosphor or a filler; or wherein the curable composition further comprises a condensation catalyst and further comprises a phosphor or a filler.

10. The hydrosilylation curable composition of claim 1, wherein the curable composition is flowable at 20 degrees Celsius ( C.) and 101.3 kilopascals (kPa); or wherein the curable composition has a cure speed in Pascals per minute (Pa/min) of from about 0.5 to about 10 Pa/min by 150 C. isothermal rheology measurements; or wherein the curable composition is flowable at 20 degrees Celsius ( C.) and 101.3 kilopascals (kPa) and the curable composition has a cure speed in Pascals per minute (Pa/min) of from about 0.5 to about 10 Pa/min by 150 C. isothermal rheology measurements.

11. A cured product of curing the hydrosilylation curable composition of claim 1.

12. The cured product of claim 11, wherein the cured product has a Young's modulus of about 20 MPa to about 300 MPa after thermal aging at 225 C. for 48 hours; or wherein the cured product has a Young's modulus before thermal aging and a Young's modulus after thermal aging at 225 C. for 48 hours, wherein the ratio of the Young's modulus of the cured product after thermal aging at 225 C. for 48 hours versus the Young's modulus of the cured product before thermal aging is less than 4.

13. The cured product of claim 11, wherein the cured product is an organosiloxane block copolymer comprising: 0 to 10 mole percent M constituent units of the formula [R.sub.3SiO.sub.1/2], 40 to 90 mole percent D constituent units of the formula [R.sub.2SiO.sub.2/2], and 10 to 80 mole percent T constituent units of the formula [RSiO.sub.3/2]; wherein: the sum of the mole percent M, D, and T constituent units is 100 mole percent; the cured product comprises 0.5 to 35 mole percent silicon bonded hydroxy (SiOH); R is independently a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation or a C.sub.1 to C.sub.30 hydrocarbyl group comprising at least one aliphatic unsaturated bond; the D constituent units [R.sub.2SiO.sub.2/2] are arranged in linear blocks having an average of from 50 to 300 D constituent units [R.sub.2SiO.sub.2/2] per linear block; the T constituent units [RSiO.sub.3/2] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole; the M constituent units [R.sub.3SiO.sub.1/2] are connected to T units; at least 30% of the non-linear blocks are crosslinked with each other; each linear block is linked to at least one non-linear block via SiOSi linkages; the organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g/mole; and the organosiloxane block copolymer comprises from about 0.5 to about 5 mole % C.sub.1 to C.sub.30 hydrocarbyl group comprising at least one aliphatic unsaturated bond.

14. The cured product of claim 13, wherein the cured product is an organosiloxane block copolymer comprising 0 to 10 mole percent M constituent units of the formula [R.sub.3SiO.sub.1/2], 40 to 90 mole percent D constituent units of the formula [R.sub.2SiO.sub.2/2], and 10 to 60 mole percent T constituent units of the formula [RSiO.sub.3/2]; wherein: the sum of the mole percent M, D, and T constituent units is 100 mole percent; the cured product comprises 0.5 to 35 mole percent silicon bonded hydroxy (SiOH); R is independently a C.sub.1 to C.sub.30 hydrocarbyl free of aliphatic unsaturation or a C.sub.1 to C.sub.30 hydrocarbyl group comprising at least one aliphatic unsaturated bond; the D constituent units [R.sub.2SiO.sub.2/2] are arranged in linear blocks having an average of from 50 to 300 D constituent units [R.sub.2SiO.sub.2/2] per linear block; the T constituent units [RSiO.sub.3/2] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole; the M constituent units [R.sub.3SiO.sub.1/2] are connected to T units; at least 30% of the non-linear blocks are crosslinked with each other; each linear block is linked to at least one non-linear block via SiOSi linkages; the organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g/mole; and the organosiloxane block copolymer comprises from about 0.5 to about 5 mole % C.sub.1 to C.sub.30 hydrocarbyl group comprising at least one aliphatic unsaturated bond.

15. The cured product of claim 11, wherein the cured product has an elongation at break before thermal aging at 225 C. for 48 hours of about 20% to about 200%; or wherein the CIE b* value after aging for 72 hours at 225 C. is from 0 to about 7; or wherein the cured product has an elongation at break before thermal aging at 225 C. for 48 hours of about 20% to about 200% and the CIE b* value after aging for 72 hours at 225 C. is from 0 to about 7.

Description

EXAMPLES

(1) The following examples are included to demonstrate specific embodiments of the invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

(2) A summary of the examples presented herein is given in Tables 1a and 1b.

