WO2025106936A1 - Matériaux de poly(méth)acrylimide présentant des propriétés thermomécaniques améliorées - Google Patents

Matériaux de poly(méth)acrylimide présentant des propriétés thermomécaniques améliorées Download PDF

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WO2025106936A1
WO2025106936A1 PCT/US2024/056301 US2024056301W WO2025106936A1 WO 2025106936 A1 WO2025106936 A1 WO 2025106936A1 US 2024056301 W US2024056301 W US 2024056301W WO 2025106936 A1 WO2025106936 A1 WO 2025106936A1
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optionally substituted
precursor polymer
reaction mixture
monomer
meth
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Marco SERVALLI
Paul Share
Jules THIERY
Ilya L. Rushkin
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Gencores Inc
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Gencores Inc
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation

Definitions

  • P(M)I poly(meth)acrylimide
  • Some embodiments relate to a process for producing such P(M)I materials and associated precursor polymer which are optionally foamed in a relatively efficient (e.g., short time) and/or advantageous manner from the perspectives of one or more of time, cost, processing condition including but not restricted to temperature and pressures, the number of processing steps and/or geometry.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation to form a solid layer of a precursor polymer, the radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; and
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation to form a solid layer of a precursor polymer, the radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 100 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and (b) imidizing at least a section of the solid layer of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation to form a layer of a precursor polymer, the radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 100 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and at the end of the irradiation, the reaction mixture has a percent conversion of at least 40%; and (b) imidizing at least a section of the layer of the precursor polymer to generate the poly(meth)acrylimide. [0012] In some embodiments, provided here, provided here
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and (b) imidizing at least a portion of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation comprising actinic radiation to form a precursor polymer, wherein:
  • the reaction mixture comprises a plurality of monomer molecules, a near-infrared dye, and an initiator, the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer, and the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm and less than or equal to 2500nm; and (b) imidizing at least a portion of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising: irradiating a material comprising a precursor polymer and a near-infrared dye with radiation comprising actinic radiation to imidize at least a portion of the precursor polymer to generate the poly(meth)acrylimide, wherein: the precursor polymer comprises an optionally substituted polyacrylate, an optionally substituted polyacrylamide, an optionally substituted polyacrylonitrile, an optionally substituted polyacrylic acid, and/or any copolymer thereof, and the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm and less than or equal to 2500.
  • a poly(meth)acrylimide prepared according to any method provided herein.
  • a process for producing poly(meth)acrylimide resins described herein proceeds by copolymerization of a (meth)acrylic acid or (meth)acrylic ester, or combination thereof, with a (meth)acrylamide or (meth)acrylonitrile, or combination thereof, with or without further copolymerizable comonomers.
  • Such a process may comprise the two or three process steps of polymerization, imidization, and, optionally, foaming.
  • the process for producing poly(meth)acrylimide resins optionally capable of forming foams proceeds by copolymerization of a (meth)acrylic acid or (meth)acrylic ester, or combination thereof, with (meth)acrylamides or (meth)acrylonitrile, or combination thereof, with or without further copolymerizable comonomers in the three process steps of polymerization in the presence of free-radical initiators activated by actinic radiation, imidization and optionally foaming.
  • the methods provided herein can be employed to generate poly(meth)acrylimide materials (e.g., resins and/or foams comprising a poly(meth)acrylimide).
  • the methods provided herein generate a poly(meth)acrylimide resin that may be capable of being foamed and/or may optionally undergo foaming.
  • the resulting P(M)I foams may be of high quality, particularly with regard to the geometry obtainable and/or thermomechanical properties, and/or may have a uniform distribution of closed cells.
  • this disclosure provides uniform PMI materials in the form of arbitrary geometries by employing photoinitiated polymerizations.
  • the present disclosure provides a process whereby a poly(meth)acrylimide is obtained without the use of an optionally substituted acrylonitrile monomer. In some embodiments, the present disclosure provides a process whereby poly(meth)acrylimide foams are obtainable without the use of an optionally substituted acrylonitrile monomer.
  • the present disclosure provides a process whereby poly(meth)acrylimide foams (P(M)I foams) are obtainable without the use of (meth)acrylonitrile.
  • This object can be achieved by a method for producing optionally foamable polymethacrylimide materials by copolymerization of methacrylic acid/esters and methacrylamides, as well as optionally further copolymerizable monomers in the presence of radical-forming initiators, thermally induced imidization of the copolymer to poly(meth)acrylimide, and optional transformation to a foamed material, which can be characterized in that the copolymerization is performed photochemically by optionally using additive manufacturing techniques.
  • FIG. 1 illustrates a dynamic mechanical analysis (DMA) plot of compressive modulus as a function of temperature for PMI foam materials produced using thermal curing and photocuring
  • FIG 2 illustrates a dynamic mechanical analysis (DMA) plot of compressive modulus as a function of temperature for PMI foam materials produced using thermal curing and photocuring compared to two different commercially available PMI foam materials.
  • FIG. 3 shows temperature measurements over time upon irradiation with a 810nm LED (0.95W/cm 2 irradiance) at the surface of precursor polymer samples without blowing agents and containing the NIR dye IR-813 at different %wt as compared to a control precursor polymer sample without the dye. Imidization temperatures can be reached in 50 s.
