High dielectric breakdown polymers; compositions; methods of making; and use thereof

A monomer according to formula (I)

• wherein
• X is O, S, NR1, C(R2)2, or C(R2)2—C(R2)2 wherein R1 is H, C1-10 alkyl, C1-10 haloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein each of the substituted aryl and substituted heteroaryl of R1 is substituted with 1, 2, 3, 4, or 5 substituents, each substituent independently is C1-20 alkyl, C1-20 haloalkyl, C1-20 alkoxy, C1-20 haloalkoxy, halo, —NH2, —NHR3, —N(R3)2, nitro, cyano, hydroxyl, aryl, heteroaryl, or a combination thereof, wherein R3 is C1-20 alkyl, and each R2 independently is H, halo, or C1-10 alkyl;
• is a single or double bond;
• a) when X is S, NR1, C(R2)2, or C(R2)2—C(R2)2 then R is a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl,
• wherein each of the substituted aryl and substituted heteroaryl of R is substituted with 1, 2, 3, 4, or 5 substituents,
• each substituent on the substituted aryl and substituted heteroaryl of group R independently is C1-20 alkyl, C1-20 haloalkyl, C1-20 alkoxy, C1-20 haloalkoxy, halo, —NH2, —NHR3, —N(R3)2, nitro, cyano, hydroxyl, aryl, heteroaryl, or a combination thereof, wherein R3 is C1-20 alkyl;
• and
• b) when X is O then R is a substituted aryl or substituted heteroaryl,
• wherein each of the substituted aryl and substituted heteroaryl of R is substituted with 1, 2, 3, 4, or 5 substituents,
• each substituent on the substituted aryl and substituted heteroaryl of group R independently is C1-20 haloalkyl, C1-20 haloalkoxy, —NHR3, —N(R3)2, cyano, aryl, heteroaryl, or a combination thereof, wherein R3 is C1-20 alkyl.

A process for producing a dielectric polymer, comprising

• conducting Ring Opening Metathesis Polymerization or vinyl addition polymerization of a monomer of formula (I)
• wherein
• X is O, S, NR1, C(R2)2, or C(R2)2—C(R2)2 wherein R1 is H, C1-10 alkyl, C1-10 haloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein each of the substituted aryl and substituted heteroaryl of R1 is substituted with 1, 2, 3, 4, or 5 substituents, each substituent independently is C1-20 alkyl, C1-20 haloalkyl, C1-20 alkoxy, C1-20 haloalkoxy, halo, —NH2, —NHR3, —N(R3)2, nitro, cyano, hydroxyl, aryl, heteroaryl, or a combination thereof, wherein R3 is C1-20 alkyl, and each R2 independently is H, halo, or C1-10 alkyl;
• is a single or double bond;
• a) when X is S, NR1, C(R2)2, or C(R2)2—C(R2)2 then R is a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl,
• wherein each of the substituted aryl and substituted heteroaryl of R is substituted with 1, 2, 3, 4, or 5 substituents,
• each substituent on the substituted aryl and substituted heteroaryl of group R independently is C1-20 alkyl, C1-20 haloalkyl, C1-20 alkoxy, C1-20 haloalkoxy, -halo, —NH2, —NHR3, —N(R3)2, nitro, cyano, hydroxyl, aryl, heteroaryl, or a combination thereof, wherein R3 is C1-20 alkyl;
• and
• b) when X is O then R is a substituted aryl or substituted heteroaryl,
• wherein each of the substituted aryl and substituted heteroaryl of R is substituted with 1, 2, 3, 4, or 5 substituents,
• each substituent on the substituted aryl and substituted heteroaryl of group R independently is C1-20 haloalkyl, C1-20 haloalkoxy, —NHR3, —N(R3)2, cyano, aryl, heteroaryl, or a combination thereof, wherein R3 is C1-20 alkyl.

A dielectric polymer, comprising

• a polymer backbone and a pendent group,
• the polymer backbone comprises
• alternating repeat units of a first rigid domain separated by single bonds, or
• alternating repeat units of a first rigid domain and a second rigid domain separated by single bonds,
• wherein the pendent group is a substituted aromatic group attached to the first rigid domain by a single bond, wherein the substituted aromatic group is a substituted aryl or substituted heteroaryl, each substituted with 1, 2, 3, 4, or 5 substituents;
• and
• each substituent independently is C1-20 haloalkyl, C1-20 haloalkoxy, —NHR3, —N(R3)2, cyano, aryl, or heteroaryl, wherein R3 is C1-20 alkyl;
• and
• wherein the dielectric polymer has one or more of the following:
• a.) Tg of greater than or equal to 150° C.;
• b.) Band gap of greater than or equal to 4.1 eV;
• c.) a maximum discharged energy density of greater than 5.0 J/cm3 with efficiency at or above 90% at a temperature of 150° C.;
• d.) a maximum discharged energy density of greater than 5.0 J/cm3 at a temperature of 150° C. and an electric field of greater than 650 MV/m or between 650 and 800 MV/m;
• and
• e.) an operating temperature from about −160 to about 250° C.