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

{
  "publication_number": "US9540540B2",
  "country": "US",
  "kind": "B2",
  "title": "Sulfone-containing polythioethers, compositions thereof, and methods of synthesis",
  "abstract": "Sulfone-containing polythioethers, compositions containing sulfone-containing polythioethers, methods of synthesizing sulfone-containing polythioethers and the use of sulfone-containing polythioethers in aerospace sealant applications are disclosed. The sulfone-containing polythioethers have sulfone groups incorporated into the backbone of the polythioether. Cured sealant compositions comprising the sulfone-containing polythioethers exhibit enhanced thermal resistance.",
  "claims": [
    "1. A sulfone-containing polythioether comprising a moiety of Formula (1): -A-CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A- (1) wherein 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) R 1 is - (CH 2) 2 - O - (CH 2) 2 - O - (CH 2) 2 -; p is 2; R 2 is - (CH 2) 2 -; m is 2; and n is an integer from 1 to 60.",
    "2. The polythioether of claim 1, wherein the polythioether comprises a sulfone-containing polythioether adduct of Formula (3), a sulfone-containing polythioether adduct of Formula (3a), or a combination thereof: R 6 -A-[- CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A-]N - R 6 (3) {R 6 -A-CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A-V′ - } z B (3a) wherein N is an integer from 1 to 10; 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 each R 6 independently comprises hydrogen or a moiety having a terminal reactive group.",
    "3. The polythioether of claim 2, wherein, B(- V) z comprises triallyl cyanurate, which has the structure: z is 3; each - V is - O - CH 2 - CH═CH 2; each - V′ - is - O - (CH 2) 3 -; and B has the structure:",
    "4. The polythioether of claim 2, wherein each R 6 is hydrogen.",
    "5. The polythioether of claim 2, wherein each R 6 is the same and the reactive group comprises - SH, - CH═CH 2, - NH 2, - OH, an epoxy group, a trialkylsilane group, a silyl group, - N═C═O, or a Michael acceptor group.",
    "6. A composition comprising: (a) the sulfone-containing polythioether of claim 1; and (b) a curing agent that is reactive with terminal groups of the sulfone-containing polythioether.",
    "7. The composition of claim 6, wherein each R 6 is hydrogen and the curing agent comprises a polyepoxy.",
    "8. A composition comprising the sulfone-containing polythioether of claim 1, wherein the composition is formulated as a sealant.",
    "9. A cured sealant prepared from the composition of claim 8.",
    "10. A method of sealing a surface, comprising: applying the composition of claim 8 to a surface; and curing the composition to provide a sealed surface.",
    "11. A thiol-terminated sulfone-containing polythioether comprising the reaction product of reactants comprising: (a) a thiol-terminated polythioether adduct 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 -] - S - V′ - }B (4a) wherein, R 1 is - (CH 2) 2 - O - (CH 2) 2 - O - (CH 2) 2 -; p is 2; R 2 is - (CH 2) 2 -; m is 2; n is an integer from 1 to 60; and 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): CH 2 ═CH - S(O) 2 - CH═CH 2 (5).",
    "12. The thiol-terminated sulfone-containing polythioether of claim 11, wherein, B(- V) z comprises triallyl cyanurate, which has the structure: z is 3; each - V is - O - CH 2 - CH═CH 2; each - V′ - is - O - (CH 2) 3 -; and B has the structure:",
    "13. The polythioether of claim 11, wherein, the adduct of Formula (4) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane and diethylene glycol divinyl ether; and the adduct of Formula (4a) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane, diethylene glycol divinyl ether, and triallyl cyanurate.",
    "14. The thiol-terminated sulfone-containing polythioether of claim 11, wherein, B(- V) z comprises triallyl cyanurate, which has the structure: z is 3; each - V is - O - CH 2 - CH═CH 2; each - V′ - is - O - (CH 2) 3 -; and B has the structure:",
    "15. A thiol-terminated sulfone-containing polythioether prepolymer comprising the reaction product of reactants comprising: (a) a thiol-terminated sulfone-containing polythioether adduct comprising a thiol-terminated sulfone-containing polythioether adduct of Formula (6), a thiol-terminated sulfone-containing polythioether adduct of Formula (6a), or a combination thereof: H-A-[- CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A-] N - H (6) {H-A-CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A-V′ - } z B (6a) wherein, N is an integer from 1 to 10; 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, R 1 is - (CH 2) 2 - O - (CH 2) 2 - O - (CH 2) 2 -; p is 2; R 2 is - (CH 2) 2 -; m is 2; n is an integer from 1 to 60; 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 polyalkenyl compound.",
