Difunctional bio-benzoxazine compounds, preparation methods and uses thereof

A compound of formula (II):

• wherein each R group is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C20 cycloalkyl, C1 to C20 alkyl-C3 to C10 heterocycloalkyl, C1 to C20 alkyloxy, C1 to C20 alkylamino, —OH, —OR1, —NH2, —NHR1, —NR12, —C(O)OH, —C(O)OR1, —C(O)NH2, —C(O)NHR1, —C(O)NR12, —O(CO)H, —O(CO)R1, —NH(CO)H, —NH(CO)R1, —NR1(CO)H, —NR1(CO)R1, —SH, —SR1, —SO2H, —SO2R1, —SO3R1, —SO3H, —SiR13, —NO2, —CN, —F, —Cl, —Br, —I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group;
• wherein each R1 is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkyl-C3 to C10 heterocycloalkyl, C1 to C20 alkoxy, C1 to C20 alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl;
• wherein 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, —OH, —NH2, —OC1 to C20 alkyl, —NHC1 to C20 alkyl, —N(C1 to C20 alkyl)2, —NO2, —CN, —F, —Cl, —Br, and —I;
• wherein R3 is independently selected from:
• C1 to C6 alkyl, C1 to C6 alkenyl, C1 to C6 alkoxy, C1 to C6alkyloxy, —C(O)OH, —C(O)O—C1 to C6 alkyl, C1 to C6 alkyl-(O)O—H, C1 to C6 alkyl-(O)O—C1 to C6 alkyl, and —OH;
• wherein R4 is hydrogen;
• wherein R6 is independently a monovalent group selected from —H, —OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms;
• wherein L2 is a direct bond, a divalent group selected from:
• C(O), O, S, S(O), S(O)2, or a hydrocarbyl linker comprising 1 to 50 carbon atoms;
• wherein y is independently 0, 1, or 2;
• and
• wherein n is independently 0, 1, 2 or 3.

A compound of either formula (IIIa) or formula (IIIb):

• wherein R is selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkyl-C3 to C10 heterocycloalkyl, C1 to C20 alkyloxy, C1 to C20 alkylamino, —OH, —OR1, —NH2, —NHR1, —NR12, —C(O)OH, —C(O)OR1, —C(O)NH2, —C(O)NHR1, —C(O)NR12, —O(CO)H, —O(CO)R1, —NH(CO)H, —NH(CO)R1, —NR1(CO)H, —NR1(CO)R1, —SH, —SR1, —SO2H, —SO2R1, —SO3R1, —SO3H, —SiR13, —NO2, —CN, —F, —Cl, —Br, —I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group;
• wherein each R1 is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkyl-C3 to C10 heterocycloalkyl, C1 to C20 alkoxy, C1 to C20 alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl;
• wherein 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, —OH, —NH2, —OC1 to C20 alkyl, —NHC1 to C20 alkyl, —N(C1 to C20 alkyl)2, —NO2, —CN, —F, —Cl, —Br, and —I;
• wherein R3 is independently selected from:
• C1 to C6 alkyl, C1 to C6 alkenyl, C1 to C6 alkoxy, C1 to C6alkyloxy, —C(O)OH, —C(O)O—C1 to C6 alkyl, C1 to C6 alkyl-(O)O—H, C1 to C6 alkyl-(O)O—C1 to C6 alkyl, and —OH;
• wherein R4 is hydrogen;
• wherein R6 is independently a monovalent group selected from —H, —OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms;
• wherein z is 0 or 1;
• wherein q=2−z;
• and
• wherein n is independently 0, 1, 2 or 3.

A process for preparing a compound of formula (II), (IIIa), or (IIIb);

