# US 11,999,817 B1 · Bismaleimide-thiol-epoxy polymer compositions, and methods of making and using the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,999,817 B1 - Document ID: US11999817B1 - Status: Granted - Kind: B1 - Application number: 17/345,475 - Filed: 2021-06-11 - Granted: 2024-06-04 - Earliest claimed: 2020-09-25 - Assignees: HRL Laboratories, LLC - Applicants: HRL Laboratories, LLC - Inventors: Ashley Dustin; Adam Gross; Andrew Nowak; Kaitlin Albanese - Web page: https://patentgrep.com/patent/US11999817B1 ## CPC - C08G 59/38: together with di-epoxy compounds - C08G 59/4014: {Nitrogen containing compounds} - C08G 59/5006: {aliphatic} - C08J 5/042: {with carbon fibres} - C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins - C08J 2363/00: Characterised by the use of epoxy resins; Derivatives of epoxy resins - 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) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Some variations provide a thermoformable and thermosettable bismaleimide-thiol-epoxy resin composition comprising: a thiol-endcapped bismaleimide monomer or oligomer; a thiol-containing species; an epoxy species; a curing catalyst; and optional additives. Other variations provide a method of making a bismaleimide-thiol-epoxy resin composition, comprising: providing a starting bismaleimide, a starting multifunctional amine, a starting multifunctional thiol, an acid catalyst, and a solvent to form a starting reaction mixture; reacting the bismaleimide, the multifunctional amine, and the multifunctional thiol to form a thiol-endcapped bismaleimide monomer or oligomer; providing a thiol-containing species; providing at least one epoxy species; providing a curing catalyst; and combining the thiol-endcapped bismaleimide monomer or oligomer, the thiol-containing species, the epoxy species, and the curing catalyst, to form a bismaleimide-thiol-epoxy resin composition. Other variations provide a method of thermoprocessing comprising: thermoforming, but not completely curing, a bismaleimide-thiol-epoxy resin composition; and, at a later time, completely curing the thermoformed bismaleimide-thiol-epoxy resin. ## Claims ### Claim 1 A bismaleimide-thiol-epoxy resin composition comprising: (a) at least one thiol-endcapped bismaleimide monomer or oligomer, wherein said at least one thiol-endcapped bismaleimide monomer or oligomer is endcapped with a multifunctional thiol; (b) at least one thiol-containing species having a thiol functionality of at least 2, wherein said at least one thiol-containing species is distinct from thiol groups contained in said at least one thiol-endcapped bismaleimide monomer or oligomer, and wherein said at least one thiol-containing species is chemically different than an unreacted amount of said multifunctional thiol; (c) at least one epoxy species having an epoxide functionality of at least 2, wherein said at least one epoxy species is distinct from said at least one thiol-endcapped bismaleimide monomer or oligomer; (d) optionally, at least one curing catalyst; and (e) optionally, at least one additive, wherein said bismaleimide-thiol-epoxy resin composition is thermoformable and thermosettable. ### Claim 2 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said at least one thiol-endcapped bismaleimide monomer or oligomer is an acid-catalyzed reaction product of (i) a bismaleimide, (ii) a multifunctional amine, and (iii) said multifunctional thiol. ### Claim 3 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said thiol functionality is at least 3. ### Claim 4 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said at least one thiol-containing species is selected from the group consisting of 1,2-bis(2-mercaptoethoxy)ethane, hexanedithiol, 1,2,4-tris(2-mercaptoethyl)cyclohexane, pentaerythritol tetrakis(3-mercaptopropionate), 4,4′-thiobisbenzenethiol, 1,4-benzenediethanethiol, and combinations thereof. ### Claim 5 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said epoxide functionality is at least 3. ### Claim 6 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said at least one epoxy species is selected from the group consisting of N,N,N′,N′-tetraglycidyl-4,4′-methylenebisbenzenamine, bisphenol A diglycidyl ether, and combinations thereof. ### Claim 7 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said at least one curing