  • FIG. 4 shows temperature measurements over time upon irradiation with a 810 nm LED (1.31 W/cm 2 irradiance) at the surface of precursor polymer samples without blowing agents and containing the NIR dye IR-813 at different %wt as compared to a control precursor polymer sample without the dye. Minimal imidization temperatures can be reached in 30 s.
  • FIG. 5 shows temperature measurements over time upon irradiation with a 810 nm LED (0.95W/cm 2 irradiance) at the surface of foamable precursor polymer samples containing the NIR dye IR-813 at different %wt as compared to a control precursor polymer sample without the dye.
  • FIG. 6 shows temperature measurements over time upon irradiation with a 810 nm LED (1.31W/cm 2 irradiance) at the surface of foamable precursor polymer samples
  • FIG. 7 shows temperature measurements over time upon irradiation with a 810 nm LED (1.48 W/cm 2 irradiance) at the surface of foamable precursor polymer samples containing the NIR dye IR-813 at different %wt as compared to a control precursor polymer sample without the dye.
  • the drop in temperature in the curves corresponds to the foaming onset.
  • FIG. 8 shows temperature measurements over time upon irradiation with a 810 nm LED (0.95 W/cm 2 irradiance) at the surface of foamable precursor polymer samples containing the NIR dye IR-783 at different %wt as compared to a control precursor polymer sample without the dye.
  • the drop in temperature in the curve corresponds to the foaming onset at around 60 s.
  • FIG. 9 shows temperature measurements over time upon irradiation with a 810 nm LED (1.31W/cm 2 irradiance) at the surface of foamable precursor polymer samples containing the NIR dye IR-783 at different %wt as compared to a control precursor polymer sample without the dye.
  • FIG. 10 shows temperature measurements over time upon irradiation with a 810 nm LED (1.48 W/cm 2 irradiance) at the surface of foamable precursor polymer samples containing the NIR dye IR-783 at different %wt as compared to a control precursor polymer sample without the dye.
  • the drop in temperature in the curves corresponds to the foaming onset.
  • a group is optionally substituted unless expressly provided otherwise.
  • the term “optionally substituted” refers to being substituted or unsubstituted.
  • alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups are optionally substituted.
  • Optionally substituted refers to a group which is substituted or unsubstituted (e.g., “substituted” or “unsubstituted” alkyl, “substituted” or “unsubstituted” alkenyl, “substituted” or “unsubstituted” alkynyl, “substituted” or “unsubstituted” heteroalkyl, “substituted” or “unsubstituted” heteroalkenyl, “substituted” or “unsubstituted” heteroalkynyl, “substituted” or “unsubstituted” carbocyclyl, “substituted” or “unsubstituted” heterocyclyl, “substituted” or “unsubstituted” aryl or “substituted” or “unsubstituted” heteroaryl group).
  • substituted means that at least one hydrogen present on a group is replaced with a permissible substituent, e.g., a substituent which upon substitution results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction.
  • a “substituted” group has a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position.
  • substituted is contemplated to include substitution with all permissible substituents of organic compounds, and includes any of the substituents described herein that results in the formation of a stable compound.
  • the present disclosure contemplates any and all such combinations in order to arrive at a stable compound.
  • heteroatoms such as nitrogen may have hydrogen substituents and/or any suitable substituent as described herein which satisfy the valencies of the heteroatoms and results in the formation of a stable moiety.
  • the disclosure is not limited in any manner by the exemplary substituents described herein.
  • each R bb is independently hydrogen, substituted (e.g., substituted with one or more halogen) or unsubstituted C1-10 alkyl, or a nitrogen protecting group.
  • each oxygen atom substituent is independently substituted (e.g., substituted with one or more halogen) or unsubstituted C 1-6 alkyl or an oxygen protecting group.
  • the substituent present on an oxygen atom is an oxygen protecting group (also referred to herein as an “hydroxyl protecting group”).
  • Oxygen protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3 rd edition, John Wiley & Sons, 1999, incorporated herein by reference.
  • Nitrogen atoms can be substituted or unsubstituted as valency permits, and include primary, secondary, tertiary, and quaternary nitrogen atoms.
  • R aa is hydrogen, substituted (e.g., substituted with one or more halogen) or unsubstituted C1-10 alkyl, or a nitrogen protecting group.
  • each nitrogen atom substituent is independently substituted (e.g., substituted with one or more halogen) or unsubstituted C1-6 alkyl or a nitrogen protecting group.
  • the substituent present on the nitrogen atom is a nitrogen protecting group (also referred to herein as an “amino protecting group”).
  • Nitrogen protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3 rd edition, John Wiley & Sons, 1999, incorporated herein by reference.
  • each instance of R aa is, independently, selected from C 1–20 alkyl, C 1–20 perhaloalkyl, C1–20 alkenyl, C1–20 alkynyl, heteroC1–20 alkyl, heteroC1–20alkenyl, heteroC1–20alkynyl, C3-10 carbocyclyl, 3-14 membered heterocyclyl, C6-14 aryl, and 5- 14 membered heteroaryl, or two R aa groups are joined to form a 3-14 membered heterocyclyl or 5-14 member
  • each carbon atom substituent is independently halogen, substituted (e.g., substituted with one or more halogen) or unsubstituted C1-6 alkyl, ⁇ OR aa , ⁇ SR aa , ⁇ N(R bb )2, –CN, –SCN, or –NO2.