(3) TABLE-US-00001 TABLE 1a Example Formulation 1 M.sup.Vi.sub.0.12T.sup.PH.sub.0.88 + M.sup.Vi.sub.2D.sup.PH.sub.80 + M.sup.H.sub.2D.sup.PH2 + M.sup.H.sub.60T.sup.PH.sub.40 + Pt cat., (SiH/Vi = 1) 2 M.sup.Vi.sub.0.12T.sup.PH.sub.0.88 + M.sup.H.sub.2D.sup.PH.sub.121 + M.sup.H.sub.2D.sup.PH2 + Pt cat., (SiH/Vi = 1) 3 M.sup.Vi.sub.0.12T.sup.PH.sub.0.88 + M.sup.H.sub.2D.sup.PH.sub.121 + M.sup.H.sub.2D.sup.PH2 + PT cat. + DBU, (SiH/Vi = 1) 4 M.sup.Vi.sub.0.14T.sup.PH.sub.0.86 + M.sup.H.sub.2D.sup.PH.sub.146 + M.sup.vi.sub.2D.sup.PH.sub.20 + M.sup.H.sub.2D.sup.PH2 + Pt cat. + DBU, (SiH/Vi = 1) 5 M.sup.Vi.sub.0.14T.sup.PH.sub.0.86 + M.sup.H.sub.2D.sup.PH.sub.146 + M.sup.H.sub.2D.sup.PH2 + Pt cat. + DBU, (SiH/Vi = 1) 6 M.sup.Vi.sub.0.14T.sup.PH.sub.0.86 + M.sup.H.sub.2D.sup.PH.sub.146 + M.sup.H.sub.2D.sup.PH2 + M.sup.H.sub.60T.sup.PH.sub.40 + Pt cat., (SiH/Vi = 1) 7 M.sub.0.14D.sup.Vi.sub.0.10T.sup.PH.sub.0.76 + M.sup.H.sub.2D.sup.PH.sub.51 + M.sup.H.sub.60T.sup.PH.sub.40 + Pt cat., (SiH/Vi = 1) 8 M.sub.0.14D.sup.Vi.sub.0.10T.sup.PH.sub.0.76 + M.sup.H.sub.2D.sup.PH.sub.146 + M.sup.H.sub.60T.sup.PH.sub.40 + Pt cat., (SiH/Vi = 1)

(4) TABLE-US-00002 TABLE 1b Formulation details Vi Resin Example Resin Linear (mol %) (wt %) 1 M.sup.Vi.sub.0.12T.sup.PH.sub.0.88 M.sup.Vi.sub.2D.sup.PH.sub.80 12.1 50.4 2 M.sup.Vi.sub.0.12T.sup.PH.sub.0.88 M.sup.H.sub.2D.sup.PH.sub.121 12.1 49.8 3 M.sup.Vi.sub.0.12T.sup.PH.sub.0.88 M.sup.H.sub.2D.sup.PH.sub.121 12.1 49.8 4 M.sup.Vi.sub.0.12T.sup.PH.sub.0.86 M.sup.H.sub.2D.sup.PH.sub.146 14.1 49.9 5 M.sup.Vi.sub.0.14T.sup.PH.sub.0.86 M.sup.H.sub.2D.sup.PH.sub.146 14.1 45.1 6 M.sup.Vi.sub.0.14T.sup.PH.sub.0.86 M.sup.H.sub.2D.sup.PH.sub.146 14.1 45.1 7 M.sub.0.14D.sup.Vi.sub.0.10T.sup.PH.sub.0.76 M.sup.H.sub.2D.sup.PH.sub.51 10 62 8 M.sub.0.14D.sup.Vi.sub.0.10T.sup.PH.sub.0.76 M.sup.H.sub.2D.sup.PH.sub.146 10 55

Example 1

(5) Loaded a 2 liter (L) 3-neck round bottom flask with Dow Corning 217 Flake phenyl-T resin (550.0 grams (g)) and toluene (725.0 g). The flask was equipped with a poly(tetrafluoroethylene) stir paddle, thermometer and a water-cooled condenser. System was setup to capture HCl gas in a water trap. Loaded an addition funnel with toluene (100.0 g) and chlorodimethylvinylsilane (78.00 g, 0.655 moles). Dissolved resin completely and then added the chlorosilane solution slowly at room temperature. Heated at 50 C. for 2 hours. Stopped mixing and removed aqueous phase. Heated at 60 C. for 1 hour. Water washed several times at 80 C. using 40 milliliters (mL) deionized (DI) water amounts for each wash to remove residual HCl. Heated to reflux and removed residual water by azeotropic distillation. Stripped resin to dryness using a rotary evaporator at an oil bath temperature of 140 C. and 1 mm Hg. Product was a clear, crunchy solid at room temperature with a T.sub.g=56 C., M.sub.n=1,720, M.sub.w=2,660 (relative to polystyrene standards). Product composition by .sup.29Si NMR (M.sup.Vi.sub.0.12T.sup.Ph.sub.0.88), SiOH=28.3 mol %.

