Silicone ligands for quantum dots
View Patent ↗The present invention relates to silicone polymer ligands for binding to quantum dots. The silicone polymer ligands contain a multiplicity of amine, carboxy, and/or phosphine binding groups suitable for attachment to quantum dots. The present invention also describes a process for the preparation of quantum dot binding ligands.
1. A quantum dot binding ligand comprising the structure of formula I:
wherein
R 1 , R 2 , R 3 , R 7 , R 8 , and R 9 are each independently C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, -L 3 -(R 11 ) q , cycloalkyl, or aryl;
R 4 and R 5 are each independently C 1-20 -alkyl, C 1-20 heteroalkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, cycloalkyl, or aryl, each optionally substituted with one or more Si(R 12 ) 3 groups;
R 6 is C 1-20 -alkyl, C 1-20 heteroalkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, cycloalkyl, or aryl, each optionally substituted with one or more Si(R 12 ) 3 groups;
each R 11 is independently NR 2a R 2b , C(O)OH, or PR 3a R 3b ;
each of R 2a and R 2b is independently H or C 1-6 alkyl;
each of R 3a and R 3b is independently H or C 1-6 alkyl;
each L 1 is independently C 2-20 alkylene, C 2-20 heteroalkylene, or C 2-8 alkylene-O—C 2-8 alkylene;
each L 2 is independently C 2-20 alkylene, C 2-20 heteroalkylene, C 2-8 alkylene-O—C 2-8 alkylene, C 2-8 alkylene-(C(O)NH—C 2-8 alkylene) q , C 2-8 heteroalkylene-(C(O)NH—C 2-8 alkylene) q , or C 3-8 alkylene-O—C 1-8 alkylene-(C(O)NH—C 2-8 alkylene) q , wherein each L 2 is substituted with one or more (R 10 ) q , Si(R 12 ) 3 , or C 3-10 cycloalkoxy;
each L 3 is independently C 2-20 alkylene, C 2-20 heteroalkylene, C 2-8 alkylene-O—C 2-8 alkylene, C 2-8 alkylene-(C(O)NH—C 2-8 alkylene) q , C 2-8 heteroalkylene-(C(O)NH—C 2-8 alkylene) q , or C 3-8 alkylene-O—C 1-8 alkylene-(C(O)NH—C 2-8 alkylene) q ;
each R 10 is independently NR 2a R 2b , C(O)OH, or PR 3a R 3b ;
each R 12 is independently C 1-6 alkyl, cycloalkyl, or aryl;
m is 0 to 1000;
n is 2 to 50; and
q is 1 to 10,
wherein at least one L 2 group is substituted by Si(R 12 ) 3 , and wherein the ligand comprises 2, 3, or 4 different kinds of n repeat units.
2. The quantum dot binding ligand of claim 1 , wherein
R 1 , R 2 , R 3 , R 7 , R 8 , and R 9 are each independently C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, -L 3 -(R 11 ) q , cycloalkyl, or aryl;
R 4 is C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, cycloalkyl, or aryl;
R 5 is C 8-20 alkyl, C 8-20 heteroalkyl, cycloalkyl, or aryl;
R 6 is C 1-20 alkyl, C 1-20 heteroalkyl, C 2-20 alkenyl, C 2-20 alkynyl, cycloalkyl, or aryl;
each L 1 and L 2 is independently C 3-8 alkylene;
each R 10 is independently NR 2a R 2b or C(O)OH;
each of R 2a and R 2b is H or C 1-6 alkyl;
each L 3 is independently C 2-20 alkylene, C 2-20 heteroalkylene, C 2-8 alkylene-O—C 2-8 alkylene, C 2-8 alkylene-(C(O)NH—C 2-8 alkylene) q , C 2-8 heteroalkylene-(C(O)NH—C 2-8 alkylene) q , or C 3-8 alkylene-O—C 1-8 alkylene-(C(O)NH—C 2-8 alkylene) q ;
m is an integer from 5 to 100;
n is an integer from 2 to 10; and
q is an integer from 1 to 10.
3. The quantum dot binding ligand of claim 1 , wherein L 1 is independently selected from the group consisting of C 3-8 alkylene and C 3-8 alkylene-O—C 2-8 alkylene.
4. The quantum dot binding ligand of claim 1 , wherein each L 1 is independently selected from the group consisting of propylene, butylene, pentylene, or n-propylene-O-isopropylene.
5. The quantum dot binding ligand of claim 1 , wherein at least one L 2 group is substituted by (R 10 ) q .
6. The quantum dot binding ligand of claim 5 , wherein the L 2 -(R 10 ) q is independently selected from the group consisting of C 3-8 alkylene-C(O)OH, C 3-8 alkylene-(C(O)OH) 2 , C 3-8 alkylene-O—C 2-8 alkylene-(C(O)OH) 3 , C 3-8 alkylene-NR 2a R 2b , C 3-8 alkylene-(C(O)NH—C 2-8 alkylene-NR 2a R 2b ) 2 , C 3-8 alkylene-PR 3a R 3b , C 3-8 alkylene-O—C 2-8 alkylene-PR 3a R 3b , and C 3-8 alkylene-(C(O)NH—C 2-8 alkylene-PR 3a R 3b ) 2 .
