Self-healing and stretchable polymeric compositions
View Patent ↗Disclosed herein a self-healing, flexible, conductive compositions. The conductive compositions include conductive polymers and acidic polyacrylamides. The compositions are useful in a wide range of applications, including wearable electronics and sensors. The compositions may be prepared using environmentally friendly procedures.
1. A method of preparing a flexible, self-healing, conductive composition comprising polymerizing a conductive polymer monomer precursor in a reaction medium to prepare a conductive polymer, wherein the reaction medium further comprises at least one acidic polyacrylamide and at least one small molecule dopant comprising from 2-10 acidic groups, to provide a flexible, self-healing, conductive composition wherein the acidic polyacrylamide comprises a repeating unit of Formula (1):
wherein:
R 1 is selected from hydrogen and methyl;
R 2a and R 2b are independently selected from hydrogen, C 1-4 alkyl, wherein R 2a and R 2b may together from a ring;
R is in each case independently selected from H, F, Cl, Br, C 1-4 alkyl, or OC 1-4 alkyl;
m is selected from 1, 2, 3, 4, 5, or 6; and
X is —SO 3 H, —PO 3 H, or —COOH.
2. The method according to claim 1 , wherein the conductive polymer monomer precursor and the acidic polyacrylamide are present in the reaction medium in a weight ratio (conductive polymer monomer precursor:acidic polyacrylamide) from 1:500 to 1:2.
3. The method according to claim 1 , wherein the conductive polymer monomer precursor and small molecule dopant are present in the reaction medium in a weight ratio (conductive polymer monomer precursor:small molecule dopant) from 1:20 to 2:1.
4. The method according to claim 1 , wherein X is —SO 3 H and R 2a and R 2b are both methyl.
5. The method according to claim 1 , wherein the acidic polyacrylamide has an average molecular weight from 200-2,500 kDa.
6. The method according to claim 1 , wherein the small molecule dopant comprises a compound of Formula (3):
wherein represents a single or double bond, and each of R d1 , R d2 , R d3 , R d4 , R d5 , and R d6 are independently selected from hydrogen, C 1-10 alkyl, OH, C 1-10 alkoxy, C 1-10 haloalkyl, C 1-10 haloalkoxy, aryl, heterocyclyl, F, Cl, Br, I, CN, COOH, SO 3 H, PO 3 H, and NO 2 , and wherein any of R d1 , R d2 , R d3 , R d4 , R d5 , and R d6 may together form a ring; providing that at least two of R d1 , R d2 , R d3 , R d4 , R d5 , and R d6 are COOH, SO 3 H, or PO 3 H.
7. The method according to claim 1 , wherein the small molecule dopant comprises phytic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, or 1,2,3,4-benzenetetracarboxylic acid.
8. The method according to claim 1 , wherein the conductive polymer comprises a poly(aniline), a poly(thiophene), or a poly(pyrrole).
9. The method according to claim 1 , wherein the conductive monomer precursor comprises a compound of Formula (4a) or (4b):
wherein R p1 , R p2 , R p3 , and R p4 are independently selected from hydrogen, C 1-10 alkyl, OH, C 1-10 alkoxy, NH 2 , C 1-10 alkylamine, C 1-10 dialkylamine, C 1-10 haloalkoxy, aryl, heterocyclyl, F, Cl, Br, I, CN, COOH, and NO 2 , and wherein either R p1 and R p2 or R p3 and R p4 may together form a ring; and
A 1 and A 2 are independently selected from OH, SH, NR p5 , wherein R p5 is hydrogen or C 1-10 alkyl.
10. A method of preparing a flexible, self-healing, conductive composition comprising polymerizing an acidic acrylamide in a reaction medium to prepare an acidic polyacrylamide, wherein the reaction medium further comprises at least one conductive polymer and at least one small molecule dopant comprising from 2-10 acidic groups to provide a flexible, self-healing, conductive composition wherein the acidic polyacrylamide comprises a repeating unit of Formula (1):
wherein:
R 1 is selected from hydrogen and methyl;
R 2a and R 2b are independently selected from hydrogen, C 1-4 alkyl, wherein R 2a and R 2b may together from a ring;
R is in each case independently selected from H, F, Cl, Br, C 1-4 alkyl, or OC 1-4 alkyl;
m is selected from 1, 2, 3, 4, 5, or 6; and
X is —SO 3 H, —PO 3 H, or —COOH.
11. The method according to claim 10 , wherein the conductive polymer and the acidic acrylamide are present in the reaction medium in a weight ratio (conductive polymer monomer precursor:acidic acrylamide) from 1:500 to 1:2.
12. The method according to claim 10 , wherein the conductive polymer and small molecule dopant are present in the reaction medium in a weight ratio (conductive polymer:small molecule dopant) from 1:20 to 2:1.
13. The method according to claim 1 , wherein X is —SO 3 H and R 2a and R 2b are both methyl.
14. The method according to claim 13 , wherein m is 1, and R is in each case H.
15. The method according to claim 10 , wherein the conductive polymer comprises a poly(aniline), a poly(thiophene), or a poly(pyrrole).
16. The method according to claim 10 , wherein the conductive polymer comprises polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), poly(3-methyl-4-hexyloxypyrrole), poly(3-methyl-4-hexyloxypyrrole), poly(thiophene), poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), poly(3-anilinesulfonic acid), or a copolymers thereof.
17. The method according to claim 10 , wherein the small molecule dopant comprises a compound of Formula (3):
wherein represents a single or double bond, and each of R d1 , R d2 , R d3 , R d4 , R d5 , and R d6 are independently selected from hydrogen, C 1-10 alkyl, OH, C 1-10 alkoxy, C 1-10 haloalkyl, C 1-10 haloalkoxy, aryl, heterocyclyl, F, Cl, Br, I, CN, COOH, SO 3 H, PO 3 H, and NO 2 , and wherein any of R d1 , R d2 , R d3 , R d4 , R d5 , and R d6 may together form a ring; providing that at least two of R d1 , R d2 , R d3 , R d4 , R d5 , and R d6 are COOH, SO 3 H, or PO 3 H.
18. The method according to claim 10 , wherein the small molecule dopant comprises phytic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, or 1,2,3,4-benzenetetracarboxylic acid.