• wherein each R group is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C20 cycloalkyl, C1 to C20 alkyl-C3 to C10 heterocycloalkyl, C1 to C20 alkyloxy, C1 to C20 alkylamino, —OH, —OR1, —NH2, —NHR1, —NR12, —C(O)OH, —C(O)OR1, —C(O)NH2, —C(O)NHR1, —C(O)NR12, —O(CO)H, —O(CO)R1, —NH(CO)H, —NH(CO)R1, —NR1(CO)H, —NR1(CO)R1, —SH, —SR1, —SO2H, —SO2R1, —SO3R1, —SO3H, —SiR13, —NO2, —CN, —F, —Cl, —Br, —I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group;
• wherein each R1 is independently selected from C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C1 to C20 alkyl-C3 to C20 heterocycloalkyl, C1 to C20 alkoxy, C1 to C20 alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl;
• wherein 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, —OH, —NH2, —OC1 to C20 alkyl, —NHC1 to C20 alkyl, —N(C1 to C20 alkyl)2, —NO2, —CN, —F, —Cl, —Br, and —I;
• wherein R3 is independently selected from:
• C1 to C6 alkyl, C1 to C6 alkenyl, C1 to C6 alkoxy, C1 to C6 alkyloxy, —C(O)OH, —C(O)O—C1 to C6 alkyl, C1 to C6 alkyl-(O)O—H, C1 to C6 alkyl-(O)O—C1 to C6 alkyl, and —OH;
• wherein R4 is hydrogen;
• wherein R6 is independently monovalent group selected from —H, —OH or a hydrocarbyl group comprising 1 to 50 carbon atoms;
• wherein L2 is a direct bond, a divalent group selected from:
• C(O), O, S, S(O), S(O)2, or a hydrocarbyl linker comprising 1 to 50 atoms;
• wherein y is independently 0, 1 or 2;
• wherein z is 0 or 1;
• wherein q=2−z;
• and
• wherein n is independently 0, 1, 2 or 3;
• said method comprising:
• i) providing:
• A) a bisphenol compound comprising a linker L2 and substituted with y R groups on each benzene ring of the bisphenol compound;
• B) a benzene-1,4-diol compound substituted with z R groups;
• or C) a benzene-1,3-diol optionally substituted with 1 R group at the 5-position;
• ii) contacting the compound from step i) with at least one furfuraldehyde substituted with n R3 groups, and at least one primary amine substituted with one R6 group;
• and
• iii) forming a compound of formula (II), (IIIa), or (IIIb).

A method for preparing a reinforced material, said method comprising:

• a) contacting a material to be reinforced with a compound of formula (I), (II), (IIIa), and (IIIb);
• wherein each R group is independently selected from:
• C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C20 cycloalkyl, C3 to C20 alkyl-C3 to C10 heterocycloalkyl, C3 to C20 alkyloxy, C1 to C20 alkylamino, —OH, —OR1, —NH2, —NHR1, —NR12, —C(O)OH, —C(O)OR1, —C(O)NH2, —C(O)NHR1, —C(O)NR12, —O(CO)H, —O(CO)R1, —NH(CO)H, —NH(CO)R1, —NR1(CO)H, —NR1(CO)R1, —SH, —SR1, —SO2H, —SO2R1, —SO3R1, —SO3H, —SiR13, —NO2, —CN, —F, —Cl, —Br, —I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group;
• wherein each R1 is independently selected from C1 to C20 alkyl, C1 to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C1 to C20 alkyl-C6 to C14 aryl, C1 to C20 alkyl-C2 to C9 heteroaryl, C1 to C20 alkyl-C3 to C10 cycloalkyl, C3 to C20 alkyl-C3 to C20 heterocycloalkyl, C1 to C20 alkoxy, C3 to C20 alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl;
• wherein R2 is independently selected from:
• C1 to C20 alkyl, C3 to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, —OH, —NH2, —OC1 to C20 alkyl, —NHC1 to C20 alkyl, —N(C1 to C20 alkyl)2, —NO2, —CN, —F, —Cl, —Br, and —I;
• wherein R3 is independently selected from:
• C1 to C6 alkyl, C1 to C6 alkenyl, C1 to C6 alkoxy, C1 to C6 alkyloxy, —C(O)OH, —C(O)OC—C1 to C6 alkyl, C1 to C6 alkyl-(O)O—H, C1 to C6 alkyl-(O)O—C1 to C6 alkyl, and —OH;
• wherein R4 is hydrogen;
• wherein R6 is independently monovalent group selected from —H, —OH or a hydrocarbyl group comprising 1 to 50 carbon atoms;
• wherein L1 is a divalent hydrocarbyl linker comprising 1 to 50 carbon atoms;
• wherein L2 is a direct bond, a divalent group selected from:
• C(O), O, S, S(O), S(O)2, or a hydrocarbyl linker comprising 1 to 50 atoms;
• wherein x is independently 0, 1, 2 or 3;
• wherein y is independently 0, 1 or 2;
• wherein z is 0 or 1;
• wherein q=2−z;
• and
• wherein n is independently 0, 1, 2 or 3;
• b) allowing said compound to self-polymerise to form a reinforced material.