  • each carbon atom substituent is independently halogen, substituted (e.g., substituted with one or more halogen moieties) or unsubstituted C 1–10 alkyl, ⁇ OR aa , ⁇ SR aa , ⁇ N(R bb )2, –CN, –SCN, or –NO2, wherein R aa is hydrogen, substituted (e.g., substituted with one or more halogen) or unsubstituted C1–10 alkyl, an oxygen protecting group (e.g., silyl, TBDPS, TBDMS, TIPS, TES, TMS, MOM, THP, t-Bu, Bn, allyl, acetyl, pivaloyl, or benzoyl) when attached to an oxygen atom, or a sulfur protecting group (e.g., acetamidomethyl, t-Bu, 3-nitro-2-pyridine sulfenyl, 2-pyridine-s
  • the molecular weight of an optional substituent is lower than 250, lower than 200, lower than 150, lower than 100, or lower than 50 g/mol.
  • Compounds described herein can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
  • the compounds described herein can be in the form of an individual enantiomer, diastereomer or geometric isomer, or can be in the form of a mixture of stereoisomers, including racemic mixtures and mixtures enriched in one or more stereoisomer.
  • Isomers can be isolated from mixtures by methods known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts; or preferred isomers can be prepared by asymmetric syntheses.
  • C 1-6 alkyl encompasses, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 1–6 , C 1–5 , C1–4, C1–3, C1–2, C2–6, C2–5, C2–4, C2–3, C3–6, C3–5, C3–4, C4–6, C4–5, and C5–6 alkyl.
  • aliphatic refers to alkyl, alkenyl, alkynyl, and carbocyclic groups.
  • heteroaliphatic refers to heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic groups.
  • alkyl refers to a radical of a straight-chain or branched saturated hydrocarbon group having from 1 to 20 carbon atoms (“C 1–20 alkyl”). In some embodiments, an alkyl group has 1 to 12 carbon atoms (“C1–12 alkyl”). In some embodiments, an alkyl group has 1 to 10 carbon atoms (“C1–10 alkyl”). In some embodiments, an alkyl group has 1 to 9 carbon atoms (“C 1–9 alkyl”).
  • an alkyl group has 1 to 8 carbon atoms (“C 1–8 alkyl”). In some embodiments, an alkyl group has 1 to 7 carbon atoms (“C 1–7 alkyl”). In some embodiments, an alkyl group has 1 to 6 carbon atoms (“C1–6 alkyl”). In some embodiments, an alkyl group has 1 to 5 carbon atoms (“C1–5 alkyl”). In some embodiments, an alkyl group has 1 to 4 carbon atoms (“C 1–4 alkyl”). In some embodiments, an alkyl group
  • 15/96 G1035.70000WO00 has 1 to 3 carbon atoms (“C 1–3 alkyl”).
  • an alkyl group has 1 to 2 carbon atoms (“C1–2 alkyl”).
  • an alkyl group has 1 carbon atom (“C1 alkyl”).
  • an alkyl group has 2 to 6 carbon atoms (“C2-6 alkyl”).
  • C 1–6 alkyl groups include methyl (C 1 ), ethyl (C 2 ), propyl (C 3 ) (e.g., n-propyl, isopropyl), butyl (C4) (e.g., n-butyl, tert-butyl, sec-butyl, isobutyl), pentyl (C5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tert-amyl), and hexyl (C6) (e.g., n-hexyl).
  • alkyl groups include n-heptyl (C 7 ), n-octyl (C 8 ), n-dodecyl (C 12 ), and the like. Unless otherwise specified, each instance of an alkyl group is independently unsubstituted (an “unsubstituted alkyl”) or substituted (a “substituted alkyl”) with one or more substituents (e.g., halogen, such as F).
  • substituents e.g., halogen, such as F
  • the alkyl group is an unsubstituted C 1–12 alkyl (such as unsubstituted C 1–6 alkyl, e.g., ⁇ CH 3 (Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, e.g., unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr)), unsubstituted butyl (Bu, e.g., unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu or s-Bu), unsubstituted isobutyl (i-Bu)).
  • unsubstituted C 1–12 alkyl such as unsubstituted C 1–6 alkyl, e.g.
  • the alkyl group is a substituted C1–12 alkyl (such as substituted C1–6 alkyl, e.g., –CH2F, –CHF2, –CF3, –CH2CH2F, –CH2CHF2, –CH2CF3, or benzyl (Bn)).
  • heteroalkyl refers to an alkyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (e.g., inserted between adjacent carbon atoms of) and/or placed at one or more terminal position(s) of the parent chain.
  • a heteroalkyl group refers to a saturated group having from 1 to 20 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–20 alkyl”). In certain embodiments, a heteroalkyl group refers to a saturated group having from 1 to 12 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–12 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 11 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC 1–11 alkyl”).
  • a heteroalkyl group is a saturated group having 1 to 10 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–10 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 9 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC 1–9 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 8 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–8 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 7 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC 1–7 alkyl”). In some embodiments, a heteroalkyl group is a
  • a heteroalkyl group is a saturated group having 1 to 5 carbon atoms and 1 or 2 heteroatoms within the parent chain (“heteroC1–5 alkyl”).
