Method for preparing light-absorbing polymeric compositions

The diacidic anthraquinone compounds having Formulae 593

• wherein R14 is selected from the group consisting of hydrogen, 1-4 groups selected from amino, C1—C10 alkylamino, C3—C8 alkenylamino, C3—C8 alkynylamino, C3—C8 cycloalkylamino, arylamino, halogen, C1—C6 alkoxy, C1—C6 alkylthio, aryl, aroyl, C1—C6 alkanoyl, C1—C6 alkanoyloxy, NHCO C1—C6 alkyl, NHCOaryl, NHCO2 C1—C6 alkyl, NHSO2 C1—C6 alkyl, NHSO2 aryl, C1—C6 alkoxycarbonyl, aryloxy, arylthio, heteroarylthio, cyano, nitro, trifluoromethyl, thiocyano, SO2C1—C6 alkyl, SO2 aryl, —SO2NH C1—C6 alkyl, —SO2N(C1—C6 alkyl)2, —SO2N(C1—C6 alkyl) aryl, CONH C1—C6 alkyl, CON(C1—C6 alkyl)2, CON(C1—C6 alkyl) aryl, C1—C6 alkyl, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino, 594
• or hydroxy;
• Q and Q′ are independently selected from the group consisting of—O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3—C8 cycloalkyl, or C1—C10 alkyl;
• R16′ is selected from hydrogen or one or two groups selected from C1—C6 alkyl, halogen and C1—C6 alkoxy;
• wherein each C1—C6 alkyl group and C1—C6 alkyl group which is a portion of another group may contain at least one substituent selected from the group consisting of hydroxy, cyano, chlorine, fluorine, C1—C6 alkoxy, C3—C8 cycloalkoxy, C1—C6 alkylcyclohexyl, hydroxmethyl cyclohexyl, aryl and heteroaryl;
• with the provision that two acidic groups containing one acidic proton each or one acidic group containing two acidic hydrogens be present in the compounds of Formula XIV, XIXc, XIXd, XIXe XIXf.

The diacidic anthrapyridone compounds having Formulae 596

• wherein R14 is selected from the group consisting of hydrogen, 1-4 groups selected from amino, C1—C10 alkylamino, C3—C8 alkenylamino, C3—C8 alkynylamino, C3—C8 cycloalkylamino, arylamino, halogen, C1—C6 alkoxy, C1—C6 alkylthio, aryl, aroyl, C1—C6 alkanoyl, C1—C6 alkanoyloxy, NHCO C1—C6 alkyl, NHCOaryl, NHCO2 C1—C6 alkyl, NHSO2 C1—C6 alkyl, NHSO2 aryl, C1—C6alkoxycarbonyl, aryloxy, arylthio, heteroarylthio, cyano, nitro, trifluoromethyl, thiocyano, SO2C1—C6 alkyl, SO2 aryl, —SO2NH C1—C6 alkyl, —SO2N(C1—C6 alkyl)2, —SO2N(C1—C6 alkyl) aryl, CONH C1—C6 alkyl, CON(C1—C6 alkyl)2, CON(C1—C6 alkyl) aryl, C1—C6 alkyl or hydroxy;
• Q and Q′ are independently selected from the group consisting of—O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3—C8 cycloalkyl, or C1—C10 alkyl;
• R15 is selected from the group consisting of hydrogen, cyano, C1—C6 alkylamino, C1—C6 alkoxy, halogen, arylthio, aryl, heteroaryl, heteroarylthio, C1—C6 alkoxycarbonyl, aroyl or arylsulfonyl;
• R16 is selected from the group consisting of hydrogen, C1—C6 alkyl, C3—C8 cycloalkyl and aryl;
• R16′ is selected from the group consisting of hydrogen or one or two groups selected from C1—C6 alkyl, halogen and C1—C6 alkoxy;
• wherein each C1—C6 alkyl group and C1—C6 alkyl group which is a portion of another group may contain at least one substituent selected from the group consisting of hydroxy, cyano, chlorine, fluorine, C1—C6 alkoxy, C3—C8 cycloalkoxy, C1—C6 alkylcyclohexyl, hydroxmethyl cyclohexyl, aryl and heteroaryl;
• with the provision that two acidic groups containing one acidic proton each or one acidic group containing two acidic hydrogens be present in the compounds of Formula XVIII, XVIIIa, XVIIIb, and XIXa.

