Metal ligand-containing prepolymers, methods of synthesis, and compositions thereof

A thiol-terminated metal ligand-containing polythioether comprising the reaction product of reactants comprising:

• (a) a thiol-terminated polythioether comprising a thiol-terminated polythioether of Formula (18a), a thiol-terminated polythioether of Formula (18b), or a combination thereof:
• HS—R1—[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n—SH (18a)
• {HS—R1—[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n—S—V′—}zB (18b)
• wherein:
• each R1 independently comprises C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein:
• s is an integer from 2 to 6;
• q is an integer from 1 to 5;
• r is an integer from 2 to 10;
• each R3 independently comprises hydrogen or methyl;
• and
• each X independently comprises —O—, —S—, or —NR5—, wherein R5 is selected from hydrogen and methyl;
• each R2 independently comprises C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein s, q, r, R3, and X are as defined for R1;
• m is an integer from 0 to 50;
• n is an integer from 1 to 60;
• p is an integer from 2 to 6;
• and
• B represents a core of a z-valent polyfunctionalizing agent B(—V)z wherein:
• z is an integer from 3 to 6;
• each V is a group comprising a terminal group reactive with terminal thiol groups;
• and
• each —V′— is derived from the reaction of —V with a thiol;
• and
• (b) a metal chelating agent R9-L-R9, wherein each R9 independently comprises a terminal group reactive with a thiol;
• and -L- comprises a metal ligand.

A thiol-terminated metal ligand-containing polythioether prepolymer comprising the reaction product of reactants comprising:

• (a) a thiol-terminated metal ligand-containing polythioether comprising a thiol-terminated metal ligand-containing polythioether of Formula (29a), a thiol-terminated metal ligand-containing polythioether of Formula (29b), or a combination thereof:
• H-A-[—R9′-L-R9′-A-]N—H (29a)
• {H-A-[—R9′-L-R9′-A-]N—V′—}zB (29b)
• wherein:
• N is an integer from 1 to 10;
• each R9′ is independently a moiety derived from the reaction of R9 of a metal chelating agent R9-L-R9 with a thiol group, wherein each R9 comprises a terminal group reactive with a thiol;
• and L comprises a metal ligand;
• each A is independently a moiety of Formula (12):
• —S—R1—[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n—S— (12)
• wherein:
• each R1 independently comprises C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein:
• s is an integer from 2 to 6;
• q is an integer from 1 to 5;
• r is an integer from 2 to 10;
• each R3 independently comprises hydrogen or methyl;
• and
• each X independently —O—, —S—, or —NR5—, wherein R5 is hydrogen or methyl;
• each R2 independently comprises C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein s, q, r, R3, and X are as defined for R1;
• m is an integer from 0 to 50;
• n is an integer from 1 to 60;
• and
• p is an integer from 2 to 6;
• B represents a core of a z-valent, alkenyl-terminated polyfunctionalizing agent B(—V)z wherein:
• z is an integer from 3 to 6;
• and
• each V is a group comprising a terminal alkenyl group;
• and
• each —V′— is derived from the reaction of —V with a thiol;
• and
• (b) a polyalkenyl compound.

A method of preparing a thiol-terminated metal ligand-containing polythioether of Formula (29a), comprising reacting (N+1) moles of a thiol-terminated polythioether of Formula (18a) with (N) moles of a metal chelating agent R9-L-R9:

• H-A-[—R9′-L-R9′-A-]N—H (29a)
• HS—R1—[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n—SH (18a)
• wherein:
• N is an integer from 1 to 10;
• each R9′ is independently a moiety derived from the reaction of R9 of a metal chelating agent R9-L-R9 with a thiol group, wherein each R9 comprises a terminal group reactive with a thiol;
• and L comprises a metal ligand;
• each A is independently a moiety of Formula (12):
• —S—R1—[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n—S— (12)
• wherein:
• each R1 independently comprises C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein:
• s is an integer from 2 to 6;
• q is an integer from 1 to 5;
• r is an integer from 2 to 10;
• each R3 independently comprises hydrogen or methyl;
• and
• each X independently comprises —O—, —S—, or —NR5—, wherein R5 comprises hydrogen or methyl;
• and
• each R2 independently comprises C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein s, q, r, R3, and X are as defined for R1;
• m is an integer from 0 to 50;
• n is an integer from 1 to 60;
• and
• p is an integer from 2 to 6.

A method of preparing a thiol-terminated metal ligand-containing polythioether of Formula (29b) comprising reacting (z) moles of a thiol-terminated metal ligand-containing polythioether of Formula (29a) with one (1) mole of a polyfunctionalizing agent B{V}z:

• {H-A-[—R9′-L-R9′-A-]N—V′—}zB (29b)
• H-A-[—R9′-L-R9′-A-]N—H (29a)
• wherein,
• N is an integer from 1 to 10;
• each R9′ is independently a moiety derived from the reaction of R9 of a metal chelating agent R9-L-R9 with a thiol group, wherein each R9 comprises a terminal group reactive with a thiol;
• and L comprises a metal ligand;
• each A is independently a moiety of Formula (12):
• —S—R1—[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n—S— (12)
• wherein:
• each R1 independently comprises C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein:
• s is an integer from 2 to 6;
• q is an integer from 1 to 5;
• r is an integer from 2 to 10;
• each R3 independently comprises hydrogen or methyl;
• and
• each X independently comprises —O—, —S—, or —NR5—, wherein R5 comprises hydrogen or methyl;
• each R2 independently comprises C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanecycloalkanediyl, or —[(—CHR3—)s—X—]q—(—CHR3—)r—, wherein s, q, r, R3, and X are as defined for R1;
• m is an integer from 0 to 50;
• n is an integer from 1 to 60;
• and
• p is an integer from 2 to 6;
• and
• B represents a core of a z-valent polyfunctionalizing agent B(—V)z wherein:
• z is an integer from 3 to 6;
• each V is a group comprising a terminal group reactive with a terminal thiol group;
• and
• each —V′— is derived from the reaction of —V with a thiol.