Bis(sulfonyl)alkanol-containing polythioethers, methods of synthesis, and compositions thereof

1. A bis(sulfonyl)alkanol-containing polythioether comprising a moiety of Formula (10):

—S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —  (10)

wherein each R 10 is independently selected from a C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH.

2. The polythioether of claim 1 , comprising a moiety of Formula (1):

-A-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-  (1)

wherein:

each R 9 is a moiety derived from the reaction of a bis(sulfonyl)-alkanol with thiol groups;

each R 10 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH;

each A is independently a moiety of Formula (2):

—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—  (2)

wherein:

each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) 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 R 3 independently comprises hydrogen or methyl; and

each X independently comprises —O—, —S—, and —NR 5 —, wherein R 5 is selected from hydrogen and methyl; and

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined for R 1 ;

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.

3. The polythioether of claim 1 , wherein each R 9 is ethane-diyl and each R 10 is methane-diyl.

4. The polythioether of claim 1 , wherein the polythioether comprises a bis(sulfonyl)alkanol-containing polythioether of Formula (3), a bis(sulfonyl)alkanol-containing polythioether of Formula (3a), or a combination thereof:

R 6 -A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -R 6   (3)

{R 6 -A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -V′—} z B  (3a)

wherein:

N is an integer from 1 to 10;

each R 9 is a moiety derived from the reaction of a bis(sulfonyl)-alkanol with thiol groups;

each R 10 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH;

each A is independently a moiety of Formula (2):

—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—  (2)

wherein:

each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) 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 R 3 independently comprises hydrogen or methyl; and

each X independently —O—, —S—, or —NR 5 —, wherein R 5 is selected from hydrogen and methyl;

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined for R 1 ;

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 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

each R 6 independently comprises hydrogen or a moiety having a terminal reactive group.

5. The polythioether of claim 4 , wherein each R 6 is hydrogen.

6. The polythioether of claim 4 , wherein each R 9 is ethane-diyl and each R 10 is methane-diyl.

7. The polythioether of claim 4 , wherein each R 6 is the same and the terminal reactive group is selected from —SH, —CH═CH 2 , —NH 2 , —OH, an epoxy group, a polyalkoxysilyl group, an isocyanate group, and a Michael acceptor group.

8. A thiol-terminated bis(sulfonyl)alkanol-containing polythioether comprising the reaction product of reactants comprising:

(a) a thiol-terminated polythioether comprising a thiol-terminated polythioether of Formula (4), a thiol-terminated polythioether of Formula (4a), or a combination thereof:

HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (4)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (4a)

wherein:

each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) 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 R 3 independently comprises hydrogen or methyl; and

each X independently comprises —O—, —S—, or —NR 5 —, wherein R 5 is selected from hydrogen and methyl;

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined for R 1 ;

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 bis(sulfonyl)alkanol of Formula (5):

R 8 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 8   (5)

wherein

each R 8 is independently selected from a group having a terminal group reactive with a terminal thiol group; and

each R 10 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH.

9. The polythioether of claim 8 , wherein the bis(sulfonyl)alkanol comprises a bis(vinylsulfonyl)alkanol of Formula (5a):

CH 2 ═CH—S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —CH═CH 2   (5a).

10. The polythioether of claim 8 , wherein the polythioether of Formula (4) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane and diethylene glycol divinyl ether.

11. The polythioether of claim 8 , wherein the polythioether of Formula (4a) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane, diethylene glycol divinyl ether, and triallyl cyanurate.

12. A thiol-terminated bis(sulfonyl)alkanol-containing polythioether prepolymer comprising the reaction product of reactants comprising:

(a) a thiol-terminated bis(sulfonyl)alkanol-containing polythioether comprising a thiol-terminated bis(sulfonyl)alkanol-containing polythioether of Formula (6), a thiol-terminated bis(sulfonyl)alkanol-containing polythioether of Formula (6a), or a combination thereof:

H-A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -H  (6)

{H-A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -V′—} z B  (6a)

wherein:

N is an integer from 1 to 10;

each R 9 is a moiety derived from the reaction of a bis(sulfonyl)-alkanol with thiol groups;

each R 10 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH;

each A is independently a moiety of Formula (2):

—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—  (2)

wherein:

each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) 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 R 3 independently comprises hydrogen or methyl; and

each X independently —O—, —S—, or —NR 5 —, wherein R 5 is selected from hydrogen and methyl;

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined for R 1 ;

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.

13. The prepolymer of claim 12 , wherein the thiol-terminated bis(sulfonyl)alkanol-containing polythioether of Formula (6), and the polyalkenyl compound comprises diethylene glycol divinyl ether, triallyl cyanurate, or a combination thereof.

14. A method of preparing a thiol-terminated bis(sulfonyl)alkanol-containing polythioether of Formula (6), comprising reacting (N+1) moles of a thiol-terminated polythioether of Formula (4) with (N) moles of a bis(sulfonyl)alkanol of Formula (5):

H-A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -H  (6)

HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (4)

R 8 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 8   (5)

wherein:

N is an integer from 1 to 10;

each R 8 is independently selected from a moiety comprising a terminal group reactive with a terminal thiol group;

each R 9 is a moiety derived from the reaction of a bis(sulfonyl)-alkanol with thiol groups;

each R 10 is independently selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH;

each A is independently a moiety of Formula (2):

—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—  (2)

wherein:

each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) 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 R 3 independently comprises hydrogen or methyl; and

each X independently comprises —O—, —S—, or —NR 5 —, wherein R 5 comprises hydrogen or methyl; and

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined for R 1 ;

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.

15. The polythioether of claim 14 , wherein the bis(sulfonyl)alkanol comprises a bis(vinylsulfonyl)alkanol of Formula (5a):

CH 2 ═CH—S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —CH═CH 2   (5a).

16. A method of preparing a thiol-terminated bis(sulfonyl)alkanol-containing polythioether of Formula (6a) comprising reacting (z) moles of a thiol-terminated bis(sulfonyl)alkanol-containing polythioether of Formula (6) with one (1) mole of a polyfunctionalizing agent of Formula (7):

{H-A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -V′—} z B  (6a)

H-A-[-R 9 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —R 9 -A-] N -H  (6)

B{V} z   (7)

wherein:

each R 9 is a moiety derived from the reaction of a bis(sulfonyl)-alkanol with thiol groups;

each R 10 is selected from C 1-3 alkanediyl and substituted C 1-3 alkanediyl, wherein one or more substituent groups is —OH;

each A is independently a moiety of Formula (2):

—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—  (2)

wherein:

each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) 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 R 3 independently comprises hydrogen or methyl; and

each X independently comprises —O—, —S—, or —NR 5 —, wherein R 5 comprises hydrogen or methyl;

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined for R 1 ;

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.

17. The polythioether of claim 16 , wherein the bis(sulfonyl)alkanol comprises a bis(vinylsulfonyl)alkanol of Formula (5a):

CH 2 ═CH—S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —CH═CH 2   (5a).

18. A composition comprising:

(a) the bis(sulfonyl)alkanol-containing polythioether of claim 1 ; and

(b) a curing agent comprising two or more terminal groups that are reactive with terminal groups of the bis(sulfonyl)alkanol-containing polythioether of claim 1 .

19. The composition of claim 18 , wherein the terminal groups of the bis(sulfonyl)alkanol-containing polythioether is thiol terminated and the curing agent comprises a polyepoxy.

20. The composition of claim 18 , comprising a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer is selected from a polythioether prepolymer, a polysulfide prepolymer, a polyformal prepolymer, and a combination of any of the foregoing.