The diacidic anthraquinone compounds having the structures:

• 604
• wherein Q is selected from the group consisting of —O—, —S— and —SO2—;
• Sub1 is a substitutent selected from the group consisting of amino, C1—C12 alkylamino, arylamino and C3—C8 cycloalkylamino;
• Q′ is selected from the group consisting of—O—, —N(CO10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3—C8 cycloalkyl, or C1—C10 alkyl;
• and R16′ is selected from the group consisting of hydrogen or one or two groups selected from C1—C6 alkyl, halogen and C1—C6 alkoxy.

The diacidic azo and disazo compounds of the formulae R6—N═N—Z (VI) and R6—N═N—R7—N═N—Z (VII), respectively wherein R6 is the residue of a diazotized aromatic or heteroaromatic amine and Z is the residue of an electron rich coupling component selected from the group consisting of the classes of anilines, 1-aminonaphthalenes, 1,2-dihydroquinolines, 1,2,3,4-teterahydroquinolines, benzomorpholines (3,4-dihydro-2H-1,4-benzoxazine), pyrazolones, pyrazoles, 3-cyano-6-hydroxy-2-pyridones, 2,3-dihydroindoles, indoles, 4-hydroxycoumarins, 4-hydroxy-2-quinolones, imidazo[2,1-b]thiazoles, julolidines (2,3,6,7-tetrahydro-1H, 5H-benzo[ij]quinolizines), 1-oxajulolidines, 1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinolines, 2,6-diamino-3 cyanopyridines, 2-aminothiazoles, 2-aminothiophenes, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), phenols, naphthols, 2,4-pentanediones or acetoacetarylides;

• R7 is a divalent aromatic or heteroaromatic radical selected from the group consisting of the classes of 1,4-phenylene, naphthalene -1, 4-diyl, thiazol-2,5-diyl and thiophene-2,5-diyl;
• with the provision that R6 or Z contains a carboxy (—CO2H) acidic group and that another acidic group selected from the group consisting of (—CO2H), —SH, —OH attached to aromatic ring, —CONHCO—, —SO2NH—CO—, —SO2NH— SO2—, and 1(H) 1, 2, 4-triazol-3-yl, be present on or as part of R6 or Z so that each R6 and Z moiety contains one acidic group.

The diacidic bisazo compounds having the formula R6—N═N—Y1—N═N—R6 (VIIa) wherein R6 is the residue of a substituted diazotized aromatic or heteroaromatic amine compound derived from the classes of aniline, 1-aminonaphthalene, 1-aminoanthraquinone, 4-aminoazobenzene, 2-aminothiazole, 2-aminobenzothiazole, 3-amino-2,1-benzisothiazole, 2-aminothieno[2,3-d]thiazole, 5-aminoisothiazole, 5-aminopyrazole, 4-aminopyrazoloisothiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,4-thiadiazole, 5-amino-1,2,3-triazole, 2-amino-1,3,4-triazole, 2(5) aminoimidazole, 3-aminopyridine, 2(3) aminothiophene, 2(3) aminobenzo[b]thiophene, 2-aminothieno[3,2-b]thiophene, 3-aminothieno[2,3-c]isothiazole, 3-amino-7-benz- 2,1-isothiazole, 3-aminobenzothienoisothiazole, 3-aminoisothiazole[3,4-d]pyrimidine, 5-amino- 1,2,3-triazole, 3(4) aminophthalimide and 5(6) amino-1,2-benzisothiazolon-1,1-dioxide and Y1 is the residue of a bis coupling component selected from the group consisting of the classes of anilines, 1,2-dihydroquinolines, 1,2,3,4-tetrahydroquinolines, benzomorpholines (3,4-dihydro-2H-1,4-benzoxazines), 3-cyano-6-hydroxy-2-pyridones, 2,6-diaminopyridines, 2,3-dihydroindoles, naphthylamines, 2-aminothiazoles, or a combination of these, with the provision that each R6 group contain one acidic group selected from the group consisting of —CO2H, —SH, —OH attached to an aromatic ring, —NHCONH—, —SO2NHCO—, —SO2NHSO2—, 1 (H)-1,2,4-triazol-3-yl-, imidazolyl, benzimidazoyl, pyrazolyl and —SO2H attached to aromatic ring.

