Electro-polarizable compound and capacitor

• US 10,153,087 B2
• Filed: 05/24/2016
• Issued: 12/11/2018
• Est. Priority Date: 04/04/2016
• Status: Active Grant

• Current Assignee: Capacitor Sciences Incorporated (Bolloré SE)
• Original Assignee: Capacitor Sciences Incorporated (Bolloré SE)
• Inventors: Lazarev, Pavel Ivan, Furuta, Paul T., Sharp, Barry K., Li, Yan, Kelly-Morgan, Ian S. G.
• Primary Examiner(s): Northington Davis, Zinna
• Application Number:
  US15/163,595
• Publication Number:
  US 20170287638A1
• Time in Patent Office: 931 Days
• Field of Search: None
• CPC Class Codes: C07D 471/22 in which the condensed systems contains four or more hetero rings
• CPC Class Codes: C09B 5/008 only N-containing hetero rings
• CPC Class Codes: C09B 5/62 Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
• CPC Class Codes: C09B 57/08 Naphthalimide dyes; Phthalimide dyes
• CPC Class Codes: H01G 4/005 Electrodes
• CPC Class Codes: H01G 4/14 Organic dielectrics
• CPC Class Codes: H01G 4/18 of synthetic material, e.g. derivatives of cellulose H01G4/16 takes precedence
• CPC Class Codes: H01G 4/32 Wound capacitors

Abstract

An electro-polarizable compound has the following general formula:

Core1 is an aromatic polycyclic conjugated molecule having two-dimensional flat form and self-assembling by pi-pi stacking in a column-like supramolecule. R1 are electron donor groups connected to Core1 and R1′ are electron acceptor groups connected to Core1, m is number of acceptor groups R1, m′ is a number of donor groups R′. The numbers m and m′ are equal to 0, 1, 2, 3, 4, 5 or 6, but both m and m′ are not both equal to 0. R2 is a substituent comprising one or more ionic groups connected to Core1 directly or via a connecting group; a number p of ionic groups R2 is 0, 1, 2, 3 or 4. The fragment marked NLE has a nonlinear effect of polarization. Core2 is a self-assembling electro-conductive oligomer, a number n of the such oligomers is 0, 2, or 4. R3 is a substituent comprising one or more ionic groups connected to Core2; a number s of the ionic groups R3 is 0, 1, 2, 3 or 4. R4 is a resistive substituent providing solubility of the compound in a solvent and electrically insulating the column-like supramolecules from each other. A number k of substituents R4 is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

Claims

1. An electro-polarizable compound having the following formula (I):

2. The electro-polarizable compound according to claim 1, wherein the acceptor groups (R1′

) are selected from —

NO₂, —

NH₃+and —

NR₃+(quaternary nitrogen salts), counterion Cl—

or Br—

, —

CHO (aldehyde), —

CRO (keto group), —

SO3H (sulfonic acids), —

SO₃R (sulfonates), —

SO₂NH₂ (sulfonamides), —

COOH (carboxylic acid), —

COOR (esters,), —

COCl (carboxylic acid chlorides), —

CONH₂ (amides,), —

CF₃, —

CCl₃,—

CN, —

C(CN)₂ wherein R is radical selected from the list consisting of alkyl, allyl (—

CH₂—

CH═

CH₂), benzyl (—

CH₂C₆H₅,) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.

3. The electro-polarizable compound according to claim 1, wherein the donor groups (R1) are selected from —

O—

(phenoxides,), —

NH₂, —

NHR, —

NR₂, —

OH, —

OR (ethers), —

NHCOR (amides), —

OCOR (esters), alkyls, —

C₆H₅, vinyls, wherein R is radical selected from the list consisting of alkyl, allyl (—

CH₂—

CH═

CH₂), benzyl (—

CH₂C₆H₅) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.

4. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from the list comprising the following structures:

13-22, where X is hydrogen (H) or an alkyl group;

5. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from the group of CH₂, CF₂, SiR₂O, CH₂CH₂O, wherein R is selected from the list consisting of H, alkyl, and fluorine.

6. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from structures 24 to 29:

7. The electro-polarizable compound according to claim 1, wherein the resistive substituent R4 is selected from the group of alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof.