catalyst is included in said bismaleimide-thiol-epoxy resin composition. ### Claim 8 (depends on 7) The bismaleimide-thiol-epoxy resin composition of claim 7, wherein said at least one curing catalyst is selected from the group consisting of 1-methylimidazole, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and combinations thereof. ### Claim 9 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said at least one additive is selected from the group consisting of a viscosity modifier, an adhesion promoter, a liquid toughener, a particulate toughener, an antioxidant, a thermal enhancer, a flame retardant, a surfactant, and combinations thereof. ### Claim 10 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said viscosity modifier is selected from the group consisting of silica, fumed silica, polyether ether ketone, polyetherketoneketone, carbon black, alumina, glycolic acid ethoxylates, methyltrialkylammonium chloride, oleylamine, polyoxypropylene-polyoxyethylene poloxamers, polyoxyethylene isooctylcyclohexyl ether, polyethylene glycol tert-octylphenyl ether, polyethylene glycol nonylphenyl ether, 3-(1-pyridinio)-1-propanesulfonate, dimethylethylammoniumpropane sulfonate, sodium 2,3-dimercaptopropanesulfonate monohydrate, and combinations thereof. ### Claim 11 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said adhesion promoter is selected from the group consisting of titanates, zirconates, silanes, and combinations thereof. ### Claim 12 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said particulate toughener is selected from the group consisting of polyether ether ketone, polyetherketoneketone, acrylonitrile-butadiene-styrene terpolymers, polyaramides, polyimides, and combinations thereof. ### Claim 13 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said antioxidant is selected from the group consisting of metal oxides, organic radical scavengers, inorganic radical scavengers, and combinations thereof. ### Claim 14 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said thermal enhancer is selected from the group consisting of metal oxides, metal carbonates, metal nitrides, metal silicates, metal silicides, and combinations thereof. ### Claim 15 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said thermal enhancer is selected from the group consisting of silica, alumina, titania, mica, CaSiO3, iron oxides, and combinations thereof. ### Claim 16 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said flame retardant is selected from the group consisting of ammonium salts, phosphate salts, phosphines, halogenated compounds, carbonate salts, hydroxide salts, borate salts, silica, and combinations thereof. ### Claim 17 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said flame retardant is selected from the group consisting of ammonium polyphosphate, magnesium hydroxide, zinc hydroxystannate, antimony trioxide, magnesium hydroxycarbonate, zinc borate, magnesium aluminum hydroxycarbonate, aluminum trihydroxide, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), bisphenol-A-bis(diphenyl phosphate), brominated polyols, melamine resins, chlorinated paraffins, and combinations thereof. ### Claim 18 (depends on 9) The bismaleimide-thiol-epoxy resin composition of claim 9, wherein said surfactant is selected from the group consisting of glycolic acid ethoxylates, methyltrialkylammonium chloride, oleylamine, polyoxypropylene-polyoxyethylene poloxamers, polyoxyethylene isooctylcyclohexyl ether, polyethylene glycol tert-octylphenyl ether, polyethylene glycol nonylphenyl ether, 3-(1-pyridinio)-1-propanesulfonate, dimethylethylammoniumpropane sulfonate, sodium 2,3-dimercaptopropanesulfonate monohydrate, and combinations thereof. ### Claim 19 (depends on 1) The bismaleimide-thiol-epoxy resin composition of claim 1, wherein said bismaleimide-thiol-epoxy resin composition is characterized by a curing time of from about 0.5 hours to about 8 hours at a curing temperature of 180° C. ### Claim 20 (depends on 1) A carbon fiber-reinforced composite comprising (i) the bismaleimide-thiol-epoxy resin composition of claim 1 and (ii) one or more continuous carbon fiber tows. ### Claim 21 A method of making a bismaleimide-thiol-epoxy resin composition, said method comprising: (i) providing a starting bismaleimide, a starting multifunctional amine, a starting multifunctional