(6) Formulation:

(7) Part A: 10.8 g M.sup.Vi.sub.0.12T.sup.Ph.sub.0.88 resin was dissolved in 15 mL toluene. To the toluene solution was added 8 g M.sup.Vi.sub.2D.sup.Ph.sub.80, 1.573 g M.sup.H.sub.2D.sup.Ph2 and 0.366 g M.sup.H.sub.60T.sup.Ph.sub.40. The toluene was removed from the system at 90 C. and 5 mm Hg vacuum with rotary evaporator.

(8) Part B: M.sup.Vi.sub.2D.sup.Ph.sub.80 (0.5 g) was combined with 0.107 g Pt catalyst using speed mixer.

(9) Part A and Part B was combined well and then cured at 120 C. for 1 hour and 160 C. for 3 hours.

Example 2

(10) A 1 L 4-neck round bottom flask was loaded with Dow Corning short chain OH terminated phenyl-methyl siloxane polymer (2640.0 g). The flask was equipped with a poly(tetrafluoroethylene) stir paddle, thermometer, and a water-cooled condenser attached to collection flask setup to collect water. A nitrogen sweep was applied. The polymer was heated to 110 C. and then added an aqueous solution (3 wt %) of KOH (2.19 g). Heating was continued at 110 C. for 7 hours 50 minutes, at which point the reaction mixture was neutralized with aqueous phosphoric acid (2.5 wt %) (6.91 g). Cooled to near room temperature and then added some toluene (293.0 g) to reduce the viscosity. The mixture was mixed overnight at room temperature. The polymer was stripped using a thin film evaporator at a jacket temperature of 235 C. and 0.2 mm Hg. The stripped polymer was dissolved in toluene at 65 wt % and then added Darco G60 activated carbon black (1 wt % based on polymer) and mixed overnight at room temperature. Filtered product solution through a 0.45 m filter. Polymer dp=121 as measured from .sup.29Si NMR, wherein dp is degree of polymerization.

(11) A 1 L 3-neck flask was dried in 100 C. oven for two hours and then installed and cooled the flask under N.sub.2. The toluene solution of D.sup.Ph.sub.121OH.sub.2 containing 308.2 g D.sup.Ph.sub.121OH.sub.2 (474 g, 65 wt % solution) was added into the flask under nitrogen, followed by adding 300 mL anhydrous toluene to dilute the solution to 40 weight percent (wt %). Triethylamine (TEA; 5 mL) was added into the mixture under nitrogen, followed by stirring for 10 min, and then 4 mL Me.sub.2SiHCl was slowly injected into the reaction mixture by syringe under nitrogen within 10 min. A white precipitate formed in the solution as soon as Me.sub.2SiHCl was added. The cloudy reaction solution was stirred at room temperature and nitrogen for several hours to complete the reaction, followed by adding 150 L deionized H.sub.2O to quench the excess Me.sub.2SiHCl and then adding 10 g Na.sub.2SO4 anhydrous to dry the reaction mixture overnight. The clear solution was obtained by filtering the mixture with 1.2 m filter paper under 30 psi air pressure. About 306 g clear SiH capped siloxane product (M.sup.H.sub.2D.sup.Ph.sub.121) was obtained by removing toluene and the trace of TEA at 90 C. and 5 mm Hg vacuum with rotary evaporator.

(12) Formulation:

(13) Part A: 10.5 g M.sup.Vi.sub.0.12T.sup.Ph.sub.0.88 resin was dissolved in 15 mL toluene. To this solution was added 9 g M.sup.H.sub.2D.sup.Ph.sub.121 and 1.575 g M.sup.H.sub.2D.sup.Ph2. Toluene was removed from the system at 90 C. and 5 mmHg vacuum with rotary evaporator.

(14) Part B: 0.105 g Pt catalyst (Dow Corning produced Pt catalysts).

(15) Part A and Part B was mixed well and then cured at 120 C. for 1 hour and 160 C. for 3 hours.