    "16. The prepolymer of claim 15, wherein the adduct is the adduct of Formula (6), and the polyalkenyl compound comprises diethylene glycol divinyl ether and triallyl cyanurate.",
    "17. A composition comprising: (a) the thiol-terminated sulfone-containing polythioether of claim 15; and (b) a curing agent that is reactive with the terminal thiol groups of the thiol-terminated sulfone-containing polythioether.",
    "18. 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-[- CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -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) CH 2 ═CH - S(O) 2 - CH═CH 2 (5) wherein: N is an integer from 1 to 10; each A is independently a moiety of Formula (2): - S - R 1 - [- S - (CH 2), - O - (R 2 - O) m - (CH 2) 2 - S - R 1 -] n - S - (2) wherein: R 1 is - (CH 2) 2 - O - (CH 2) 2 - O - (CH 2) 2 -; p is 2; R 2 is - (CH 2) 2 -; m is 2; and n is an integer from 1 to 60.",
    "19. A method of preparing a thiol-terminated sulfone-containing polythioether adduct of Formula (6a) comprising reacting a thiol-terminated sulfone-containing polythioether of Formula (6) with a polyfunctionalizing agent of Formula (7): {H-A-CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A-V′ - }B (6a) H-A-CH 2 - CH 2 - S(O) 2 - CH 2 - CH 2 -A-H (6) B{ - V} z (7) wherein: each A is independently a moiety of Formula (2): - S - R 1 -[- S - (CH 2), - O - (R 2 - O) m - (CH 2) 2 - S - R 1 -] n - S - (2) wherein: R 1 is - (CH 2) 2 - O - (CH 2) 2 - O - (CH 2) 2 -; p is 2; R 2 is - (CH 2) 2 -; m is 2; and n is an integer from 1 to 60; 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.",
    "20. The method of claim 19, wherein, B(- V) z comprises triallyl cyanurate, which has the structure: z is 3; each - V is - O - CH 2 - CH═CH 2; each - V′ - is - O - (CH 2) 3 -; and B has the structure:"
  ],
  "description_excerpt": "This application is a continuation of U.S. application Ser. No. 13/833,827, filed on Mar. 15, 2013, which is incorporated by reference in its entirety.\n\nThe present disclosure relates to sulfone-containing polythioethers, compositions containing sulfone-containing polythioethers, methods of synthesizing sulfone-containing polythioethers and uses of sulfone-containing polythioethers in aerospace sealant applications. The sulfone-containing polythioethers contain sulfone groups incorporated into the backbone of the polythioether.\n\nSealants useful in aerospace and other applications must satisfy demanding mechanical, chemical, and environmental requirements. For example, it is desirable that aerospace sealants function over at temperature range such as from about −67° F. to about 360° F. Michael addition curing chemistries employing divinyl sulfone and sulfur-containing polymers have been shown to produce aerospace sealants having faster cure rates and enhanced performance including fuel resistance and thermal resistance. For example, in the systems disclosed in U.S. application Ser. No. 13/529,237, filed on Jun. 21, 2012, sulfur-containing polymer adducts such as polythioether adducts containing terminal Michael acceptor groups such as vinyl sulfone groups are reacted with a curing agent such as a thiol-terminated sulfur-containing polymer to form a cured composition.",
  "cpc": [
    "C09D 181/02",
    "C07C 317/04",
    "C07C 317/18",
    "C08F 228/04",
    "C08G 75/00",
    "C08G 75/02",
    "C08G 75/029",
    "C08G 75/20",
    "C08G 75/23",
    "C08L 81/00",
    "C08L 81/02",
    "C08L 81/04",
    "C08L 81/06",
    "C09K 3/10"
  ],
  "ipc": [
    "C07C 317/04",
    "C08G 75/02",
    "C09D 181/02",
    "C07C 317/18",
    "C08F 228/04",
    "C08G 75/00",
    "C08G 75/20",
    "C08G 75/23",
    "C08L 81/00",
    "C08L 81/02",
    "C08L 81/04"
  ],
  "assignees": [
    "PRC Desoto International Inc"
  ],
  "inventors": [
    "Chandra Rao",
    "Juexiao Cai",
    "Renhe Lin"
  ],
  "filing_date": "2015-05-11",
  "publication_date": "2017-01-10",
  "grant_date": "2017-01-10",
  "priority_date": "2013-03-15",
  "application_number": "US-201514708314-A",
  "family_id": "50549420",
  "cited_by_count": 45,
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}