Low density fuel resistant sulfur-containing polymer compositions and uses thereof

{
  "publication_number": "US9422451B2",
  "country": "US",
  "kind": "B2",
  "title": "Low density fuel resistant sulfur-containing polymer compositions and uses thereof",
  "abstract": "Low-density compositions and sealants prepared from sulfur-containing prepolymer compositions that exhibit enhanced fuel resistance are disclosed. The low density and enhanced fuel resistance is realized by using polyphenylene sulfide fillers.",
  "claims": [
    "1. A composition, comprising: from 45 wt % to 70 wt % of a sulfur-containing prepolymer, wherein the sulfur-containing prepolymer comprises: a thiol-terminated polythioether comprising a backbone comprising the structure of Formula (1): - R 1 -[- S - (CH 2) 2 - O-(- R 2 - O -) m - (CH 2) 2 - S - R 1] n - (1) wherein, each R 1 is independently selected from C 2-10 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, heterocyclic, -[(- CHR 3 -) p - X -] q - (CHR 3) r -, wherein each R 3 is selected from hydrogen and methyl; each R 2 is independently selected from C 2-10 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, heterocyclic, and -[(- CH 2 -) p - X -] q - (CH 2) r -; each X is independently selected from O, S, and - NR -, wherein R is selected from hydrogen and methyl; m is an integer from 0 to 50; n is an integer ranging from 1 to 60; p is an integer ranging from 2 to 6; q is an integer ranging from 1 to 5; and r is an integer ranging from 2 to 10; a thiol-terminated polysulfide having a weight average molecular weight from 1,100 Daltons to 8,000 Daltons; or a combination thereof; and from 5 wt % to 40 wt % thermoplastic polyphenylene sulfide resin particles, wherein wt % is based on the total weight of the composition.",
    "2. The composition of claim 1, wherein the thiol-terminated polythioether prepolymer comprises a thiol-terminated polythioether of Formula (2a), a thiol-terminated polythioether prepolymer of Formula (2b), and a combination thereof: HS - R 1 -[- S - (CH 2) 2 - O - (R 2 - O) m - (CH 2) 2 - S - R 1 -] n - SH (2a) {HS - R 1 -[- S - (CH 2) 2 - O - (R 2 - O) m - (CH 2) 2 - S - R 1 -] n - S - V′ - } z B (2b) wherein, each R 1 independently is selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and -[(- CHR 3 -) p - X -] q -(- CHR 3 -) r -, wherein, p 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 is independently selected from hydrogen and methyl; and each X is independently selected from - O -, - S -, and - NR -, wherein R is selected from hydrogen and methyl; each R 2 is independently selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and -[(- CHR 3 -) p - X -] q -(- CHR 3 -) r -, wherein p, q, r, R 3, and X are as defined as for R 1; m is an integer from 0 to 50; n is an integer from 1 to 60; B represents a core of a z-valent, polyfunctionalizing agent B(- V) z wherein, z is an integer from 3 to 6; and each V is a moiety comprising a terminal group reactive with a thiol; and each - V′ - is derived from the reaction of - V with a thiol, wherein the terminal group reactive with a thiol group comprises an alkanediyl group.",
    "3. The composition of claim 1, wherein the thiol-terminated polythioether prepolymer comprises the reaction product of reactants comprising: (a) a dithiol of Formula (3): HS - R 1 - SH (3) wherein, R 1 is selected from C 2-6 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and -[- (CHR 3) p - X -] - (CHR 3) r -; wherein, each R 3 is independently selected from hydrogen and methyl; each X is independently selected from - O -, - S -, - NH -, and - NR - wherein R is selected from hydrogen and methyl; p is an integer from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10; and (b) a divinyl ether of Formula (4): CH 2 ═CH - O-[- R 2 - O -] m CH═CH 2 (4) wherein, m is an integer from 0 to 50; and each R 2 is independently selected from C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and -[(- CHR 3 -) p - X -] q -(- CHR 3 -) r -, wherein, each R 3 is independently selected from hydrogen and methyl; each X is independently selected from O, S, NH, and - NR - wherein R is selected from hydrogen and methyl; p is an integer from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10.",
    "4. The composition of claim 3, wherein the reactants further comprise a polyfunctional compound.",
    "5. The composition of claim 1, further comprising an inorganic filler.",
    "6. The composition of claim 1, wherein the composition further comprises from 1 wt % to 10 wt % of an inorganic filler, wherein wt % is based on the total weight of the composition.",
    "7. The composition of claim 1, wherein the composition further comprises from 20 wt % to 40 wt % of an inorganic filler, where wt % is based on the total weight of the composition.",
    "8. The composition of claim 1, formulated as a sealant.",
    "9. The composition of claim 8, comprising a polyepoxy curing agent.",
    "10. A cured sealant prepared from the composition of claim 8.",
    "11. A method of sealing one or more surfaces, comprising: applying the composition of claim 8 to one or more surfaces; and curing the composition to seal the one or more surfaces.",
    "12. A composition, comprising: (a) from 45 wt % to 70 wt % of a thiol-terminated sulfur-containing prepolymer, wherein the thiol-terminated sulfur-containing prepolymer comprises: (i) a thiol-terminated polythioether comprising a backbone comprising the structure of Formula (1): - R 1 -[- S - (CH 2) 2 - O-(- R 2 - O -) m - (CH 2) 2 - S - R 1] n - (1) wherein, each R 1 is independently selected from C 2-10 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, heterocyclic, -[(- CHR 3 -) p - X -] q - (CHR 3) r -, wherein each R 3 is selected from hydrogen and methyl; each R 2 is independently selected from C 2-10 n-alkanediyl, C 3-6 branched alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, heterocyclic, and -[(- CH 2 -) p - X -] q - (CH 2) r -; each X is independently selected from O, S, and - NR -, wherein R is selected from hydrogen and methyl; m is an integer from 0 to 50; n is an integer ranging from 1 to 60; p is an integer ranging from 2 to 6; q is an integer ranging from 1 to 5; and r is an integer ranging from 2 to 10; (ii) a thiol-terminated polysulfide having a weight average molecular weight from 1,100 Daltons to 8,000 Daltons; or (iii) a combination thereof; and (b) from 5 wt % to 40 wt % of thermoplastic polyphenylene sulfide resin particles; (c) from 1 wt % to 10 wt % of an inorganic filler; and (d) a polyepoxy curing agent comprising a novolac epoxy resin, a bisphenol A/epichlorohydrin derived epoxy resin, or a combination thereof wherein wt % is based on the total weight of the composition.",
    "13. The composition of claim 12, formulated as a sealant.",
    "14. A cured sealant prepared from the composition of claim 12.",
    "15. A method of sealing one or more surfaces, comprising: applying the composition of claim 12 to one or more surfaces; and curing the composition to seal the one or more surfaces.",
    "16. The composition of claim 1, wherein the thermoplastic polyphenylene sulfide resin particles are characterized by a density from 1.3 g/cc to 1.4 g/cc.",
    "17. The composition of claim 1, wherein the composition is characterized by a specific gravity from 1.1 to 1.4.",
    "18. The composition of claim 12, wherein the composition is characterized by a specific gravity from 1.1 to 1.4."
  ],
  "description_excerpt": "The present disclosure relates to low density fuel-resistant sulfur-containing polymer compositions and sealants having enhanced fuel resistance.\n\nIn certain applications such as in the aircraft and vehicular industries, it can be desirable to reduce the overall weight of materials. For example, the weight of a polymeric composition can be reduced by incorporating low density fillers. In aerospace applications, coatings and sealants must meet a number of demanding performance requirements that include adhesion, tensile strength, elongation, and high temperature stability, and these properties must be maintained following exposure to aviation fuel. Low density fillers such as hollow polymeric microspheres are effective in reducing the overall density of the polymeric composition but tend to swell upon exposure to aviation fuel and cause degradation in the physical properties of a cured coating or sealant. Inorganic fillers provide reinforcing effects but increase the density of the cured coating or sealant.\n\nLow density coating and sealant compositions exhibiting enhanced fuel resistance are desired.\n\nThe fuel resistance of sulfur-containing prepolymers based sealants can be improved by incorporating a polyphenylene sulfide filler into the sealant. The use of polyphenylene sulfide fillers provides low density coating and sealant compositions suitable for use in aerospace applications.\n\nIn a first aspect, compositions are provided, comprising: a sulfur-containing prepolymer; and a filler comprising a polyphenylene sulfide filler, wherein the composition is characterized by a specific gravity from 1.1 to 1.4.",
  "cpc": [
    "C09D 181/02",
    "B60K 15/03",
    "B60K 2015/03493",
    "C08G 75/00",
    "C08G 75/02",
    "C08L 63/00",
    "C08L 81/00",
    "C08L 81/02",
    "C09D 163/00",
    "C09D 5/34",
    "C09D 7/61",
    "C09D 7/65",
    "C09K 2200/0682",
    "C09K 3/10",
    "C09K 3/1012"
  ],
  "ipc": [
    "B60K 15/03",
    "C09D 163/00",
    "C09D 181/02",
    "C08F 283/00",
    "C08F 290/06",
    "C08G 59/14",
    "C08G 75/00",
    "C08G 75/02",
    "C08G 75/04",
    "C08K 5/00",
    "C08L 63/00",
    "C08L 81/00"
  ],
  "assignees": [
    "PRC Desoto International Inc"
  ],
  "inventors": [
    "Chandra Rao",
    "Marfi Ito",
    "Renhe Lin"
  ],
  "filing_date": "2015-01-09",
  "publication_date": "2016-08-23",
  "grant_date": "2016-08-23",
  "priority_date": "2015-01-09",
  "application_number": "US-201514593069-A",
  "family_id": "55349936",
  "cited_by_count": 43,
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}