WO2025080931A1 - Résines à double durcissement pour matériaux à module mixte - Google Patents

Résines à double durcissement pour matériaux à module mixte Download PDF

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WO2025080931A1
WO2025080931A1 PCT/US2024/050904 US2024050904W WO2025080931A1 WO 2025080931 A1 WO2025080931 A1 WO 2025080931A1 US 2024050904 W US2024050904 W US 2024050904W WO 2025080931 A1 WO2025080931 A1 WO 2025080931A1
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resin composition
dual cure
cure resin
prepolymer
optionally
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R. Nicholas CARMEAN
Matthew Panzer
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Carbon Inc
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Carbon Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic

Definitions

  • the present invention relates to compositions and methods for use in additive manufacturing.
  • the present invention relates to resin compositions and methods of using the same in additive manufacturing.
  • Tougheners such as polybutadiene are commonly used in rigid thermoset materials to improve the notched impact toughness of otherwise relatively brittle materials.
  • tougheners When such tougheners are used in additive manufacturing, they are generally unreactive during printing and frequently introduced as particulates, for example, as core-shell rubber particles.
  • reactive diluents often with relatively high glass transition temperatures, may be needed to dissolve the particulates, to lower the viscosity, and to increase the green printed stiffness.
  • the inclusion of such reactive diluents may limit the final performance of the material and may inhibit thermal network formation in dual cure materials, particularly in highly vitrified and/or crosslinked green UV-networks.
  • Monomers and/or prepolymers that provide rubbery or “elastomeric” materials may be included in dual cure materials to improve the performance of rigid networks with desirable thermomechanical properties.
  • the present invention uses elastomeric-producing light polymerizable monomers and/or prepolymers to react with light or radiati on -initiated radicals to produce printed “green” parts that include or contain monomers and/or prepolymers that are solidified by exposure to heat, microwave irradiation and/or moisture.
  • the low glass transition temperature (T g ) of the elastomer-producing monomers and/or prepolymers may produce a rubbery polymer scaffold that may allow for improved thermal network conversion of heat solidified monomers, particularly in highly crosslinked systems, and which may allow for the formation of three-dimensional objects having high heat deflection temperatures.
  • the rubbery or elastomeric UV-network is capable of surviving baking temperatures required to anneal commonly used rigid, heat cured, thermoset materials.
  • the low-T g polymer scaffold may allow for the use of solvent to lower the viscosity of the liquid resin without introducing irreversible defects in the final baked part and can allow for the use of volatile blocking groups.
  • dual cure resin compositions for additive manufacturing that include an elastomer-producing light polymerizable monomer and/or prepolymer; a monomer and/or prepolymer that is solidified by exposure to heat, microwave irradiation, and/or moisture; a photoinitiator; optionally, one or more additional light polymerizable monomers and/or prepolymers; and optionally, a thiol crosslinker.
  • Also provided according to embodiments of the invention are methods of forming a three- dimensional object using a resin composition of the invention.
  • such methods include (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a dual cure resin composition of the invention; (c) irradiating the build region with actinic radiation or light through the optically transparent member to solidify at least a portion of the dual cure resin composition in contact with the carrier; (d) advancing said carrier away from the build surface; (e) repeating steps (b) through (d) to form a solid polymer scaffold; wherein the solid polymer scaffold is a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and wherein the three-dimensional intermediate is further reacted to form the three-dimensional object.
  • amino includes primary, secondary and tertiary amine functional groups.
  • aryl refers to an aromatic functional group including but not limited to phenyl or benzyl, and includes unsubstituted and substituted aryl groups (e.g., substituted with a hydroxyl, nitrile, silyl, epoxy, glycidyl, vinyl, and/or carboxyl).
  • silyl refers to -SiHs and longer saturated silyl chains (e.g., those having 2-10 Si atoms) and includes both straight chain, branched, and/or cyclic silyl groups.
  • the silyl group may be unsubstituted or substituted (e.g., substituted with a hydroxyl, nitrile, silyl, epoxy, glycidyl, vinyl, and/or carboxyl).
  • dual cure resins for additive manufacturing.
  • Such resins include an elastomer-producing light polymerizable monomer and/or prepolymer (which solidify in a “first cure” via UV polymerization); a monomer and/or prepolymer that is solidified by exposure to heat, microwave irradiation, and/or moisture (and which predominantly solidify in a “second cure” by exposure to heat, microwave irradiation, and/or moisture); and a photoinitiator.
  • the elastomer-producing light polymerizable monomers and/or prepolymers from the first cure may combine with more rigid materials from the second cure to form elastomeric phases within a rigid material.
  • Such elastomeric phases may provide the toughening properties traditionally provided by particulate tougheners (e.g., by core-shell rubbers).
  • the elastomeric phases within the polymer matrix may increase the impact strength of the more rigid materials and the dual cure materials may require a greater amount of energy for crack propagation relative to the rigid materials alone.
