Amido-Amine Hardener

A polymeric or co-polymeric compound comprising a repeating unit of formula (4):

• wherein:
• R is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkyloxy, C1 to C20 alkylamino, —OH, —OR2, —NH2, —NHR2, —NR22, —C(O)OH, —C(O)OR2, —C(O)NH2, —C(O)NHR2, —C(O)NR22, —O(CO)H, —O(CO)R2, —NH(CO)H, —NH(CO)R2, —NR2(CO)H, —NR2(CO)R2, —SH, —SR2, —SO2H, —SO2R2, —SO3R2, —SO3H, —SiR23, —NO2, —CN, —F, —Cl, —Br, and —I;
• each R1 group is independently selected from:
• —H, C1 to C10 alkyl, C1 to C10 haloalkyl, C3 to C12 cycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, C6 to C12 aryl, and C3 to C12 heteroaryl;
• each R2 is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkoxy, and C1 to C20 alkylamino;
• Y is independently selected from a C1 to C250 hydrocarbyl group;
• Y1 is independently selected from hydrogen or a C1 to C250 hydrocarbyl group;
• Z is independently selected from a C2 to C250 hydrocarbyl group comprising at least one primary or secondary amine;
• Z1 is independently either hydrogen or a C1 to C250 hydrocarbyl group;
• and
• L is a linking group which connects the repeating unit to a single adjacent repeating unit of the polymer or co-polymer, and is selected from —CR9R10—;
• each represents the attachment point between the linking group, L, of one repeating unit and a single adjacent repeating unit;
• each R9 group is independently selected from:
• —H, C1 to C10 alkyl, C1 to C10 haloalkyl, C3 to C12 cycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, C6 to C12 aryl, C3 to C12 heteroaryl, and —C(O)H;
• each R10 group is independently selected from:
• —H, C1 to C10 alkyl, C1 to C10 haloalkyl, C3 to C12 cycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, C6 to C12 aryl, and C3 to C12 heteroaryl;
• or R9 and R10 are taken together to form a C3 to C12 cycloalkyl;
• n is independently 1 or 2;
• m is independently 1 or 2;
• x is independently 0 or 1;
• and
• with the proviso that n+m+x=2 or 3.

A polymeric or co-polymeric compound comprising a repeating unit of formula (5):

• wherein:
• R is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkyloxy, C1 to C20 alkylamino, —OH, —OR2, —NH2, —NHR2, —NR22, —C(O)OH, —C(O)OR2, —C(O)NH2, —C(O)NHR2, —C(O)NR22, —O(CO)H, —O(CO)R2, —NH(CO)H, —NH(CO)R2, —NR2(CO)H, —NR2(CO)R2, —SH, —SR2, —SO2H, —SO2R2, —SO3R2, —SO3H, —SiR23, —NO2, —CN, —F, —Cl, —Br, and —I;
• each R1 group is independently selected from:
• —H, C1 to C10 alkyl, C1 to C10 haloalkyl, C3 to C12 cycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, C6 to C12 aryl, and C3 to C12 heteroaryl;
• each R2 is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkoxy, and C1 to C20 alkylamino;
• Y is independently a C1 to C250 hydrocarbyl group;
• Y1 is independently either hydrogen or a C1 to C250 hydrocarbyl group;
• Z is independently a C2 to C250 hydrocarbyl group comprising at least one primary or secondary amine;
• Z1 is independently either hydrogen or a C1 to C250 hydrocarbyl group;
• and
• R4, R5 and R6 are independently selected from:
• —H, C1 to C10 alkyl, —F, —CL, —Br, —I, —OH, —OR1, —CN, —C(O)OH, —C(O)OR1, —C(O)NH2, —C(O)NHR1, —C(O)NR12, —O(CO)H, or —O(CO)R1;
• each represents an attachment point between one repeating unit and a single adjacent repeating unit;
• R11 is either a direct bond or —OC(O)—;
• n is independently 1, 2 or 3;
• m is independently 1, 2 or 3;
• x is independently 0 to 2;
• and
• with the proviso that n+m+x=2 to 4.

A method of preparing a compound selected from the group consisting of an aromatic or heteroaromatic amide Mannich base for use as an epoxy resin curative and/or accelerator, or a polymeric hydroxy benzamide Mannich base for use as an epoxy resin curvature and/or accelerator, said method comprising one of:

• a)
• i) reacting an optionally substituted aromatic or heteroaromatic acid, or ester thereof, selected from hydroxy benzoic acid, hydroxypyridine carboxylic acid, pyrrole carboxylic acid, thiophene carboxylic acid, and furan carboxylic acid or an ester thereof, with a first polyamine having at least two nucleophilic amines, to form an aromatic or heteroaromatic amide;
• ii) performing a Mannich reaction using the aromatic or heteroaromatic amide, an aldehyde, and a second amine having at least one nucleophilic amine
• b)
• i) performing a polycondensation reaction with an optionally substituted hydroxy benzoic acid, or ester thereof, and a first aldehyde, ketone or hexamine to give a polymeric hydroxy benzoic acid, or ester thereof;
• ii) reacting the polymeric hydroxy benzoic acid, or ester thereof, with a first polyamine having at least two nucleophilic amines, to give a polymeric hydroxy benzamide;
• iii) performing a Mannich reaction using the polymeric hydroxy benzamide, a second aldehyde, and a second amine having at least one nucleophilic amine
• c)
• i) performing a vinyl polymerisation reaction with optionally substituted and alkenyl substituted hydroxy benzoic acid, or ester thereof, to give a polymeric hydroxy benzoic acid, or ester thereof;
• ii) reacting the polymeric hydroxy benzoic acid, or ester thereof, with a first polyamine having at least two nucleophilic amines, to give a polymeric hydroxy benzamide;
• iii) performing a Mannich reaction using the polymeric hydroxy benzamide, an aldehyde, and a second amine having at least one nucleophilic amine.