  • a heteroalkyl group is a saturated group having 1 to 4 carbon atoms and 1or 2 heteroatoms within the parent chain (“heteroC1–4 alkyl”).
  • a heteroalkyl group is a saturated group having 1 to 3 carbon atoms and 1 heteroatom within the parent chain (“heteroC 1–3 alkyl”).
  • a heteroalkyl group is a saturated group having 1 to 2 carbon atoms and 1 heteroatom within the parent chain (“heteroC1–2 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 carbon atom and 1 heteroatom (“heteroC 1 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 2 to 6 carbon atoms and 1 or 2 heteroatoms within the parent chain (“heteroC2-6 alkyl”). Unless otherwise specified, each instance of a heteroalkyl group is independently unsubstituted (an “unsubstituted heteroalkyl”) or substituted (a “substituted heteroalkyl”) with one or more substituents.
  • the heteroalkyl group is an unsubstituted heteroC1–12 alkyl. In certain embodiments, the heteroalkyl group is a substituted heteroC1–12 alkyl.
  • alkenyl refers to a radical of a straight-chain or branched hydrocarbon group having from 1 to 20 carbon atoms and one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 double bonds). In some embodiments, an alkenyl group has 1 to 20 carbon atoms (“C 1-20 alkenyl”). In some embodiments, an alkenyl group has 1 to 12 carbon atoms (“C 1–12 alkenyl”).
  • an alkenyl group has 1 to 11 carbon atoms (“C 1–11 alkenyl”). In some embodiments, an alkenyl group has 1 to 10 carbon atoms (“C1–10 alkenyl”). In some embodiments, an alkenyl group has 1 to 9 carbon atoms (“C1–9 alkenyl”). In some embodiments, an alkenyl group has 1 to 8 carbon atoms (“C 1–8 alkenyl”). In some embodiments, an alkenyl group has 1 to 7 carbon atoms (“C1–7 alkenyl”). In some embodiments, an alkenyl group has 1 to 6 carbon atoms (“C1–6 alkenyl”).
  • an alkenyl group has 1 to 5 carbon atoms (“C 1–5 alkenyl”). In some embodiments, an alkenyl group has 1 to 4 carbon atoms (“C1–4 alkenyl”). In some embodiments, an alkenyl group has 1 to 3 carbon atoms (“C1–3 alkenyl”). In some embodiments, an alkenyl group has 1 to 2 carbon atoms (“C 1–2 alkenyl”). In some embodiments, an alkenyl group has 1 carbon atom (“C 1 alkenyl”). The one or more carbon- carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl).
  • C1–4 alkenyl groups include methylidenyl (C1), ethenyl (C2), 1-propenyl (C3), 2- propenyl (C 3 ), 1-butenyl (C 4 ), 2-butenyl (C 4 ), butadienyl (C 4 ), and the like.
  • C 1–6 alkenyl groups include methylidenyl (C1), ethenyl (C2), 1-propenyl (C3), 2- propenyl (C 3 ), 1-butenyl (C 4 ), 2-butenyl (C 4 ), butadienyl (C 4 ), and the like.
  • alkenyl groups include the aforementioned C 2-4 alkenyl groups as well as pentenyl (C 5 ), pentadienyl (C5), hexenyl (C6), and the like. Additional examples of alkenyl include heptenyl (C7), octenyl (C8), octatrienyl (C8), and the like. Unless otherwise specified, each instance of an alkenyl group is independently unsubstituted (an “unsubstituted alkenyl”) or substituted (a “substituted alkenyl”) with one or more substituents.
  • heteroalkenyl refers to an alkenyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (e.g., inserted between adjacent carbon atoms of) and/or placed at one or more terminal position(s) of the parent chain.
  • a heteroalkenyl group refers to a group having from 1 to 20 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–20 alkenyl”).
  • a heteroalkenyl group refers to a group having from 1 to 12 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC 1–12 alkenyl”). In certain embodiments, a heteroalkenyl group refers to a group having from 1 to 11 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–11 alkenyl”). In certain embodiments, a heteroalkenyl group refers to a group having from 1 to 10 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–10 alkenyl”).
  • a heteroalkenyl group has 1 to 9 carbon atoms at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC 1–9 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 8 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–8 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 7 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–7 alkenyl”).
  • a heteroalkenyl group has 1to 6 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC 1–6 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 5 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–5 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 4 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (“heteroC 1–4 alkenyl”). In some embodiments, a
  • heteroalkenyl group has 1 to 3 carbon atoms, at least one double bond, and 1 heteroatom within the parent chain (“heteroC1–3 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 2 carbon atoms, at least one double bond, and 1 heteroatom within the parent chain (“heteroC 1–2 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 6 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–6 alkenyl”).
  • each instance of a heteroalkenyl group is independently unsubstituted (an “unsubstituted heteroalkenyl”) or substituted (a “substituted heteroalkenyl”) with one or more substituents.
  • the heteroalkenyl group is an unsubstituted heteroC1–20 alkenyl.
  • the heteroalkenyl group is a substituted heteroC 1–20 alkenyl.