  • the incorporation of the elastomeric component may increase the ductility of more rigid systems through a variety of mechanisms such as crazing, cavitation, shear yielding, and others.
  • the mechanism of toughening will be dependent on the composition resin and morphology of the network.
  • the incorporation of the elastomer-producing light polymerizable monomers and/or prepolymer may obviate the need for toughening particulates in the resin.
  • dual cure resins having a reduced concentration of particulate filler and/or toughener or dual cure resins that are free or substantially free of particulate filler and/or toughener.
  • the viscosity of the elastomer-producing light polymerizable monomers and/or prepolymers in the resin may be suitably low and the particulate filler and/or toughener may be reduced or eliminated, in some embodiments, the concentration of reactive diluent may be reduced, or the composition may be free or substantially free of reactive diluent.
  • the elastomer-producing light polymerizable monomer and/or prepolymer has a structure of Formula I:
  • the monomer(s) and/or prepolymer(s) solidified by exposure to heat, microwave irradiation, and/or moisture include a cyanate ester (e.g., bisphenol-E cyanate ester), an epoxy group (e.g., bisphenol-A-diglycidyl ether), a blocked isocyanate (e.g., IPDI trimer blocked, for example, with TBAEMA or MEKO), and/or a reactive isocyanate.
  • cyanate ester e.g., bisphenol-E cyanate ester
  • an epoxy group e.g., bisphenol-A-diglycidyl ether
  • a blocked isocyanate e.g., IPDI trimer blocked, for example, with TBAEMA or MEKO
  • a reactive isocyanate e.g., a reactive isocyanate.
  • Other monomers that may be used include, but are not limited to, those found in U.S. Patent Nos. 9,676,96
  • polythiol crosslinkers for use in the present invention include, but are not limited to: thiogly colic acid (CAS #68-11-1); glyceryl mercaptoacetate (CAS #30618-84-9);
  • the dual cure resin may further include other components, such as, for example, a light absorber(s) (e.g., a pigment, dye, UV absorber) and/or an odor scavenger.
  • a light absorber(s) e.g., a pigment, dye, UV absorber
  • odor scavenger e.g., an odor scavenger.
  • Suitable examples of light absorbers include, but are not limited to: (1) titanium dioxide (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxypenyltriazine, and/or benzotriazole ultraviolet light absorb
  • odor scavengers include carbon black, zeolite, a-/ -/y- cyclodextrin, chitosan, and the like.
  • a resin composition of the invention may further include a stabilizer.
  • a “stabilizer” as used herein includes, but is not limited to, hydroquinones (e.g., hydroquinone and hydroquinone monomethyl ether) and catechols (e.g., 4-tert-butylcatechol) for stabilizing reactive monomers or oligomers such as acrylates or methacrylates.
  • Stabilizers can also include antioxidants and additives used for increasing the long-term stability of printed polymer-based materials. Examples include hindered amine light stabilizers, primary and secondary antioxidants, including hindered or semi-hindered phenols, thiosynergists, phosphites, hydroxylamines, and hindered amines.
  • the resin compositions may include solid particles suspended or dispersed therein. Any suitable solid particles can be used and the type and amount of such particles may depend on the end product being fabricated.
  • the particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof.
  • the particles can be nonconductive, semi -conductive, or conductive (including metallic and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or nonmagnetic.
  • the particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc.
  • the particles can be of any suitable size (for example, ranging from 1 nm to 20 pm average diameter).
  • Fillers when included, may be solid or liquid, organic or inorganic, and may include reactive and non-reactive rubbers, siloxanes, acrylonitrile-butadiene rubbers, reactive and non- reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.), inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, including combinations of all of the foregoing.
  • reactive and non-reactive rubbers including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.
  • inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes
  • One or more polymeric and/or inorganic tougheners can be used as a filler in the present invention.
  • the toughener may be uniformly distributed in the form of particles in the cured product. The particles could be less than 5 microns (pm) in diameter.
  • Such tougheners include, but are not limited to, those formed from elastomers, branched polymers, hyperbranched polymers, dendrimers, rubbery polymers, rubbery copolymers, block copolymers, core-shell particles, oxides or inorganic materials such as clay, polyhedral oligomeric silsesquioxanes (POSS), carbonaceous materials (e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes), ceramics and silicon carbides, with or without surface modification or functionalization.
  • PES polyhedral oligomeric silsesquioxanes
  • Core-shell rubbers are particulate materials (particles) having a rubbery core and may be used in some resin compositions of the invention. Such materials are known and described in, for example, U.S. Patent Application Publication No. 2015/0184039, as well as US Patent Application Publication No. 2015/0240113, and U.S. Pat. Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere.
  • the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)).
  • such solid polymer electrolytes have a conductivity of at least 10' 9 S/cm.
  • the composition and/or polymer of the invention includes one or more dopants (e.g. cations and/or anions) that alter the ionic conductivity of at least one polymer therein.