Example 3

(16) Part A: 10.5 g M.sup.Vi.sub.0.12T.sup.Ph.sub.0.88 resin was dissolved in 15 mL toluene. To the toluene solution was added 9 g M.sup.H.sub.2D.sup.Ph.sub.121, 1.575 g M.sup.H.sub.2D.sup.Ph2, and DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene). Toluene was removed from the system at 90 C. and 5 mm Hg vacuum with rotary evaporator.

(17) Part B: 0.105 g Pt catalyst (Dow Corning produced Pt catalysts).

(18) Part A and Part B was mixed well and then cured at 120 C. for 1 hour and 160 C. for 3 hours.

Example 4

(19) A 3 L 3-neck round bottom indented Morton type flask was loaded with DI water (741.2 g). The flask was equipped with a poly(tetrafluoroethylene) stir paddle, thermometer, and a water-cooled condenser. The water was cooled down to 5 C. using an ice-water bath. A pre-mixed solution of phenyltrichlorosilane (355.4 g, 1.680 moles), vinyldimethylchlorosilane (38.61 g, 0.320 moles), and toluene (385.2 g) was added slowly with an addition funnel. The ice-water bath was immediately removed after addition was complete, and then a heating mantle was applied. Continued to mix for 15 minutes with no additional heat applied. Transferred reaction mixture into a 2 L round bottom flask with a bottom drain and then removed the aqueous layer. Added DI water (64.2 g), heated at 80 C. for 10 minutes and then removed the aqueous phase. Repeated the following process several times until the final wash water had a pH of 4.0. Added 2-propanol (16.05 g) and DI water (48.15 g), heated at 80 C. for 10 minutes and removed aqueous phase. Heated to reflux and removed residual water via azeotropic distillation. Distilled off volatiles (191.2 g) to remove residual 2-propanol reaching a vapor temperature of 110 C. Added toluene (153.0 g) to reduce the solids content to 40 wt %. Heated to 85 C. and then added a solution of 5 wt % dimethylamine in water (0.205 g). Heated at reflux for around 2 hours at 85 C. added more 5 wt % dimethylamine in water solution (0.103 g). Heated at reflux for 130 minutes. Washed four times at 80 C. using 25 mL of DI water for each wash. Heated to reflux and removed residual water by azeotropic distillation. Stripped resin to dryness using a rotary evaporator at an oil bath temperature of 150 C. and 1 mm Hg. Product was a crunchy solid at room temperature with an M.sub.n=2,070; M.sub.w=3,490 (relative to polystyrene standards). Product composition by .sup.29Si NMR (M.sup.Vi.sub.0.14T.sup.Ph.sub.0.86), SiOH=24.8 mol %

(20) OH terminated siloxane, D.sup.Ph.sub.146OH.sub.2, is a Dow Corning intermediate which was ordered from DC manufacture.

(21) A 1 L 3-neck flask was dried in 100 C. oven for two hours and then installed and cooled the flask under N.sub.2. 301.6 g (464 g 65 wt % solution) D.sup.Ph.sub.146OH.sub.2 was added into the flask under nitrogen, followed by adding 200 mL anhydrous toluene to dilute the solution to 45 wt %. To the toluene solution was added 6.3 mL triethylamine (TEA) under nitrogen, followed by stirring for 10 minutes, and then 5 mL Me.sub.2SiHCl was slowly injected into the reaction mixture by syringe under nitrogen within 10 minutes. A white precipitate formed in the solution immediately after Me.sub.2SiHCl was added. The cloudy reaction solution was stirred at room temperature and nitrogen for several hours to complete the reaction, followed by adding 400 L deionized H.sub.2O to quench the excess Me.sub.2SiHCl and then adding 10 g Na.sub.2SO4 anhydrous to dry the reaction mixture overnight. The clear solution was obtained by filtering the mixture with 1.2 m filter paper under 30 psi air pressure. About 300 g clear SiH capped siloxane product (M.sup.H.sub.2D.sup.Ph.sub.1461) was obtained by removing toluene and the trace of TEA at 90 C. and 5 mmHg vacuum with rotary evaporator.

(22) Formulation:

(23) Part A: 10.4 g M.sup.Vi.sub.0.14T.sup.Ph.sub.0.86 resin was dissolved in 15 mL toluene. To the toluene solution was added 7.2 g M.sup.H.sub.2D.sup.Ph.sub.146, 1.2 g M.sup.Vi.sub.2 D.sup.Ph.sub.20, 2.25 g M.sup.H.sub.2D.sup.Ph2, and DBU. Toluene was removed from the system at 90 C. and 5 mmHg vacuum with rotary evaporator.