  • alkynyl refers to a radical of a straight-chain or branched hydrocarbon group having from 1 to 20 carbon atoms and one or more carbon-carbon triple bonds (e.g., 1, 2, 3, or 4 triple bonds) (“C1-20 alkynyl”). In some embodiments, an alkynyl group has 1 to 10 carbon atoms (“C 1-10 alkynyl”). In some embodiments, an alkynyl group has 1 to 9 carbon atoms (“C1-9 alkynyl”). In some embodiments, an alkynyl group has 1 to 8 carbon atoms (“C1- 8 alkynyl”).
  • an alkynyl group has 1 to 7 carbon atoms (“C1-7 alkynyl”). In some embodiments, an alkynyl group has 1 to 6 carbon atoms (“C 1-6 alkynyl”). In some embodiments, an alkynyl group has 1 to 5 carbon atoms (“C1-5 alkynyl”). In some embodiments, an alkynyl group has 1 to 4 carbon atoms (“C1-4 alkynyl”). In some embodiments, an alkynyl group has 1 to 3 carbon atoms (“C 1-3 alkynyl”). In some embodiments, an alkynyl group has 1 to 2 carbon atoms (“C 1-2 alkynyl”).
  • an alkynyl group has 1 carbon atom (“C1 alkynyl”).
  • the one or more carbon- carbon triple bonds can be internal (such as in 2-butynyl) or terminal (such as in 1-butynyl).
  • Examples of C 1-4 alkynyl groups include, without limitation, methylidynyl (C 1 ), ethynyl (C 2 ), 1-propynyl (C3), 2-propynyl (C3), 1-butynyl (C4), 2-butynyl (C4), and the like.
  • C1-6 alkenyl groups include the aforementioned C2-4 alkynyl groups as well as pentynyl (C5), hexynyl (C 6 ), and the like. Additional examples of alkynyl include heptynyl (C 7 ), octynyl (C8), and the like. Unless otherwise specified, each instance of an alkynyl group is independently unsubstituted (an “unsubstituted alkynyl”) or substituted (a “substituted alkynyl”) with one or more substituents. In certain embodiments, the alkynyl group is an unsubstituted C 1-20 alkynyl.
  • the alkynyl group is a substituted C 1-20 alkynyl.
  • heteroalkynyl refers to an alkynyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur
  • a heteroalkynyl group refers to a group having from 1 to 20 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC 1–20 alkynyl”). In certain embodiments, a heteroalkynyl group refers to a group having from 1 to 10 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–10 alkynyl”).
  • a heteroalkynyl group has 1 to 9 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–9 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 8 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC 1–8 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 7 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–7 alkynyl”).
  • a heteroalkynyl group has 1 to 6 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC 1–6 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 5 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–5 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 4 carbon atoms, at least one triple bond, and 1or 2 heteroatoms within the parent chain (“heteroC1–4 alkynyl”).
  • a heteroalkynyl group has 1 to 3 carbon atoms, at least one triple bond, and 1 heteroatom within the parent chain (“heteroC1–3 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 2 carbon atoms, at least one triple bond, and 1 heteroatom within the parent chain (“heteroC 1–2 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 6 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–6 alkynyl”).
  • each instance of a heteroalkynyl group is independently unsubstituted (an “unsubstituted heteroalkynyl”) or substituted (a “substituted heteroalkynyl”) with one or more substituents.
  • the heteroalkynyl group is an unsubstituted heteroC1–20 alkynyl.
  • the heteroalkynyl group is a substituted heteroC 1–20 alkynyl.
  • carbocyclyl refers to a radical of a non-aromatic cyclic hydrocarbon group having from 3 to 14 ring carbon atoms (“C3-14 carbocyclyl”) and zero heteroatoms in the non-aromatic ring system.
  • a carbocyclyl group has 3 to 14 ring carbon atoms (“C 3-14 carbocyclyl”).
  • a carbocyclyl group has 3 to 13 ring carbon atoms (“C3-13 carbocyclyl”).
  • a carbocyclyl group has 3 to 12 ring carbon atoms (“C3-12 carbocyclyl”).
  • a carbocyclyl group has 3 to 11 ring carbon atoms (“C 3-11 carbocyclyl”).
  • a carbocyclyl group has 3 to 10 ring carbon atoms (“C 3-10 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 8 ring carbon atoms (“C3-8 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 7 ring carbon atoms (“C3-7 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 6 ring carbon atoms (“C 3-6 carbocyclyl”). In some embodiments, a carbocyclyl group has 4 to 6 ring carbon atoms (“C4-6 carbocyclyl”).
  • a carbocyclyl group has 5 to 6 ring carbon atoms (“C5-6 carbocyclyl”). In some embodiments, a carbocyclyl group has 5 to 10 ring carbon atoms (“C 5-10 carbocyclyl”).
  • Exemplary C3-6 carbocyclyl groups include cyclopropyl (C3), cyclopropenyl (C3), cyclobutyl (C4), cyclobutenyl (C4), cyclopentyl (C5), cyclopentenyl (C5), cyclohexyl (C6), cyclohexenyl (C 6 ), cyclohexadienyl (C 6 ), and the like.
  • Exemplary C 3-8 carbocyclyl groups include the aforementioned C 3-6 carbocyclyl groups as well as cycloheptyl (C 7 ), cycloheptenyl (C 7 ), cycloheptadienyl (C7), cycloheptatrienyl (C7), cyclooctyl (C8), cyclooctenyl (C8), bicyclo[2.2.1]heptanyl (C7), bicyclo[2.2.2]octanyl (C8), and the like.
