Linear-hyperbranched polymers as performance additives for solid electrolytic capacitors
View Patent ↗Provided herein is an improved capacitor and a method for forming an improved capacitor. The method includes providing an anode and forming a dielectric on the anode. A linear-hyperbranched polymer is formed and a conductive polymer dispersion is prepared comprising at least one conducting polymer, one polyanion and the linear-hyperbranched polymer. A layer of the conductive polymer dispersion if formed wherein said dielectric is between the anode and the layer.
1. A method for forming a capacitor comprising:
providing an anode;
forming a dielectric on said anode;
preparing a linear-hyperbranched polymer;
preparing a conductive polymer dispersion comprising at least one conducting polymer, one polyanion and said linear-hyperbranched polymer; and
forming a layer of said conductive polymer dispersion wherein said dielectric is between said anode and said layer.
2. The method for forming a capacitor of claim 1 wherein said anode comprises a valve metal or a conductive compound of said valve metal.
3. The method for forming a capacitor of claim 1 wherein said cathode comprises a conductive polymer or manganese dioxide.
4. The method forming a capacitor of claim 3 wherein said conductive polymer is selected from the group consisting of polypyrrole, polyaniline, polythiophene and substituted derivatives thereof.
5. The method for forming a capacitor of claim 1 wherein said dielectric is an oxide of said anode.
6. The method for forming a capacitor of claim 1 wherein said linear-hyperbranched polymer comprises a linear portion.
7. The method for forming a capacitor of claim 6 wherein said linear portion comprises at least two reactive groups.
8. The method for forming a capacitor of claim 7 wherein said reactive groups are selected from the group consisting of hydroxyl, amino and epoxy.
9. The method for forming a capacitor of claim 6 wherein said linear portion comprises at least one pendant group selected from polyimide-ester-amide, polyesteramide and polyesteramine.
10. The method for forming a capacitor of claim 6 wherein said linear portion comprises:
wherein R 21 and R 25 are terminating groups;
R 22 , R 23 and R 24 are independently alkyls or substituted alkyls of 1 to 50 carbons;
n is an integer; and
wherein R 21 , R 22 , R 23 , R 24 , R 25 and n are selected such that the molecular weight of said linear portion is no more than 1000.
11. The method for forming a capacitor of claim 10 wherein said R 21 and R 25 are selected from the atoms necessary to form hydroxyl, amine or epoxy.
12. The method for forming a capacitor of claim 1 wherein said preparing of said linear-hyperbranched polymer comprises reacting a diol, an anhydride and an acrylate to form a linear portion.
13. The method for forming a capacitor of claim 12 wherein said diol is OH—R 1 —OH wherein R 1 is a linear polymer with reactive groups.
14. The method for forming a capacitor of claim 12 wherein said anhydride is defined by:
wherein R 2 is a linear alkyl of 1 to 6 carbons, which may be substituted, or the atoms necessary to form a ring which may be substituted.
15. The method for forming a capacitor of claim 14 wherein said ring is an aromatic ring.
16. The method for forming a capacitor of claim 12 wherein said acrylate is defined by:
wherein R 3 is a linear alkyl of 1 to 50 carbons which may be substituted, an ether or polyether which may be substituted.
17. The method for forming a capacitor of claim 16 wherein said acrylate is defined by:
wherein R7 is hydrogen or methyl and n is an integer of no more than 10.
18. The method for forming a capacitor of claim 16 wherein said acrylate is selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate (HEA), 2,2-bis(hydroxymethyl)propyl acrylate;
19. The method for forming a capacitor of claim 12 wherein said preparing of said linear-hyperbranched polymer comprises reacting said linear portion with a hydroxyl amine.
20. The method for forming a capacitor of claim 19 wherein said hydroxyl amine is defined by
wherein R 5 and R 5′ are independently selected from linear alkyls of 1-6 carbons which may be substituted.
21. The method for forming a capacitor of claim 20 wherein said hydroxyl amine is selected from:
22. The method for forming a capacitor of claim 1 wherein said linear-hyperbranched polymer comprises at least Generation 1 branching.
23. The method for forming a capacitor of claim 22 wherein said linear-hyperbranched polymer comprises at least Generation 2 branching.
24. The method for forming a capacitor of claim 22 wherein said linear-hyperbranched polymer has an acid number of at least 100 to no more than 1000.
25. The method for forming a capacitor of claim 24 wherein said linear-hyperbranched polymer has an acid number of no more than 500.
26. The method for forming a capacitor of claim 24 wherein said linear-hyperbranched polymer has an acid number of no more than 200.
27. The method for forming a capacitor of claim 1 wherein said binder has no more than 10 wt % sulfonate.
28. The method for forming a capacitor of claim 27 wherein said binder has no more than 0.1 wt % sulfonate.
29. The method for forming a capacitor of claim 1 wherein binder has no more than 10 wt % primary or secondary amines.
30. The method for forming a capacitor of claim 29 wherein binder has no more than 0.1 wt % primary or secondary amines.
31. The method for forming a capacitor of claim 1 further comprising cross-linking said cathode.
32. The method for forming a capacitor of claim 31 wherein cross-linking includes reacting reactive groups of said cathode with a crosslinker.