  • dopants e.g. cations and/or anions
  • Examples of cationic dopants include but are not limited to Li + , Na + , K + , Ag + , Mg2 + , Ca 2+ , Ba 2+ , and Zn 2+ .
  • CLIP employs features of a bottom-up three-dimensional fabrication as described above, but the irradiating and/or advancing steps are carried out while also concurrently maintaining a stable or persistent liquid interface between the growing object and the build surface or window, such as by: (i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and (ii) continuously maintaining a gradient of polymerization zone (such as an active surface) between the dead zone and the solid polymer scaffold and in contact with each thereof, the gradient of polymerization zone in some embodiments comprising the light polymerizable component in partially-cured form.
  • a gradient of polymerization zone such as an active surface
  • the further curing or heating step (whether carried out in a liquid or gas fluid) is carried out at an elevated pressure (e.g., elevated sufficiently to reduce volatilization or out-gassing of residual monomers, prepolymers, chain extenders, and/or reactive diluents, etc.).
  • elevated pressure e.g., elevated sufficiently to reduce volatilization or out-gassing of residual monomers, prepolymers, chain extenders, and/or reactive diluents, etc.
  • Suitable pressure ranges are from 10 or 15 psi to 70 or 100 psi, or more.
  • a polymer and/or three-dimensional object of the invention is included in an explosive and/or propellant device. Accordingly, also provided according to embodiments of the invention is an explosive device and/or vehicle that includes a polymer and/or three-dimensional object of the invention.
  • the three-dimensional object is a part or all of an energetic storage device such as a battery and the three-dimensional object may be conductive. Accordingly, also provided are energy storage devices such as batteries that include a three- dimensional object or a polymer of the invention.
  • Example 1 Methacrylate-functionalized polybutadiene-co-acrylonitrile as UV scaffold
  • the components listed in the tables below were added to a container and thoroughly mixed (either by an overhead stirrer or a centrifugation mixer such as TE1INKY mixer) to obtain a homogeneous resin.
  • the mixture was then used to produce a test specimen either by flood curing in a predefined mold or with additive manufacturing processes.
  • the formed test specimen was then heated on a progressively ramped schedule from room temperature to 220 °C for 12 hours or 140 °C for 12 hours. To test thermal stability, samples were also placed in an oven and held at 125 °C for 1000 hours.
  • Table IB Properties of Polymer formed from composition in Table 1A As reflected in FIG. 1, the polymer formed from the composition in Table 1 A shows a heat deflection temperature of 206 °C. This sample also showed a desirable IZOD impact strength of 70 J/m. After remaining at 125°C for 1000 hours, samples had notched IZOD impact values that were 80-90% of the original value.
  • Prepolymers were prepared by adding a blocking agent to a solution of IPDI-trimer, Desomodur Z 4470A, and mixing in a centrifugal mixer until the isocyanate is fully reacted.
  • Two blocking agents were screened: tert-butylamino methacrylate (TB) and methylethyl ketone oxime (MEKO), but others can be used to inhibit chain extension of the isocyanate. These blocking groups can also be used individually.
  • the stoichiometry of the isocyanate to blocking group was 1 : 1 and the reaction was complete without the need for additional heating. Antioxidants can be added to these materials to improve their thermal stability.
  • resin compositions of the invention may produce objects having desirable notched impact strengths and/or heat deflection temperatures.
  • the components listed in the tables below were added to a container and thoroughly mixed (either by an overhead stirrer or a centrifugation mixer such as TE1INKY mixer) to obtain a homogeneous resin.
  • the mixture was then used to produce a test specimen either by flood curing in a predefined mold or with additive manufacturing processes.
  • the formed test specimen was then heated on a progressively ramped schedule from room temperature to 220 °C for 12 hours or 140 °C for 12 hours. To understand the thermal stability, samples were also placed in an oven and held at 125 °C for 1000 hours.
  • Table 2A Epoxy Resin Composition
  • Table 2B Properties of Polymer formed from composition in Table 2A
  • Table 2D Properties of Polymer formed from composition in Table 2C
  • resin compositions of the invention may produce objects having desirable impact strength.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne des compositions de résine à double durcissement utiles pour la fabrication additive qui comprennent un monomère et/ou un prépolymère polymérisable à la lumière produisant un élastomère ; un monomère et/ou un prépolymère qui est solidifié par exposition à la chaleur, à l'irradiation par micro-ondes et/ou à l'humidité ; un photo-initiateur ; éventuellement, un ou plusieurs monomères et/ou prépolymères polymérisables à la lumière supplémentaires ; et éventuellement, un agent de réticulation thiol. L'invention concerne également des procédés de formation d'un polymère et/ou d'un objet tridimensionnel avec la résine, et des polymères et/ou des objets tridimensionnels produits.
PCT/US2024/050904 2023-10-12 2024-10-11 Résines à double durcissement pour matériaux à module mixte Pending WO2025080931A1 (fr)

Applications Claiming Priority (2)

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US202363589675P 2023-10-12 2023-10-12
US63/589,675 2023-10-12

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WO2025080931A1 true WO2025080931A1 (fr) 2025-04-17

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