  • Exemplary C3-10 carbocyclyl groups include the aforementioned C 3-8 carbocyclyl groups as well as cyclononyl (C9), cyclononenyl (C9), cyclodecyl (C10), cyclodecenyl (C10), octahydro-1H-indenyl (C9), decahydronaphthalenyl (C10), spiro[4.5]decanyl (C10), and the like.
  • Exemplary C3-8 carbocyclyl groups include the aforementioned C 3-10 carbocyclyl groups as well as cycloundecyl (C11), spiro[5.5]undecanyl (C11), cyclododecyl (C12), cyclododecenyl (C12), cyclotridecane (C13), cyclotetradecane (C14), and the like.
  • the carbocyclyl group is either monocyclic (“monocyclic carbocyclyl”) or polycyclic (e.g., containing a fused, bridged or spiro ring system such as a bicyclic system (“bicyclic carbocyclyl”) or tricyclic system (“tricyclic carbocyclyl”)) and can be saturated or can contain one or more carbon-carbon double or triple bonds.
  • Carbocyclyl also includes ring systems wherein the carbocyclyl ring, as defined above, is fused with one or more aryl or heteroaryl groups wherein the point of attachment is on the carbocyclyl ring, and in such instances, the number of carbons continue to designate the number of carbons in the carbocyclic ring system.
  • each instance of a carbocyclyl group is independently unsubstituted (an “unsubstituted carbocyclyl”) or substituted (a “substituted carbocyclyl”) with one or more substituents.
  • the carbocyclyl group is an unsubstituted C 3-14 carbocyclyl.
  • the carbocyclyl group is a substituted C 3-14 carbocyclyl.
  • “carbocyclyl” is a monocyclic, saturated carbocyclyl group having from 3 to 14 ring carbon atoms (“C3-14 cycloalkyl”).
  • a cycloalkyl group has 3 to 10 ring carbon atoms (“C 3-10 cycloalkyl”).
  • a cycloalkyl group has 3 to 10 ring carbon atoms (“C 3-10 cycloalkyl”).
  • cycloalkyl group has 3 to 8 ring carbon atoms (“C 3-8 cycloalkyl”). In some embodiments, a cycloalkyl group has 3 to 6 ring carbon atoms (“C3-6 cycloalkyl”). In some embodiments, a cycloalkyl group has 4 to 6 ring carbon atoms (“C4-6 cycloalkyl”). In some embodiments, a cycloalkyl group has 5 to 6 ring carbon atoms (“C 5-6 cycloalkyl”). In some embodiments, a cycloalkyl group has 5 to 10 ring carbon atoms (“C5-10 cycloalkyl”).
  • C5-6 cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C5).
  • Examples of C3-6 cycloalkyl groups include the aforementioned C 5-6 cycloalkyl groups as well as cyclopropyl (C 3 ) and cyclobutyl (C4).
  • Examples of C3-8 cycloalkyl groups include the aforementioned C3-6 cycloalkyl groups as well as cycloheptyl (C7) and cyclooctyl (C8).
  • each instance of a cycloalkyl group is independently unsubstituted (an “unsubstituted cycloalkyl”) or substituted (a “substituted cycloalkyl”) with one or more substituents.
  • the cycloalkyl group is an unsubstituted C3-14 cycloalkyl.
  • the cycloalkyl group is a substituted C3-14 cycloalkyl.
  • heterocyclyl refers to a radical of a 3- to 14-membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“3–14 membered heterocyclyl”).
  • heterocyclyl groups that contain one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valency permits.
  • a heterocyclyl group can either be monocyclic (“monocyclic heterocyclyl”) or polycyclic (e.g., a fused, bridged or spiro ring system such as a bicyclic system (“bicyclic heterocyclyl”) or tricyclic system (“tricyclic heterocyclyl”)), and can be saturated or can contain one or more carbon- carbon double or triple bonds.
  • Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • Heterocyclyl also includes ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more carbocyclyl groups wherein the point of attachment is either on the carbocyclyl or heterocyclyl ring, or ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring, and in such instances, the number of ring members continue to designate the number of ring members in the heterocyclyl ring system.
  • each instance of heterocyclyl is independently unsubstituted (an “unsubstituted heterocyclyl”) or substituted (a “substituted heterocyclyl”) with one or more substituents.
  • the heterocyclyl group is an unsubstituted 3–14 membered heterocyclyl. In certain embodiments, the heterocyclyl group is
  • heterocyclyl is substituted or unsubstituted, 3- to 7-membered, monocyclic heterocyclyl, wherein 1, 2, or 3 atoms in the heterocyclic ring system are independently oxygen, nitrogen, or sulfur, as valency permits.
  • a heterocyclyl group is a 5–10 membered non-aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5–10 membered heterocyclyl”).
  • a heterocyclyl group is a 5–8 membered non-aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5–8 membered heterocyclyl”).
  • a heterocyclyl group is a 5–6 membered non-aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5–6 membered heterocyclyl”).
  • the 5–6 membered heterocyclyl has 1–3 ring heteroatoms selected from nitrogen, oxygen, and sulfur.