(24) Part B: 0.104 g Pt catalyst (Dow Corning produced Pt catalysts).

(25) Part A and Part B was mixed well and then at 120 C. for 1 hour and 160 C. for 3 hours.

Example 5

(26) Part A: 9.6 g M.sup.Vi.sub.0.14T.sup.Ph.sub.0.86 resin was dissolved in 15 mL toluene. To the toluene solution was added 10 g M.sup.H.sub.2D.sup.Ph.sub.146, 1.7 g M.sup.H.sub.2D.sup.Ph2, and DBU. Toluene was removed from the system at 90 C. and 5 mmHg vacuum with rotary evaporator.

(27) Part B: 0.106 g Pt catalyst (Dow Corning produced Pt catalysts).

(28) Part A and Part B was mixed well and then cured at 120 C. for 1 hour and 160 C. for 3 hours.

Example 6

(29) Part A: 9.6 g M.sup.Vi.sub.0.14T.sup.Ph.sub.0.86 resin was dissolved in 15 mL toluene. To the toluene solution was added 10 g M.sup.H.sub.2D.sup.Ph.sub.146, 1.36 g M.sup.H.sub.2D.sup.Ph2, and 0.316 g M.sup.H.sub.60T.sup.Ph.sub.40. Toluene was removed from the system at 90 C. and 5 mmHg vacuum with rotary evaporator.

(30) Part B: 0.106 g Pt catalyst (Dow Corning produced Pt catalysts).

(31) Part A and Part B was mixed well and cured at 120 C. for 1 hour and 160 C. for 3 hours.

Example 7

(32) A 3 L 3-neck round bottom indented Morton type flask was loaded with phenyltrimethoxysilane (267.7 g, 1.35 mols), hexamethyldisiloxane (21.92 g, 0.27 mol) and methylvinyldimethoxysilane (23.8 g, 0.18 mol), followed by adding 92 L FC24 (500 ppm in reaction mixture). The flask was equipped with a poly(tetrafluoroethylene) stir paddle, thermometer, and a water-cooled condenser. DI water (43.7 g, 2.426 mols) was added slowly at room temperature (about 25 C.) and the temperature rose up to 54 C. with the completion of adding water, followed by heating at 60 C. for 3 hours. Then, about 127.4 g methanol formed was removed at 85 C. 114 g toluene was added to make the NVC of the formed resin about 65%. 1.46 g KOH solution (10 wt % in water) was added to neutralize FC24 and base body the resin. Aqueous phase was removed by refluxing and then the mixture was refluxed for 3 hours. 0.7 g HCl solution (10 wt % in water) was added at 80 C., followed by stirring to mix them until cooling to room temperature. The reaction mixture was transferred into a 1 L round bottom flask with a bottom drain, followed by adding 203.75 g toluene and washing with 50 mL water for three times at 80 C. Residual water was removed by azeotropic distillation. The mixture was filtered through a 5 m filter and stripped to dry using a rotovapor at 125 C. Product composition by .sup.29Si NMR (M.sub.0.14D.sup.Vi.sub.0.1T.sup.Ph.sub.0.76).

(33) OH terminated siloxane, D.sup.Ph.sub.51OH.sub.2, is a Dow Corning intermediate which was ordered from DC manufacture.

(34) A 1 L 3-neck flask was dried in 100 C. oven for two hours and then installed and cooled the flask under N.sub.2. 196.5 g (302.3 g 65 wt % solution) D.sup.Ph.sub.51OH.sub.2 was added into the flask under nitrogen, followed by adding 100 mL anhydrous toluene to dilute the solution to 50 wt %. To the toluene solution was added 10.6 mL triethylamine (TEA) under nitrogen, followed by stirring for 10 minutes, and then 8.4 mL Me.sub.2SiHCl was slowly injected into the reaction mixture by syringe under nitrogen within 6 minutes. A white precipitate formed in the solution immediately after Me.sub.2SiHCl was added. The cloudy reaction solution was stirred at room temperature and nitrogen for several hours to complete the reaction, followed by adding 500 L deionized H.sub.2O to quench the excess Me.sub.2SiHCl and then adding 10 g Na.sub.2SO4 anhydrous to dry the reaction mixture overnight. The clear solution was obtained by filtering the mixture with 1.2 m filter paper under 30 psi air pressure. About 181 g clear SiH capped siloxane product (M.sup.H.sub.2D.sup.Ph.sub.51) was obtained by removing toluene and the trace of TEA at 90 C. and 5 mmHg vacuum with rotary evaporator.

