Sulfone-containing polythioethers, compositions thereof, and methods of synthesis

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

• (a) a thiol-terminated polythioether adduct comprising a thiol-terminated sulfone-containing adduct of Formula (4), a thiol-terminated sulfone-containing adduct of Formula (4a), or a combination thereof:
• HS—R1-[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1-]n—SH (4)
• {HS—R1-[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1-]nS—V′—}zB (4a)
• 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 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, alkenyl-terminated polyfunctionalizing agent B(—V)z wherein:
• z is an integer from 3 to 6;
• 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 sulfone of Formula (5):
• CH2═CH—S(O)2—CH═CH2 (5).

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

• (a) a thiol-terminated sulfone-containing adduct comprising a thiol-terminated polythioether adduct of Formula (6), a thiol-terminated polythioether adduct of Formula (6a), or a combination thereof:
• H-A-[-CH2—CH2—S(O)2—CH2—CH2-A-]N-H (6)
• {H-A-CH2—CH2—S(O)2—CH2—CH2-A-V′—}zB (6a)
• wherein
• N is an integer from 1 to 10;
• each A is independently a moiety of Formula (2):
• —S—R1-[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n-S— (2)
• 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 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;
• B represents a core of a z-valent, alkenyl-terminated polyfunctionalizing agent B(—V)z wherein:
• z is an integer from 3 to 6;
• 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 sulfone-containing polythioether adduct of Formula (6), comprising reacting (N+1) moles of a thiol-terminated polythioether of Formula (4) with (N) moles of a sulfone of Formula (5):

• H-A-[-CH2—CH2—S(O)2—CH2—CH2-A-]N-H (6)
• HS—R1-[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1-]n—SH (4)
• CH2═CH—S(O)2—CH═CH2 (5)
• wherein:
• N is an integer from 1 to 10;
• each A is independently a moiety of Formula (2):
• —S—R1-[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n-S— (2)
• 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 sulfone-containing polythioether adduct of Formula (6a) comprising reacting (z) moles of a thiol-terminated sulfone-containing polythioether of Formula (6) with one (1) mole of a polyfunctionalizing agent of Formula (7):

• {H-A-CH2—CH2—S(O)2—CH2—CH2-A-V′—}zB (6a)
• H-A-CH2—CH2—S(O)2—CH2—CH2-A-H (6)
• B{V}z (7)
• wherein:
• each A is independently a moiety of Formula (2):
• —S—R1-[—S—(CH2)p—O—(R2—O)m—(CH2)2—S—R1—]n-S— (2)
• 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, alkenyl-terminated polyfunctionalizing agent B(—V)z wherein:
• z is an integer from 3 to 6;
• each V is a group comprising a terminal alkenyl group;
• and
• each —V′— is derived from the reaction of —V with a thiol.