33. The method for forming a capacitor of claim 32 wherein said crosslinker is selected from a silane and a ethylene glycol diglycidyl ether.
34. The method for forming a capacitor of claim 33 wherein said crosslinker is selected from the group consisting of:
35. A process of manufacturing a capacitor comprising:
providing an anode;
forming a dielectric on said anode;
forming a linear-hyperbranched polymer by reacting a diol a anhydride and an acrylate to form a linear portion and then reacting said linear portion with a hydroxyl amine;
forming a dispersion comprising said linear-hyperbranched polymer and a conductor; and
forming a cathode of said dispersion with said dielectric between said cathode and said anode.
36. The process of manufacturing a capacitor of claim 35 wherein said anode comprises a valve metal or a conductive compound of said valve metal.
37. The process of manufacturing a capacitor of claim 35 wherein said cathode comprises a conductive polymer or manganese dioxide.
38. The process of manufacturing a capacitor of claim 35 wherein said dielectric is an oxide of said anode.
39. The process of manufacturing a capacitor of claim 35 wherein said linear-hyperbranched polymer comprises a linear portion.
40. The process of manufacturing a capacitor of claim 39 wherein said linear portion comprises at least two reactive end groups selected from the group consisting of hydroxyl, amino and epoxy.
41. The process of manufacturing a capacitor of claim 39 wherein said linear portion comprises at least one of polyamide-ester-amide, polyesteramide and polyesteramine.
42. The process of manufacturing a capacitor of claim 39 wherein said linear portion comprises:
wherein R 21 and R 25 are terminating groups;
R 22 , R 23 and R 24 are independently alkyls or substituted alkyl of 1 to 50 carbons;
n is an integer and
wherein R 21 , R 22 , R 23 , R 24 , R 25 and n are selected such that the molecular weight of said linear portion is no more than 1000.
43. The process of manufacturing a capacitor of claim 35 wherein said preparing of said linear-hyperbranched polymer comprises reacting a diol, an anhydride and an acrylate to form a linear portion.
44. The process of manufacturing a capacitor of claim 43 wherein said diol is OH—R 1 —OH wherein R 1 is a linear alkyl with a molecular weight of no more than 1000.
45. The process of manufacturing a capacitor of claim 43 wherein said anhydride is defined by:
wherein R 2 is a linear alkyl of 1 to 6 carbons, which may be substituted, or the atoms necessary to form a ring which may be substituted.
46. The process of manufacturing a capacitor of claim 45 wherein said ring is an aromatic ring.
47. The process of manufacturing a capacitor of claim 43 wherein said acrylate is defined by:
wherein R 3 is a linear alkyl of 1 to 6 carbons which may be substituted, an ether or polyether which may be substituted.
48. The process of manufacturing a capacitor of claim 47 wherein said acrylate is defined by:
wherein R7 is hydrogen or methyl and n is an integer of no more than 10.
49. The process of manufacturing a capacitor of claim 47 wherein said acrylate is selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate (HEA), 2,2-bis(hydroxymethyl)propyl acrylate;
50. The process of manufacturing a capacitor of claim 43 wherein said preparing of said linear-hyperbranched polymer comprises reacting said linear portion with a hydroxyl amine.
51. The process of manufacturing a capacitor of claim 50 wherein said hydroxyl amine is defined by
wherein R 5 and R 5′ are independently selected from linear alkyls of 1-6 carbons which may be substituted.
52. The process of manufacturing a capacitor of claim 51 wherein said hydroxyl amine is selected from:
53. The process of manufacturing a capacitor of claim 35 wherein said linear-hyperbranched polymer comprises at least Generation 1 branching.
54. The process of manufacturing a capacitor of claim 53 wherein said linear-hyperbranched polymer comprises at least Generation 2 branching.
55. The process of manufacturing a capacitor of claim 53 wherein said linear-hyperbranched polymer has an acid number of at least 100 to no more than 500.
56. The process of manufacturing a capacitor of claim 55 wherein said linear-hyperbranched polymer has an acid number of no more than 200.
57. The process of manufacturing a capacitor of claim 35 wherein said dispersion has a performance additive with no more than 10 wt % sulfonate.
58. The process of manufacturing a capacitor of claim 57 wherein said performance additive has no more than 0.1 wt % sulfonate.
59. The process of manufacturing a capacitor of claim 35 wherein said dispersion has a performance additive with no more than 10 wt % primary or secondary amines.
60. The process of manufacturing a capacitor of claim 59 wherein said performance additive has no more than 10 wt % primary or secondary amines.
61. The process of manufacturing a capacitor of claim 35 further comprising cross-linking said cathode with a crosslinker.
62. The process of manufacturing a capacitor of claim 61 wherein cross-linking includes reacting reactive groups of said cathode with a crosslinker.
63. The process of manufacturing a capacitor of claim 62 wherein said crosslinker is selected from a silane and a ethylene glycol diglycidyl ether.
64. The process of manufacturing a capacitor of claim 63 wherein said crosslinker is selected from the group consisting of: