# US 4,391,924 A · High temperature thermobarrier compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,391,924 A - Document ID: US4391924A - Status: Granted - Kind: A - Application number: 06/436,105 - Filed: 1982-10-22 - Granted: 1983-07-05 - Earliest claimed: 1979-08-28 - Assignees: Goodyear Aerospace Corporation - Inventors: John R. Uram, Jr. - Web page: https://patentgrep.com/patent/US4391924A ## CPC - B32B 17/10018: {comprising only one glass sheet} - B32B 17/10302: {Edge sealing} - B32B 17/10733: {containing epoxy} - B32B 17/10917: {between two pre-positioned glass layers} - C08G 59/40: characterised by the curing agents used - C08G 59/4078: {boron containing compounds} - C08J 9/32: from compositions containing microballoons, e.g. syntactic foams - C08K 5/55: Boron-containing compounds {(C08K5/0091 takes precedence)} - B32B 2369/00: Polycarbonates - Y10T 428/24149: Honeycomb-like - Y10T 428/31507: Of polycarbonate - Y10T 428/31515: As intermediate layer - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract High temperature-resistant thermobarriers have a filler therein. The filler can be an opaque thermobarrier material, a fabric or cloth such that a laminated thermobarrier is formed, or preformed bubbles of glass, ceramic or plastic such that a syntactic foam thermobarrier is formed. The thermobarrier contains a boroxine compound therein as well as epoxy resins and various phosphorus compounds and/or aromatic alcohols. Generally, the syntactic foam thermobarriers give the best heat protection. ## Claims ### Claim 1 A high heat-resistant thermobarrier composition, comprising: a blend having (a) about 100 parts by weight of an epoxy resin; (b) from about 5 to about 30 parts by weight of the boroxine having the formula ##STR11## where R is a group having from 1 to 18 carbon atoms; (c) from about 1 to about 10 parts by weight of a phenyl substituted alkyl alcohol, said alkyl alcohol having from 1 to 20 carbon atoms; and (d) a heat-resistant filler, the amount of said filler being sufficient to form a thixotropic blend. ### Claim 2 (depends on 1) A high heat-resistant thermobarrier composition according to claim 1, wherein said heat-resistant filler is selected from the group consisting of opaque materials, cloths or fabrics, microspheres, and combinations thereof; wherein said opaque material is selected from the group consisting of an inorganic compound in an amount from about 1 to about 80 percent by weight, carbon black or graphite in an amount of from 1 percent to about 30 percent by weight, and a silicone material in an amount of from about 1 percent to about 75 percent by weight; wherein said cloth or fabric filler is selected from the class consisting of ceramic, glass, polyaramid, or combinations thereof, the amount of said cloth or fabric filler ranging from about 50 to about 65 percent by weight; wherein said microspheres is selected from the group consisting of from about 25 percent to about 70 percent by weight of a ceramic, from about 5 percent to about 25 percent by weight of a glass, from about 5 percent to about 25 percent by weight of a phenolic, from about 5 percent to about 25 percent by weight of an inorganic silicate, and from about 5 percent to about 30 percent by weight of carbon or graphite; and wherein said percentage is based upon the total amount of said filler and said blend. ### Claim 3 (depends on 2) A high heat-resistant thermobarrier composition according to claim 2, wherein R of said boroxine is an alkyl having from 1 to 5 carbon atoms, wherein the amount of said boroxine compound ranges from about 8 to about 15 parts per 100 parts of said epoxy compound, and wherein said alkyl alcohol has from 1 to 10 carbon atoms, and wherein the amount of said alcohol ranges from about 1 to about 5 parts by weight per 100 parts of said epoxy. ### Claim 4 (depends on 3) A high heat-resistant thermobarrier composition according to claim 3, wherein said opaque inorganic filler is selected from the group consisting of aluminum oxide trihydrated, aluminum oxide trihydrated dispersions, ammonium bromide, ammonium fluoborate, ammonium orthophosphate, ammonium polyphosphate, ammonium sulfamate, antimony oxide, antimony oxide dispersions, antimony oxide, barium metaborate, barium borate, magnesium sulfate heptahydrate, molybdic oxide, molybdates, molybdenum complex, multi-metal complex, organic-inorganic additive, sodium antimonate, zinc borate, and zinc borate dispersions, wherein the amount of said inorganic filler ranges from about 10 percent to about 60 percent, wherein said opaque silicone filler is selected from the group consisting of silica dioxide, hydrated magnesium silicate, anhydrous alkali aluminum silicate, amorphous precipitated silica, crystalline quartz, microcrystalline quartz, diatomaceous silica, and fused vitrified silica, wherein the amount of said silica filler ranges from about 10 to about 60 percent, and wherein the amount of said carbon black or graphite opaque filler ranges from about 2 percent to about 20 percent; and wherein said cloth or fabric filler exists in an amount of from about 55 to about 60 percent. ### Claim 5 (depends on 3) A high heat-resistant thermobarrier composition according to claim 3, wherein said filler is said microspheres, and wherein the amount of said ceramic microspheres ranges from about 35 percent to about 60 percent, wherein the amount of said glass microspheres ranges from about 10 to about 25 percent, wherein the amount of said phenolic microspheres ranges from about 15 to about 20 percent, wherein the amount of said silicate microspheres ranges from about 10 to about 20 percent, and wherein the amount of said carbon or graphite microspheres ranges from about 10 to about 20 percent. ### Claim 6 (depends on 4) A high heat-resistant thermobarrier composition according to claim 4, wherein said boroxine is said trimethoxyboroxine, and wherein said alcohol is benzyl alcohol. ### Claim 7 (depends on 5) A high heat-resistant thermobarrier composition according to claim 5, wherein said boroxine is said trimethoxyboroxine, and wherein said alcohol is benzyl alcohol. ### Claim 8 A high heat-resistant thermobarrier composition, comprising: a blend having (a) about 100 parts by weight of an epoxy resin; (b) from about 5 to about 30 parts by weight of a boroxine having the formula ##STR12## where R is a group having from 1 to 18 carbon atoms; (c) from about 1 to about 40 parts by weight of a phosphorus compound having the formula ##STR13## where R.sub.3 is selected from the group consisting of hydrocarbon radicals having from 1 to 24 carbon atoms, halo-substituted organic radicals having from 1 to 24 carbon atoms, and multihalo-substituted organic radicals having from 1 to 24 carbon atoms, and where R.sub.3 may be the same or different radicals; where R.sub.4 is selected from the group consisting of all the radicals of R.sub.3, oxygen, and radicals of the formula: --O--R.sub.6, where R.sub.6 is selected from the group consisting of all the radicals of R.sub.3, organo-phosphorus polymeric radicals, and organo-phosphorus esters; where R.sub.5 is selected from the group consisting of hydrogen, hydroxy, oxygen, sulfur, halogen, or no radicals at all, and where Z is selected from the group consisting of oxygen, sulfur, or no radical at all; and (d) a heat-resistant filler, the amount of said filler being sufficient to form a thixotropic blend. ### Claim 9 (depends on 8) A high heat-resistant thermobarrier composition according to claim 8, wherein said phosphorus compound is a phosphite compound, and including from about 1 to about 10 parts by weight of a phenyl substituted alkyl alcohol, said alkyl alcohol having from 1 to 20 carbon atoms. ### Claim 10 (depends on 9) A high heat-resistant thermobarrier composition according to claim 9, wherein said heat-resistant filler is selected from the group consisting of opaque materials, cloths or fabrics, microspheres, and combinations thereof; wherein said opaque material is selected from the group consisting of an inorganic compound in an amount from about 1 to about 80 percent by weight, carbon black or graphite in an amount of from about 1 to about 30 percent, and a silicone material in an amount of from about 1 percent to about 75 percent by weight; wherein said cloth or fabric filler is selected from the class consisting of ceramic, glass, polyaramid, or combinations thereof, the amount of said cloth or fabric filler ranging from about 50 to about 65 percent by weight; wherein said microspheres is selected from the group consisting of from about 25 to about 70 percent by weight of a ceramic, from about 5 to about 25 percent by weight of a glass, from about 5 to about 25 percent by weight of a phenolic, from about 5 to about 25 percent by weight of an inorganic silicate, and from about 5 to about 30 percent by weight of carbon or graphite; and wherein said percentage is based upon the total amount of said filler and said blend. ### Claim 11 (depends on 10) A high heat-resistant thermobarrier composition according to claim 10, wherein said opaque inorganic filler is selected from the group consisting of aluminum oxide trihydrated, aluminum oxide trihydrated dispersions, ammonium bromide, ammonium fluorborate, ammonium orthophosphate, ammonium polyphosphate, ammonium sulfamate, antimony oxide, antimony oxide dispersions, antimony oxide transparent, barium metaborate, barium borate, magnesium sulfate heptahydrate, molybdic oxide, molybdates, molybdenum complex, multi-metal complex, organic-inorganic additive, sodium antimonate, zinc borate, and zinc borate dispersions, wherein the amount of said inorganic filler ranges from about 10 to about 60 percent, wherein said opaque silicone filler is selected from the group consisting of silica dioxide hydrated magnesium silicate, anhydrous alkali, alumina silicate, amorphous pyrogenic silica, amorphous precipitated silica, crystalline quartz, microcrystalline quartz, diatomaceous silica, and fused vitrified silica, wherein the amount of said silica filler ranges from about 10 to about 60 percent, and wherein the amount of said carbon black or graphite opaque filler ranges from about 2 percent to about 20 percent; and wherein said cloth or fabric filler exists in an amount of from about 55 percent to about 60 percent. ### Claim 12 (depends on 10) A high heat-resistant thermobarrier composition according to claim 10, wherein said filler is said microspheres, and wherein the amount of said ceramic microspheres ranges from about 35 to about 60 percent, wherein the amount of said glass microspheres ranges from about 10 to about 25 percent, wherein the amount of said phenolic microspheres ranges from about 15 to about 20 percent, wherein the amount of said silicate microspheres ranges from about 10 to about 20 percent, and wherein the amount of said carbon or graphite microspheres ranges from about 10 to about 20 percent. ### Claim 13 (depends on 11) A high heat-resistant thermobarrier composition according to claim 11, wherein R of said boroxine is an alkyl having from 1 to 5 carbon atoms, wherein the amount of said boroxine compound ranges from about 8 to about 15 parts per 100 parts of said epoxy compound, and wherein said alkyl alcohol has from 1 to 10 carbon atoms, and wherein the amount of said alcohol ranges from about 1 to about 5 parts by weight per 100 parts of said epoxy, wherein said phosphite compounds are selected from the group consisting of diphenyl phosphite, trisnonylphenyl phosphite, triphenyl phosphite, diphenylisooctyl phosphite, phenyl diisodecyl phosphite, diphenylisodecyl phosphite, and wherein the amount of said phosphite compound ranges from about 5 to about 40 parts by weight. ### Claim 14 (depends on 13) A high heat-resistant thermobarrier composition according to claim 13, wherein said boroxine is said trimethoxyboroxine, and wherein said alcohol is benzyl alcohol. ### Claim 15 (depends on 12) A high heat-resistant thermobarrier composition according to claim 12, wherein R of said boroxine is an alkyl having from 1 to 5 carbon atoms, wherein the amount of said boroxine compound ranges from about 8 to about 15 parts per 100 parts of said epoxy compound, and wherein said alkyl alcohol has from 1 to 10 carbon atoms, and wherein the amount of said alcohol ranges from about 1 to about 5 parts by weight per 100 parts of said epoxy, wherein said phosphite compounds are selected from the group consisting of diphenyl phosphite, trisnonylphenyl phosphite, triphenyl phosphite, diphenylisooctyl phosphite, phenyl diisodecyl phosphite, diphenylisodecyl phosphite, and wherein the amount of said phosphite compound ranges from about 5 to about 40 parts by weight. ### Claim 16 (depends on 15) A high heat-resistant thermobarrier composition according to claim 15, wherein said boroxine is said trimethoxyboroxine, and wherein said alcohol is benzyl alcohol. ### Claim 17 (depends on 8) A high heat-resistant thermobarrier composition according to claim 8, wherein said phosphorus compound is a phosphate compound, wherein said heat-resistant filler is selected from the group consisting of opaque materials, cloths or fabrics, microspheres, and combinations thereof, and wherein said opaque material is selected from the group consisting of an inorganic compound in an amount from about 1 to about 80 percent by weight, carbon black or graphite in an amount of from about 1 percent to about 30 percent by weight, and a silicone