7. The quantum dot binding ligand of claim 5 , wherein the L 2 -(R 10 ) q is independently selected from the group consisting of C 3-8 alkylene-C(O)OH, C 3-8 alkylene-(C(O)OH) 2 , and C 3-8 alkylene-NR 2a R 2b .
8. The quantum dot binding ligand of claim 5 , wherein the L 2 -(R 10 ) q is independently selected from the group consisting of:
9. The quantum dot binding ligand of claim 1 , wherein the Si(R 12 ) 3 is Si(CH 3 ) 3 .
10. The quantum dot binding ligand of claim 1 , comprising 2 different kinds of n repeat units.
11. The quantum dot binding ligand of claim 1 , wherein at least one L 2 group is substituted by (R 10 ) q and at least one L 2 group is substituted by Si(R 12 ) 3 .
12. The quantum dot binding ligand of claim 1 , wherein
R 1 , R 2 , R 3 , R 7 , R 8 , and R 9 are each independently C 1-3 alkyl;
R 4 and R 5 are each independently C 1-3 alkyl; and
R 6 is C 1-3 alkyl.
13. The quantum dot binding ligand of claim 12 , having the structure of formula II:
14. A method of making a quantum dot binding ligand of claim 1 , which comprises:
reacting:
(a) a thiol functional siloxane polymer of formula IV:
wherein
R 1 , R 2 , R 3 , R 7 , R 8 , and R 9 are each independently C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, -L 3 -(R 11 ) q , cycloalkyl, or aryl;
R 4 and R 5 are each independently C 1-20 -alkyl, C 1-20 heteroalkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, cycloalkyl, or aryl, each optionally substituted with one or more Si(R 12 ) 3 groups;
R 6 is C 1-20 -alkyl, C 1-20 heteroalkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, cycloalkyl, or aryl,
each optionally substituted with one or more Si(R 12 ) 3 groups;
each R 11 is independently NR 2a R 2b , C(O)OH, or PR 3a R 3b ;
each R 12 is independently C 1-6 alkyl, cycloalkyl, or aryl;
L 1 is C 2-20 alkylene, C 2-20 heteroalkylene, or C 2-8 alkylene-O—C 2-8 alkylene;
L 3 is C 2-20 alkylene, C 2-20 heteroalkylene, C 2-8 alkylene-O—C 2-8 alkylene, C 2-8 alkylene-(C(O)NH—C 2-8 alkylene) q , C 2-8 heteroalkylene-(C(O)NH—C 2-8 alkylene) q , or
C 3-8 alkylene-O—C 1-8 alkylene-(C(O)NH—C 2-8 alkylene) q ;
m is 0 to 1000;
n is 2 to 50; and
q is 1 to 10;
(b) with a first alkene of formula V:
wherein
L 4 is C 2-18 alkylene, C 2-18 heteroalkylene, C 2-6 alkylene-O—C 2-8 alkylene, C 2-6 alkylene-(C(O)NH—C 2-8 alkylene) q , C 2-6 heteroalkylene-(C(O)NH—C 2-8 alkylene) q , or C 3-6 alkylene-O—C 1-8 alkylene-(C(O)NH—C 2-8 alkylene) q , wherein L 4 is substituted with (R 10 ) q , Si(R 12 ) 3 , or C 3-10 cycloalkoxy;
each R 10 is independently NR 2a R 2b , C(O)OH, or PR 3a R 3b ;
each R 12 is independently C 1-6 alkyl, cycloalkyl, or aryl;
each of R 2a and R 2b is independently H or C 1-6 alkyl;
each of R 3a and R 3b is independently H or C 1-6 alkyl; and
q is 1 to 10;
in the presence of heat, light, or an initiator,
to obtain a compound of formula I.
15. The method of claim 14 , further comprising reacting the mixture of (b) with:
(c) a second alkene of formula V:
wherein
L 4 is C 2-18 alkylene, C 2-18 heteroalkylene, C 2-6 alkylene-O—C 2-8 alkylene, C 2-6 alkylene-(C(O)NH—C 2-8 alkylene) q , C 2-6 heteroalkylene-(C(O)NH—C 2-8 alkylene) q , or C 3-6 alkylene-O—C 1-8 alkylene-(C(O)NH—C 2-8 alkylene) q , wherein L 4 is substituted with (R 10 ) q , Si(R 12 ) 3 , or C 3-10 cycloalkoxy;
each R 10 is independently NR 2a R 2b , C(O)OH, or PR 3a R 3b ;
each R 12 is independently C 1-6 alkyl, cycloalkyl, or aryl;
each of R 2a and R 2b is independently H or C 1-6 alkyl;
each of R 3a and R 3b is independently H or C 1-6 alkyl; and
q is 1 to 10;
in the presence of heat, light, or an initiator,
to obtain a compound of formula I.
16. A composition comprising:
a quantum dot binding ligand of claim 1 ; and
at least one population of light emitting quantum dots.
17. The composition of claim 16 , wherein the quantum dot binding ligand has the structure of formula II:
18. The composition of claim 16 , wherein the light emitting quantum dots are InP.
19. The composition of claim 16 , further comprising a matrix material.
20. The quantum dot binding ligand of claim 1 , comprising 3 different kinds of n repeat units.