(35) Formulation:

(36) Part A: 7 g M.sub.0.14D.sup.Vi.sub.0.1T.sup.Ph.sub.0.76 resin was dissolved in 7 g toluene. To the toluene solution was added 3.5 g M.sup.H.sub.2D.sup.Ph.sub.51, 0.814 g M.sup.H.sub.60T.sup.Ph.sub.40. Toluene was removed from the system at 90 C. and 5 mmHg vacuum with rotary evaporator.

(37) Part B: 0.226 g Pt catalyst (Dow Corning produced Pt catalysts to make 2 ppm Pt in the formulation).

(38) Part A and Part B was mixed well and then cured at 120 C. for 1 hour and 160 C. for 3 hours.

Example 8

(39) Formulation:

(40) Part A: 6 g M.sub.0.14D.sup.Vi.sub.0.1T.sup.Ph.sub.0.76 resin was dissolved in 7 g toluene. To the toluene solution was added 4.15 g M.sup.H.sub.2D.sup.Ph.sub.146, 0.763 g M.sup.H.sub.60T.sup.Ph.sub.40. Toluene was removed from the system at 90 C. and 5 mmHg vacuum with rotary evaporator.

(41) Part B: Part B: 0.11 g Pt catalyst (Dow Corning produced Pt catalysts to make 1 ppm Pt in the formulation).

(42) Part A and Part B was mixed well and then cured at 120 C. for 1 hour and 160 C. for 3 hours.

(43) The Young's modulus of selected cured hydrosilylation curable compositions of the various embodiments of the present invention before and after thermal aging at 225 C. for 48 hours; elongation at break before and after thermal aging of selected cured hydrosilylation curable compositions of the various embodiments of the present invention; and the CIE b* values before and after aging for 72 hours at 225 degrees Celsius ( C.) of selected cured hydrosilylation curable compositions of the various embodiments of the present invention are given below in Table 2.

(44) TABLE-US-00003 TABLE 2 Young's Modulus Young's Modulus % Elongation % Elongation before thermal after thermal at break before at break after CIE b* CIE b* Example aging (MPa) aging (MPa) thermal aging thermal aging before aging after aging 1 0.6 3.63 32.80 7.5 0.6 3.63 2 43.6 122.7 91.90 29.20 1.18 2.41 3 93 153.1 35 14.60 0.65 2.47 4 101.8 200.6 22 5.84 1.61 6.45 5 46.4 123 45.50 10.60 Not Not determined determined 6 44.2 119.1 22 5.84 0.83 5.07 7 125 221 41.7 15 Not Not determined determined 8 56 61.5 72.2 42 Not Not determined determined

(45) In some embodiments the invention comprises the hydrosilylation curable composition as formulated in any one of Examples 1 to 7, alternatively any one of Examples 1 to 8. In some embodiments the hydrosilylation curable composition is selected from a group of any six of the hydrosilylation curable compositions of Examples 1 to 7, alternatively any seven of Examples 1 to 8. That is, any one of the hydrosilylation curable compositions of Examples 1 to 7, alternatively of Examples 1 to 8 may be excluded from some embodiments. For example, the hydrosilylation curable composition may be as formulated in any one of Examples 1 to 6, alternatively any one of Examples 2 to 7, alternatively any one of Examples 1 and 3 to 8. In other embodiments the hydrosilylation curable composition is as formulated in Example 1, alternatively Example 2, alternatively Example 3, alternatively Example 4, alternatively Example 5, alternatively Example 6, alternatively Example 7, alternatively Example 8.

(46) In some embodiments the invention comprises the cured product of curing the hydrosilylation curable composition as formulated in any one of Examples 1 to 7, alternatively any one of Examples 1 to 8. In some embodiments the cured product is selected from a group of any six of the Examples 1 to 7, alternatively any seven of Examples 1 to 8. That is, any one of the cured products of Examples 1 to 7, alternatively any one of Examples 1 to 8 may be excluded from some embodiments. For example, the cured product may be as prepared in any one of Examples 1 to 6, alternatively any one of Examples 2 to 7, alternatively any one of Examples 1 and 3 to 8. In other embodiments the cured product may be as prepared in Example 1, alternatively Example 2, alternatively Example 3, alternatively Example 4, alternatively Example 5, alternatively Example 6, alternatively Example 7, alternatively Example 8.