material in an amount of from about 1 percent to about 75 percent by weight; wherein said cloth or fabric filler is selected from the class consisting of ceramic, glass, polyaramid, or combinations thereof, the amount of said cloth or fabric filler ranging from about 50 to about 65 percent by weight; wherein said microspheres is selected from the group consisting of from about 25 percent to about 70 percent by weight of a ceramic, from about 5 percent to about 25 percent by weight of a glass, from about 5 percent to about 25 percent by weight of a phenolic, from about 5 percent to about 25 percent by weight of an inorganic silicate, and from about 5 percent to about 30 percent by weight of carbon or graphite; wherein said percentage is based upon the total amount of said filler and said blend. ### Claim 18 (depends on 17) A high heat-resistant thermobarrier composition according to claim 17, wherein said opaque inorganic filler is selected from the group consisting of aluminum oxide trihydrated, aluminum oxide trihydrated dispersions, ammonium bromide, ammonium fluoborate, ammonium orthophosphate, ammonium polyphosphate, ammonium sulfamate, antimony oxide, antimony oxide dispersions, antimony oxide transparent, barium metaborate, barium borate, magnesium sulfate heptahydrate, molybdic oxide, molybdates, molybdenum complex, multimetal complex, organic-inorganic additive, sodium antimonate, zinc borate, and zinc borate dispersions, wherein the amount of said inorganic filler ranges from about 10 to about 60 percent, wherein said opaque silicone filler is selected from the group consisting of silica dioxide, hydrated magnesium silicate, anhydrous alkali aluminum silicate, amorphous pyrogenic silica, amorphous precipitated silica, crystalline quartz, microcrystalline quartz, diatomaceous silica, and fused vitrified silica, wherein the amount of said silica filler ranges from about 10 to about 60 percent, and wherein the amount of said carbon black or graphite opaque filler ranges from about 2 percent to about 20 percent; wherein said cloth or fabric filler exists in an amount of from about 55 to about 60 percent. ### Claim 19 (depends on 18) A high heat-resistant thermobarrier composition according to claim 18, wherein R of said boroxine is an alkyl having from 1 to 5 carbon atoms, wherein the amount of said boroxine compound ranges from about 8 to about 15 parts per 100 parts of said epoxy compound, and wherein the amount of said phosphate compound ranges from about 5 to about 30 parts by weight per 100 parts of said epoxy resin, and wherein said phosphate compound is selected from the group consisting of tri(beta, beta' dichloroisopropyl)phosphate, tri(beta chloroethyl)phosphate, bis chloroethyl phosphate ester, a phosphate polymer of the formula ##STR14## where n is a number from 1 to 20, and combinations thereof. ### Claim 20 (depends on 17) A high heat-resistant thermobarrier composition according to claim 17, wherein said filler is said microspheres, and wherein the amount of said ceramic microspheres ranges from about 35 percent to about 60 percent, wherein the amount of said glass microspheres ranges from about 10 to about 25 percent, wherein the amount of said phenolic microspheres ranges from about 15 to about 20 percent, wherein the amount of said silicate microspheres ranges from about 10 percent to about 20 percent, and wherein the amount of said carbon or graphite microspheres ranges from about 10 percent to about 20 percent. ### Claim 21 (depends on 19) A high heat-resistant thermobarrier composition according to claim 19, wherein said boroxine is trimethoxyboroxine. ### Claim 22 (depends on 20) A high heat-resistant thermobarrier composition according to claim 20, wherein R of said boroxine is an alkyl having from 1 to 5 carbon atoms, wherein the amount of said boroxine compound ranges from about 8 to about 15 parts per 100 parts of said epoxy compound, and wherein the amount of said phosphate compound ranges from about 5 to about 30 parts by weight per 100 parts of said epoxy resin, and wherein said phosphate compound is selected from the group consisting of tri(beta, beta' dichloroisopropyl)phosphate, tri(beta chloroethyl)phosphate, bis chloroethyl phosphate ester, a phosphate polymer of the formula: ##STR15## where n is a number from 1 to 20, and combinations thereof. ### Claim 23 (depends on 22) A high heat-resistant thermobarrier composition according to claim 22, wherein said boroxine is trimethoxyboroxine.