8. The electro-polarizable compound of claim 1, wherein the aromatic polycyclic conjugated molecule (Core1) and the groups R1 and R1′

form a non- centrosymmetric molecular structure.

9. The electro-polarizable compound of claim 1, wherein the aromatic polycyclic conjugated molecule (Core1), the groups R1 and R1′

and the resistive substituents (R4) form a non-centrosymmetric molecular structure.

10. The electro-polarizable compound of claim 1 having the following formula (II):

11. The electro-polarizable compound of claim 10, wherein a length of the non-conjugated part of the electro-polarizable compound is selected such that the resistivity of the electro-polarizable compound is greater than 10¹⁸ ohm·

cm.

12. The electro-polarizable compound of claim 10, wherein a length of the non-conjugated part of the electro-polarizable compound is selected such that the resistivity of the electro-polarizable compound is between 10¹⁸ ohm·

cm and 10²⁴ ohm·

cm.

13. The electro-polarizable compound of claim 10, wherein the resistive substituent R4 is a polycyclic alkyl group and a polycyclic halo-alkyl group, wherein in the polycyclic halo-alkyl group is connected to the apex of Core1 on which the electrophilic group (acceptor) R1 is connected, or the apex of Core1 on which the nucleophilic group (donor) R1′

is connected, but not both.

14. The electro-polarizable compound of claim 10, wherein the resistive substituent R4 is a resistive polycyclic substituent selected from the list consisting of C₂₅H₃₄ and C₂₅H₃₅ or C₂₅F₃₄ and C₂₅F₃₅ and located on the apex phenyl, naphthyl, or anthryl rings of Core1.

15. The electro-polarizable compound of claim 10 having the following formula (III):

16. The electro-polarizable compound according to claim 15, wherein the set of the electron donor and acceptor groups consists of two donor groups —

NH₂ and two acceptor groups —

NO₂ (m is equal to

     4) located on rylene rings, or on apex phenyl, naphthyl, and/or anthryl ring positions of the Core1, or on both rylene rings positions and apex phenyl, naphthyl, and/or anthryl ring positions and the fragment having a nonlinear effect of polarization (NLE) is represented by following chemical structure;

17. The electro-polarizable compound of claim 10 having a formula (V):

18. A solution comprising an organic solvent and at least one type of electro-polarizable compound according to claim 1.

19. The solution according to claim 18, comprising a mixture of different electro-polarizable compounds.

20. The solution according to claim 18, wherein the mixture of the electro-polarizable compounds comprises rylene fragments of different length.

21. The solution according to claim 18, wherein the organic solvent is selected from the list comprising ketones, carboxylic acids, hydrocarbons, cyclic hydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, and any combination thereof.

22. The solution according to claim 18, wherein the organic solvent is selected from the list comprising acetone, xylene, toluene, ethanol, methylcyclohexane, ethyl acetate, diethyl ether, octane, chloroform, methylene chloride, dichloroethane, trichloroethene, tetrachloroethene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran, pyridine, triethylamine, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and any combination thereof.

23. A solution according to claim 18, wherein the solution is a lyotropic liquid crystal solution.

24. A metadielectric layer comprising a mixture of the electro-polarizable compounds according to claim 1, wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with one or more R1 groups, and wherein the one or more R1 and/or R1′

groups form a resistive envelope and solubilize the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.

25. The metadielectric layer according to claim 24, wherein the column-like supramolecules are formed by the electro-polarizable compounds comprising rylene fragments of different length.

26. The metadielectric layer according to claim 24, wherein the metadielectric layer'"'"'s relative permittivity is greater than or equal to 1000.

27. The metadielectric layer according to claim 24, wherein the layer'"'"'s resistivity is greater than or equal to 10¹³ ohm/cm.

28. A meta-capacitor comprising two metal electrodes positioned parallel to each other and which can be rolled or flat and planar with said metadielectric layer between said electrodes, wherein the metadielectric layer comprises one or more types of the electro-polarizable compounds according to claim 1 wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one group R1 or R1′

, the electro-conductive oligomers and the ionic groups which have electronic and/or ionic type of polarizability are placed into a resistive dielectric envelope formed by resistive substituents R1 and/or R1′

providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.