The diacidic methine, arylidene, polymethine, azamethine, 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene -2-oxypyrroline and aryl isoindoline corresponding to formulae VIII, VIIIa, VIIIb, IX, X, XI and XII, respectively:

• 616
• wherein R11 is the residue of an aniline, 1-naphthylamine, 1,2-dihydroquinoline, 1,2,3,4-tetrahydroquinoline, 1,3,3-trimethyl-2-methyleneindole, 1,3-dihydro-2-methylene-1,1,3-trimethyl-2H-benz[e]indole, imidazo [2,1-b] thiazole, benzomorpholine (3,4-dihydro-2H-1,4,benzoxazine), indole, 2,3-dihydroindole, 2-aminothiazole, julolidine (2,3,6,7-tetrahydro-1H, 5H- benz [ii] quinolizine, 1-oxajulolidine, 4H-pyrrolo [3,2,1-ij]-quinoline, phenol, naphthol, thiophenol, pyrrole, pyrazole, furan, thiophene, carbazole, phenothiazine or phenoxazine compound;
• R12 is selected from the group consisting of hydrogen, C1—C10 alkyl, C3—C8 alkenyl, C3—C8-alkynyl, C3—C8 cycloalkyl, aryl, [Parenopenst]CH2CH2O[Parenclosest]1-3 R13 and C1—C4 alkylene- C3—C8 cycloalkylene, wherein the C1—C6 alkyl groups may be substituted by at least one group selected from the group consisting of carboxy, C1—C6 carbalkoxy, C1—C6 alkanoyloxy, cyano, hydroxy, chlorine, fluorine, C1—C6 alkoxy, C3—C8 cycloalkyl or aryl;
• R13 is selected from the group consisting of hydrogen, C1—C6 alkoxy or C1—C6 alkanoyloxy;
• wherein D is the residue of an active methylene compound selected from the group consisting of malononitrile, α-cyanoacetic acid esters, malonic acid esters, α-cyanacetic acid amides, α-C1—C6 alkylsulfonylacetonitriles, α-arylsulfonylacetonitriles, α-C1—C6 alkanoylacetonitriles, α-aroylacetonitriles, α-heteroarylacetonitriles, bis(heteroaryl)methanes, 1,3-indanediones, 2-furanones, benzo-2-furanones, naphtho-2-furanones, 2-indolones, 3-cyano-1,6-dihydro-4-methyl-2,6-dioxy (2H)-pyridines, benzo (b) thieno-3-ylidene propane dinitrile-5,5-dioxides, 1,3-bis (dicyanomethylene) indanes, barbituric acid, 5-pyrazolones, dimedone, 3-oxo-2,3-dihydro-1-benzothiophene-1,1-dioxides or aryl-C(CH3)C═C(CN)2, with the proviso that two acidic functional groups selected from the group consisting of —CO2H, —SH, —OH attached to aromatic ring, —CONHCO—, —SO2NHCO—, —SO2NHSO2—, 1(H) -1,2,4, -triazol-3-yl, imidazolyl, benzimidazolyl, pyrazolyl and SO2H attached to aromatic ring be present or one diacidic sulfamoyl (—SO2NH2) be present.

A method comprising reacting

• a) at least one diacidic monomer, comprising about 1 to 100 mole % of at least one light-absorbing monomer having a light absorption maximum between about 300 nm and about 1200 nm and 99-0 mole % of a non-light absorbing monomer which does not absorb significant light at wavelengths above 300 nm or has a light absorption maximum below 300 nm, with
• b) an organic compound having the formula
• X—B—X1
• wherein B is a divalent organic radical selected from the group consisting of C2—C12 alkylene, C3—C8 cycloalkylene, C1—C4 alkylene- C3— C8-cycloalkylene- C1—C4 alkylene, C1—C4 alkylene-arylene- C1—C4 alkylene, C2— C4-alkylene-L-arylene-L- C2—C4 alkylene and C2—C4 alkylene-(L- C2—C4 alkylene)1-4, wherein L is a linking group selected from the group consisting of —O—, —S—, —SO2—, —NH—, —N(C1—C6 alkyl)—, —N(aryl)—, —N(SO2 C1—C6 alkyl)—, —N(SO2aryl)—, —SO2N(C1—C6 alkyl)— and combinations thereof;
• X and X1 are reactive groups and are independently selected from the group consisting of bromine, iodine and R—SO2O;
• wherein R is selected from the group consisting of C1—C6 alkyl;
• C1—C alkyl substituted with chlorine, fluorine, C1—C6 alkoxy, aryl, aryloxy, arylthio or C3—C8 cycloalkyl;
• C3—C8 cycloalkyl or aryl,
• wherein said reaction is carried out in a solvent in the presence of a base to form a light absorbing composition comprising a mixture of a polymer having the formula 653
• and a cyclic compound having the general formula 654
• wherein B is as defined above, n is at least 2, m is 1, 2, 3 or 4 and A comprises the residue of said diacidic monomer.