thiol, an acid catalyst, and optionally a solvent to form a starting reaction mixture; (ii) reacting said starting bismaleimide, said starting multifunctional amine, and said starting multifunctional thiol to form at least one thiol-endcapped bismaleimide monomer or oligomer; (iii) providing at least one thiol-containing species having a thiol functionality of at least 2, wherein said at least one thiol-containing species is distinct from thiol groups contained in said at least one thiol-endcapped bismaleimide monomer or oligomer, and wherein said at least one thiol-containing species is chemically different than an unreacted amount of said multifunctional thiol from step (ii); (iv) providing at least one epoxy species having an epoxide functionality of at least 2; (v) providing at least one curing catalyst; (vi) optionally, providing at least one additive; and (vii) combining said at least one thiol-endcapped bismaleimide monomer or oligomer, said at least one thiol-containing species, said at least one epoxy species, said at least one curing catalyst, and, if step (vi) is conducted, said at least one additive, to form a bismaleimide-thiol-epoxy resin composition. ### Claim 22 (depends on 21) The method of claim 21, wherein said starting bismaleimide is selected from the group consisting of 4,4′-bis(maleimido)diphenylmethane, N,N′-(1,3-phenylene)dimaleimide, and combinations thereof. ### Claim 23 (depends on 21) The method of claim 21, wherein said starting multifunctional amine is selected from the group consisting of 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, phenyldiamine, 4,4′-(difluoromethylene)bisbenzenamine, bis(4-aminophenyl)methanone, and combinations thereof. ### Claim 24 (depends on 21) The method of claim 21, wherein said starting multifunctional thiol is selected from the group consisting of 1,2-bis(2-mercaptoethoxy)ethane, hexanedithiol, 1,2,4-tris(2-mercaptoethyl)cyclohexane, pentaerythritol tetrakis(3-mercaptopropionate), 4,4′-thiobisbenzenethiol, 1,4-benzenediethanethiol, and combinations thereof. ### Claim 25 (depends on 21) The method of claim 21, said method further comprising curing said bismaleimide-thiol-epoxy resin composition. ### Claim 26 A method of thermoprocessing a bismaleimide-thiol-epoxy resin composition, said method comprising: (i) providing a bismaleimide-thiol-epoxy resin composition comprising: at least one thiol-endcapped bismaleimide monomer or oligomer; at least one thiol-containing species having a thiol functionality of at least 2, wherein said at least one thiol-containing species is distinct from thiol groups contained in said at least one thiol-endcapped bismaleimide monomer or oligomer, and wherein said at least one thiol-containing species is chemically different than an unreacted amount of said multifunctional thiol; at least one epoxy species having an epoxide functionality of at least 2; at least one curing catalyst; and optionally, at least one additive; (ii) thermoforming, but not completely curing, said bismaleimide-thiol-epoxy resin composition, to generate a thermoformed bismaleimide-thiol-epoxy resin; and (iii) separately from step (ii), completely curing said thermoformed bismaleimide-thiol-epoxy resin. ### Claim 27 (depends on 26) The method of claim 26, wherein said thermoforming in step (ii) is B-staging of said bismaleimide-thiol-epoxy resin composition. ### Claim 28 (depends on 27) The method of claim 27, wherein said B-staging comprises exposing said bismaleimide-thiol-epoxy resin composition to a temperature from about 25° C. to about 100° C. for a time from about 5 minutes to about 2 weeks. ### Claim 29 (depends on 27) The method of claim 27, wherein said B-staging comprises exposing said bismaleimide-thiol-epoxy resin composition to a temperature from about 10° C. to about 30° C. for a time from about 1 hour to about 24 hours. ### Claim 30 (depends on 26) The method of claim 26, wherein said thermoforming in step (ii) comprises exposing said bismaleimide-thiol-epoxy resin composition to a temperature from about 25° C. to about 100° C. ### Claim 31 (depends on 26) The method of claim 26, wherein said completely curing in step (iii) is conducted in about 8 hours or less. ### Claim 32 (depends on 26) The method of claim 26, wherein said completely curing in step (iii) is conducted at a temperature of about 200° C. or less.