US 11,655,378 B2
Electroactive polymer solution comprising conjugated heteroaromatic polymer, electroactive coating comprising the same, and objects comprising electroactive coating
Chien-Chung Han, Hsinchu (TW); Ting-Chia Ku, Taichung (TW); and Jo-Wen Chiang, Taichung (TW)
Assigned to PolyM technology corporation, Hsinchu (TW)
Filed by PolyM technology corporation, Hsinchu (TW)
Filed on Nov. 3, 2019, as Appl. No. 16/672,507.
Application 16/672,507 is a division of application No. 15/456,595, filed on Mar. 13, 2017, granted, now 10,519,328.
Application 15/456,595 is a continuation in part of application No. 14/306,251, filed on Jun. 17, 2014, granted, now 9,627,147, issued on Apr. 18, 2017.
Application 14/306,251 is a continuation in part of application No. 13/662,533, filed on Oct. 28, 2012, granted, now 9,790,330, issued on Oct. 17, 2017.
Prior Publication US 2020/0062973 A1, Feb. 27, 2020
This patent is subject to a terminal disclaimer.
Int. Cl. C09D 5/24 (2006.01); C09D 125/06 (2006.01); H01G 9/00 (2006.01); H01G 9/15 (2006.01); H01G 9/025 (2006.01); C08G 73/06 (2006.01); H01B 1/12 (2006.01); C08G 61/12 (2006.01); C09D 179/04 (2006.01); C09D 5/08 (2006.01); H01G 11/70 (2013.01); C09D 7/65 (2018.01); H01G 11/48 (2013.01)
CPC C09D 5/24 (2013.01) [C08G 61/125 (2013.01); C08G 61/126 (2013.01); C08G 73/0611 (2013.01); C09D 5/08 (2013.01); C09D 7/65 (2018.01); C09D 125/06 (2013.01); C09D 179/04 (2013.01); H01B 1/127 (2013.01); H01B 1/128 (2013.01); H01G 9/0036 (2013.01); H01G 9/025 (2013.01); H01G 9/15 (2013.01); H01G 11/70 (2013.01); C08G 2261/145 (2013.01); C08G 2261/1412 (2013.01); C08G 2261/3221 (2013.01); C08G 2261/3222 (2013.01); C08G 2261/3223 (2013.01); C08G 2261/94 (2013.01); H01G 11/48 (2013.01)] 16 Claims
 
1. A solution for forming an electroactive coating, containing a conjugated heteroaromatic polymer, being transitional metal free, and being prepared directly from a composition comprising:
at least one compound of formula (1) or (2) as a monomer,

OG Complex Work Unit Chemistry
wherein in formula (1),
X is selected from the group consisting of S, O, Se, Te, PR2 and NR2, wherein R2 is selected from the group consisting of hydrogen, and substituted and unsubstituted alkyl, aryl, heteroaryl, alkanoyl, and aryloyl groups,
Y is hydrogen (H), or a precursor of a good leaving group Y. . . whose conjugate acid (HY) has a pKa of less than 45,
Z is hydrogen (H), silyl, or a precursor of a good leaving group Z. . . whose conjugate acid (HZ) has a pKa of less than 45,
b is 0, 1 or 2, and
each R1 is a substituent, wherein when b=2, the two R1 are the same or different and may joint together to form a ring;
the at least one compound of formula (1) comprises at least one compound of formula (1) with Z═H and Y≠H;

OG Complex Work Unit Chemistry
in formula (2),
X is the same or different at each occurrence, and is independently selected from the group consisting of S, O, Se, Te, PR2 and NR2, wherein R2 is selected from the group consisting of hydrogen, and substituted and unsubstituted alkyl, aryl, heteroaryl, alkanoyl, and aryloyl groups,
Y is hydrogen (H), or a precursor of a good leaving group Y. . . whose conjugate acid (HY) has a pKa of less than 45,
Z is hydrogen (H), silyl, or a precursor of a good leaving group Z. . . whose conjugate acid (HZ) has a pKa of less than 45,
Ar is a substituted or unsubstituted, mono- or poly-nuclear, aryl or heteroaryl ring,
m, o and p are each independently an integer equal to or greater than 0, with a proviso that m+p≥1,
each k is independently 0, 1 or 2, each R5 is a substituent, wherein any two R5 on the same ring or on two neighboring rings, or R5 and a substituent group on a neighboring Ar ring, may join together to form another ring; and
the at least one compound of formula (2) comprises at least one compound of formula (2) with Z═H and Y≥H;
an acid as a polymerization catalyst selected from the group consisting of a protic acid, a polymeric acid, and a non-transitional Lewis acid; and
at least one functional component, selected from the group consisting of a solvent, a polymerization retardant, a polymer binder or a precursor of polymer binder, a dopant, a latent dopant, a dielectric layer protection agent, a dielectric layer repair agent, a plasticizer, an impact modifier, a reinforcing filler, a blowing agent, a crosslinking agent, an ultraviolet stabilizer, a flame retardant, a photoresist, a thickening agent, a defoaming agent, an emulsifier, a surfactant, and a dispersion stabilizer,
wherein
the at least one functional component contains at least the polymerization retardant and the polymer binder or the precursor of polymer binder, wherein the polymerization retardant comprises at least one Lewis base having a stronger basicity than the monomer,
the conjugated heteroaromatic polymer contains, as a dopant therefor, the acid as the polymerization catalyst, and
condition i), ii) or iii) below is satisfied:
i) that the electroactive coating comprises an O-containing polymer, a N-containing polymer or a P-containing polymer that serves as both the polymerization retardant and the polymer binder, wherein the O-containing polymer is selected from the group consisting of substituted and unsubstituted poly(ethylene oxide)s, poly(propylene oxide)s, poly(ethylene glycol)s, poly(propylene glycol)s, poly(vinyl acetate)s, poly[ethylene-co-(vinyl acetate)]s, polyvinyl alcohols and poly[ethylene-co-(vinyl alcohol)]s, the N-containing polymer is selected from the group consisting of substituted and unsubstituted polyvinylpyridines and polyvinylpyrrolidones, and the P-containing polymer is selected from the group consisting of substituted and unsubstituted poly(ethylene phosphate)s and poly(propylene phosphate)s;
ii) that the polymer binder comprises a polymeric acid, wherein the polymeric acid also serves as the dopant, or as the acid as the polymerization catalyst, and the polymeric acid is selected from the group consisting of poly(glycolic acid)s, poly(lactic acid)s, sulfonated polystyrenes that do not include polystyrenesulfonic acid, sulfonated poly(vinyl naphthalene)s, sulfonated poly(vinyl arene)s that do not include polystyrenesulfonic acid, sulfonated poly(vinyl heteroarene)s, sulfonated copolymers or terpolymers comprising at least one substituted or unsubstituted styrene repeat unit, oligophosphoric acids, polyphosphoric acids, oligometaphosphoric acids, polymetaphosphoric acids, and combination mixtures, copolymers and terpolymers thereof;
iii) that the polymer binder comprises a thermoplastic plastic or a thermosetting plastic, wherein the thermoplastic plastic is selected from the group consisting of substituted and unsubstituted PET, poly(butylene terephthalate)s, poly(4-hydroxybenzoate)s, polystyrene, poly(styrene sulfonate)s, poly(alkyl styrenesulfonate)s, PS-PMMA copolymers, lignin, asphaltenes, bitumens, styrene-butadiene rubbers, ABS, polyarylates, polybenzimidazoles, poly(p-xylylene)s and polyvinylpyridines, and polymer mixtures, copolymers and terpolymers thereof.