Organosiloxane compositions and uses thereof
View Patent ↗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.
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 1 R 2 R 3 SiO 1/2 ] a [R 1 R 2 R 4 SiO 1/2 ] b [R 1 R 5 SiO 2/2 ] c [R 1 SiO 3/2 ] d ,
wherein R 1 , R 2 , and R 3 are independently a C 1 to C 30 hydrocarbyl group free of aliphatic unsaturation, and R 4 and R 5 are independently a C 1 to C 30 hydrocarbyl group free of aliphatic unsaturation or a C 2 to C 30 hydrocarbyl group comprising aliphatic unsaturation,
0≤subscript a<0.1,
0<subscript b<0.2,
0≤subscript c<0.2,
subscript d=(1−a−b−c),
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 1 R 2 R 8 SiO 1/2 ] e [R 1 R 9 SiO 2/2 ] f [R 1 SiO 3/2 ] g , wherein R 1 and R 2 are independently a C 1 to C 30 hydrocarbyl free of aliphatic unsaturation, R 8 and R 9 are independently a H, a C 1 to C 30 hydrocarbyl free of aliphatic unsaturation or a silane radical of the formula —[R 10 R 11 Si] p [R 10 R 11 SiH] (wherein R 10 , R 11 is independently a H or a C 1 to C 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 is≥2 per crosslinker molecule; and
(e) a hydrosilylation catalyst;
and at least one of:
(c) an SiH siloxane having the formula
[R 1 R 2 R 6 SiO 1/2 ][R 1 R 2 SiO 2/2 ] m [O 1/2 SiR 6 R 2 R 1 ],
wherein R 1 and R 2 is independently a C 1 to C 30 hydrocarbyl free of aliphatic unsaturation,
R 6 independently is H or a silane radical of the formula —[SiR 1 R 2 ] p [R 1 R 2 SiH],
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 1 R 2 R 7 SiO 1/2 ][R 1 R 2 SiO 2/2 ] n [O 1/2 SiR 7 R 1 R 2 ],
wherein R 1 and R 2 is independently a C 1 to C 30 hydrocarbyl free of aliphatic unsaturation,
R 7 is a C 2 to C 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 4 or R 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 1 R 2 R 8 SiO 1/2 ] e [R 1 R 9 SiO 2/2 ] f and a crosslinker of the formula [R 1 R 2 R 8 SiO 1/2 ] e [R 1 SiO 3/2 ] g in a ratio of about 5:1 to about 3:1 w/w, wherein R 1 , R 2 , R 8 , R 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 0≤subscript c<0.1; or wherein 0.05<subscript b<0.15 or 0.08<subscript b<0.15 and 0≤subscript 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 3 SiO 1/2 ],
40 to 90 mole percent D constituent units of the formula [R 2 SiO 2/2 ], and
10 to 80 mole percent T constituent units of the formula [RSiO 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 1 to C 30 hydrocarbyl free of aliphatic unsaturation or a C 1 to C 30 hydrocarbyl group comprising at least one aliphatic unsaturated bond;
the D constituent units [R 2 SiO 2/2 ] are arranged in linear blocks having an average of from 50 to 300 D constituent units [R 2 SiO 2/2 ] per linear block;
the T constituent units [RSiO 3/2 ] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole;
the M constituent units [R 3 SiO 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 —Si—O—Si— 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 1 to C 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 3 SiO 1/2 ],
40 to 90 mole percent D constituent units of the formula [R 2 SiO 2/2 ], and
10 to 60 mole percent T constituent units of the formula [RSiO 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 1 to C 30 hydrocarbyl free of aliphatic unsaturation or a C 1 to C 30 hydrocarbyl group comprising at least one aliphatic unsaturated bond;
the D constituent units [R 2 SiO 2/2 ] are arranged in linear blocks having an average of from 50 to 300 D constituent units [R 2 SiO 2/2 ] per linear block;
the T constituent units [RSiO 3/2 ] are arranged in non-linear blocks having a molecular weight of at least 500 g/mole;
the M constituent units [R 3 SiO 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 —Si—O—Si— 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 1 to C 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.