  • the 5–6 membered heterocyclyl has 1–2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5–6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur.
  • Exemplary 3-membered heterocyclyl groups containing 1 heteroatom include azirdinyl, oxiranyl, and thiiranyl.
  • Exemplary 4-membered heterocyclyl groups containing 1 heteroatom include azetidinyl, oxetanyl, and thietanyl.
  • Exemplary 5-membered heterocyclyl groups containing 1 heteroatom include tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5- dione.
  • Exemplary 5-membered heterocyclyl groups containing 2 heteroatoms include dioxolanyl, oxathiolanyl and dithiolanyl.
  • Exemplary 5-membered heterocyclyl groups containing 3 heteroatoms include triazolinyl, oxadiazolinyl, and thiadiazolinyl.
  • Exemplary 6- membered heterocyclyl groups containing 1 heteroatom include piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl.
  • Exemplary 6-membered heterocyclyl groups containing 2 heteroatoms include piperazinyl, morpholinyl, dithianyl, and dioxanyl.
  • Exemplary 6-membered heterocyclyl groups containing 3 heteroatoms include triazinyl.
  • Exemplary 7-membered heterocyclyl groups containing 1 heteroatom include azepanyl, oxepanyl and thiepanyl.
  • Exemplary 8-membered heterocyclyl groups containing 1 heteroatom include azocanyl, oxecanyl and thiocanyl.
  • Exemplary bicyclic heterocyclyl groups include indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, tetra- hydrobenzothienyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolinyl,
  • aryl refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 ⁇ electrons shared in a cyclic array) having 6–14 ring carbon atoms and zero heteroatoms provided in the aromatic ring system (“C6-14 aryl”).
  • aromatic ring system e.g., having 6, 10, or 14 ⁇ electrons shared in a cyclic array
  • an aryl group has 6 ring carbon atoms (“C6 aryl”; e.g., phenyl).
  • an aryl group has 10 ring carbon atoms (“C 10 aryl”; e.g., naphthyl such as 1–naphthyl and 2-naphthyl).
  • an aryl group has 14 ring carbon atoms (“C14 aryl”; e.g., anthracyl).
  • Aryl also includes ring systems wherein the aryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the radical or point of attachment is on the aryl ring, and in such instances, the number of carbon atoms continue to designate the number of carbon atoms in the aryl ring system.
  • each instance of an aryl group is independently unsubstituted (an “unsubstituted aryl”) or substituted (a “substituted aryl”) with one or more substituents.
  • the aryl group is an unsubstituted C6- 14 aryl.
  • the aryl group is a substituted C6-14 aryl.
  • heteroaryl refers to a radical of a 5-14 membered monocyclic or polycyclic (e.g., bicyclic, tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 ⁇ electrons shared in a cyclic array) having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-14 membered heteroaryl”).
  • the point of attachment can be a carbon or nitrogen atom, as valency permits.
  • Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • Heteroaryl includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the point of attachment is on the heteroaryl ring, and in such instances, the number of ring members continue to designate the number of ring members in the heteroaryl ring system.
  • Heteroaryl also includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more aryl groups wherein the point of attachment is either on the aryl or heteroaryl ring, and in such instances, the number of ring members designates the number of ring members in the fused polycyclic (aryl/heteroaryl) ring system.
  • Polycyclic heteroaryl groups wherein one ring does not contain a heteroatom e.g., indolyl, quinolinyl, carbazolyl, and the like
  • the point of attachment can be on either ring, e.g., either the ring bearing a heteroatom (e.g., 2-indolyl) or the ring that does not contain a heteroatom (e.g., 5-indolyl).
  • the heteroaryl is substituted or unsubstituted, 5- or 6-membered, monocyclic heteroaryl, wherein 1, 2, 3, or 4 atoms in the heteroaryl ring system are independently oxygen, nitrogen, or sulfur.
  • the heteroaryl is substituted or unsubstituted, 9- or 10-membered, bicyclic heteroaryl, wherein 1, 2, 3, or 4 atoms in the heteroaryl ring system are independently oxygen, nitrogen, or sulfur.
  • a heteroaryl group is a 5-10 membered aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-10 membered heteroaryl”).
  • a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-8 membered heteroaryl”).
  • a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-6 membered heteroaryl”).
  • the 5- 6 membered heteroaryl has 1–3 ring heteroatoms selected from nitrogen, oxygen, and sulfur.
  • Exemplary 5-membered heteroaryl groups containing 1 heteroatom include pyrrolyl, furanyl, and thiophenyl.
  • Exemplary 5-membered heteroaryl groups containing 2 heteroatoms include imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl.
  • Exemplary 5- membered heteroaryl groups containing 3 heteroatoms include triazolyl, oxadiazolyl, and
  • Exemplary 5-membered heteroaryl groups containing 4 heteroatoms include tetrazolyl.
  • Exemplary 6-membered heteroaryl groups containing 1 heteroatom include pyridinyl.
  • Exemplary 6-membered heteroaryl groups containing 2 heteroatoms include pyridazinyl, pyrimidinyl, and pyrazinyl.
  • Exemplary 6-membered heteroaryl groups containing 3 or 4 heteroatoms include triazinyl and tetrazinyl, respectively.
  • Exemplary 7- membered heteroaryl groups containing 1 heteroatom include azepinyl, oxepinyl, and thiepinyl.
