Silicone ligands for quantum dots

Patent metadata

Field	Value
Publication number	US-9969844-B2
Application number	US-201514801314-A
Country	US
Kind code	B2
Filing date	Jul 16, 2015
Priority date	Jul 16, 2014
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

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.

First claim

What is claimed is:

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 heteroalky

Assignees

• Nanosys Inc

Inventors

• Furuta Paul T

Classifications

• C09K11/025 Primary

  non-luminescent particle coatings or suspension media · CPC title

• C08G77/28

  sulfur-containing groups · CPC title

• C09K11/70

  containing phosphorus · CPC title

• C08G77/382

  containing atoms other than carbon, hydrogen, oxygen or silicon · CPC title

• C08G77/392 Primary

  containing sulfur · CPC title