Metal ester polymer compositions, methods of manufacture, and uses thereof

Patent metadata

Field	Value
Publication number	US-9657145-B2
Application number	US-201514950940-A
Country	US
Kind code	B2
Filing date	Nov 24, 2015
Priority date	Jan 29, 2015
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

Disclosed are transition metal or group II metal ester polymers where the metal is an alkaline earth, transition metal or aluminum; methods of manufacture, and uses thereof. The metal ester polymers exhibit both high dielectric constant and low conductivity suitable for use as dielectric insulating materials.

First claim

The invention claimed is:

1. A transition metal or group II metal ester polymer comprising units of formula (I), (II), or (III):

wherein
R 1 is halogen, —OH, H 2 O, amine, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 3-12 cycloalkyl, substituted or unsubstituted C 6-12 aryl, substituted or unsubstituted C 3-6 heteroalkyl, substituted or unsubstituted C 2-12 alkynyl, or substituted or unsubstituted C 2-12 alkynyl;
R 2 and R 3 are each independently C 1-12 alkoxy, amine, monoC 1-12 alkyl amine, or di C 1-12 alkyl amine;
X is Ca, Cd, Cu, Zn, or a combination thereof;
A is a substituted or unsubstituted C 1-36 hydrocarbylene, a divalent heteroaryl, or an ether; and
m is 0 or 1.

2. The polymer of claim 1 , wherein the polymer is coordinated with a high dielectric constant ligand.

3. The polymer of claim 2 , wherein the high dielectric constant ligand is water; ammonia; hydrogen sulfide; an alcohol; an amine; or a thiol.

4. The polymer of claim 1 , wherein R 1 is halogen.

5. The polymer of claim 1 , wherein R 2 and R 3 are each independently unsubstituted —OC 1-6 alkyl.

6. The polymer of claim 1 , wherein A is substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 3-12 cycloalkyl, substituted or unsubstituted C 6-12 aryl, substituted or unsubstituted C 3-6 heteroalkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 2-12 alkynyl, substituted or unsubstituted C 6-12 heteroaryl, or a substituted or unsubstituted C 1-36 alkyl whose chain is interrupted by one or more units of substituted or unsubstituted C 6-12 aryl or one or more units of substituted or unsubstituted C 6-12 heteroaryl.

7. The polymer of claim 1 , wherein A is substituted or unsubstituted C 1-12 alkyl.

8. The polymer of claim 1 , wherein A is —O—(—R 4 —O—) n — wherein each R 4 is independently a divalent C 1-8 alkyl or divalent C 3-12 cycloalkyl, and n is 1 to 12, specifically 1 to 10, and more specifically 1 to 6.

9. The polymer of claim 1 , wherein the polymer is poly(chloroaluminum glutarate), poly(chloroaluminum sebacate), poly(chloroaluminum poly(ethyleneglycol)bis(carboxymethyl) ether-250), poly(chloroaluminum poly(ethyleneglycol)bis(carboxymethyl) ether-600), poly(chloroaluminum 20:80 glutarate:poly(ethyleneglycol)bis(carboxymethyl) ether-600), poly(chloroaluminum 50:50 glutarate:poly(ethyleneglycol)bis(carboxymethyl) ether-600), poly(chloroaluminum 80:20 glutarate:poly(ethyleneglycol)bis(carboxymethyl) ether-600), poly(chloroaluminum 50:50 poly(ethyleneglycol)bis(carboxymethyl) ether-250:3,3-dimethylglutarate), poly(chloroaluminum 60:40 poly(ethyleneglycol)bis(carboxymethyl) ether-250:3,3-dimethylglutarate), poly(chloroaluminum 75:25 poly(ethyleneglycol)bis(carboxymethyl) ether-250:3,3-dimethylglutarate), poly(chloroaluminum 80:20 poly(ethyleneglycol)bis(carboxymethyl) ether-250:3,3-dimethylglutarate), poly(chloroaluminum 90:10 poly(ethyleneglycol)bis(carboxymethyl) ether-250:3,3-dimethylglutarate), poly(chloroaluminum 95:5 poly(ethyleneglycol)bis(carboxymethyl) ether-250:3,3-dimethylglutarate), poly(cadmium sebacate), poly(copper sebacate), poly(zinc sebacate), poly(50:50 cadmium:zinc sebacate), poly(calcium sebacate), poly(diethoxytitanium poly(ethyleneglycol)bis(carboxymethyl) ether-250), or combinations comprising at least one of the foregoing.

10. The polymer of claim 1 , wherein a dielectric constant, ∈, of the polymer is greater than or equal to 3.0.

11. The polymer of claim 1 , wherein the polymer has a thermogravimetric analysis onset temperature of greater than or equal to 200° C.

12. A process for producing the polymer of claim 1 , comprising
a. contacting an organic dicarboxylic acid or derivative thereof and a diorganoaluminum halide;
b. contacting an organic dicarboxylic acid or derivative thereof and a metal dihalide, wherein the metal is Ca, Cd, Cu, Zn, or a combination thereof; or
c. contacting an organic dicarboxylic acid or derivative thereof and a dialkoxytitanium dihalide.

13. The process of claim 12 , wherein contacting is in the presence of solvent.

14. A composition comprising the polymer of claim 1 .

15. An article comprising the polymer of claim 1 .

16. The article of claim 15 , wherein the article is a capacitor, field effect transistor, electromechanical system, printed circuit, or photovoltaic.

Assignees

• Univ Connecticut

Inventors

• Sotzing Gregory Allen
• Baldwin Aaron

Classifications

• C08G63/681

  containing elements not provided for by groups C08G63/682 - C08G63/698 · CPC title

• C08G63/81 Primary

  using solvents (C08G63/79 takes precedence) · CPC title

• C08G79/00 Primary

  Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon {with or without the latter elements in the main chain of the macromolecule} · CPC title

• C08G79/10

  a linkage containing aluminium · CPC title

• C08G79/14

  a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon · CPC title