  • Exemplary 5,6-bicyclic heteroaryl groups include indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzoisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzthiazolyl, benzisothiazolyl, benzthiadiazolyl, indolizinyl, and purinyl.
  • Exemplary 6,6-bicyclic heteroaryl groups include naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl.
  • Exemplary tricyclic heteroaryl groups include phenanthridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenothiazinyl, phenoxazinyl, and phenazinyl.
  • the term “unsaturated bond” refers to a double or triple bond.
  • the term “unsaturated” or “partially unsaturated” refers to a moiety that includes at least one double or triple bond. [0065] The term “saturated” or “fully saturated” refers to a moiety that does not contain a double or triple bond, e.g., the moiety only contains single bonds.
  • acyl groups include aldehydes ( ⁇ CHO), carboxylic acids ( ⁇ CO 2 H), ketones, acyl halides, esters, amides, imines, carbonates, carbamates, and ureas.
  • Acyl substituents include, but are not limited to, any of the substituents described herein, that result in the formation of a stable moiety (e.g., aliphatic, alkyl, alkenyl, alkynyl, heteroaliphatic, heterocyclic, aryl, heteroaryl, acyl, oxo, imino, thiooxo, cyano, isocyano, amino, azido, nitro, hydroxyl, thiol, halo, aliphaticamino, heteroaliphaticamino, alkylamino, heteroalkylamino, arylamino, heteroarylamino, alkylaryl, arylalkyl, aliphaticoxy, heteroaliphaticoxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphaticthioxy, heteroaliphaticthioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy, acy
  • a “counterion” is a charged group associated with an oppositely charged group in order to maintain electronic neutrality.
  • the term “salt” refers to any and all salts, and encompasses pharmaceutically acceptable salts. Salts include ionic compounds that result from the neutralization reaction of an acid and a base. A salt is composed of one or more cations (positively charged ions) and one or more anions (negative ions) so that the salt is electrically neutral (without a net charge). Salts of the compounds of the present disclosure include those derived from inorganic and organic acids and bases.
  • acid addition salts are salts of an amino group formed with inorganic acids, such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, and perchloric acid, or with organic acids, such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, or malonic acid or by using other methods known in the art such as ion exchange.
  • inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, and perchloric acid
  • organic acids such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, or malonic acid or by using other methods known in the art such as ion exchange.
  • salts include adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2–hydroxy–ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2– naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate,
  • Salts derived from appropriate bases include alkali metal, alkaline earth metal, ammonium and N + (C1–4 alkyl)4 salts.
  • Representative alkali or alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, and the like. Further salts include ammonium, quaternary ammonium, and amine cations formed using counterions such as
  • thermal treatment refers to any method capable of generating heat to induce a chemical reaction or physical process; such methods include but are not limited to, supplying heat using hot-air convection furnaces, magnetic induction, microwave radiation, infrared radiation, near-infrared radiation, optionally combined with near-infrared dyes such as but not limited to, cyanines, porphyrine dyes, squaraine dyes, phtalocyanines, squarylium salts, diimonium salts, and dithiolene complexes.
  • additive manufacturing refers to any process involving vat photopolymerization, material jetting, binder jetting, powder bed fusion, material extrusion, directed energy deposition, sheet lamination, extrusion, and/or layer casting.
  • Vat photopolymerization techniques include stereolithography (SLA), Digital Light Processing (DLP), and Continuous Liquid Interface Production (CLIP).
  • SLA stereolithography
  • DLP Digital Light Processing
  • CLIP Continuous Liquid Interface Production
  • Stepolithography or “SLA” refers to a form of 3D printing technology used for creating models, prototypes, patterns, and production of parts in a layer-by-layer fashion using photopolymerization, a process by which light causes chains of molecules to link, forming polymers.
  • DLP Digital Light Processing
  • 3D printing and stereolithography a process that takes a design created in a 3D modeling software and uses DLP technology to print a 3D object.
  • DLP is a display device based on optical micro-electro-mechanical technology that uses a digital micromirror device. DLP may use a light source in printers to cure resins into solid 3D objects.
  • At least one instance refers to 1, 2, 3, 4, or more instances, but also encompasses a range, e.g., for example, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 4, from 2 to 3, or from 3 to 4 instances, inclusive.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation to form a solid layer of a precursor polymer, the radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; and (b) imidizing the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation to form a solid layer of a precursor polymer, the radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 100 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and (b) imidizing at least a section of the solid layer of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation to form a layer of a precursor polymer, the radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules;
  • the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer;
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 100 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and at the end of the irradiation, the reaction mixture has a percent conversion of at least 40%; and (b) imidizing at least a section of the layer of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules; at the start of the irradiation, a percent conversion of the reaction mixture is less than 10%; the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer; the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 100 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and at the end of the irradiation, the reaction mixture comprises liquid in an amount of less than 20%; (b) imidizing at least a portion of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation comprising actinic radiation, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules;
  • the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer;
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm and less than or equal to 2500 nm and/or comprises electron beam radiation; and (b) imidizing at least a portion of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising the steps of: (a) irradiating a reaction mixture with radiation comprising actinic radiation to form a precursor polymer, wherein: at the start of the irradiation, the reaction mixture comprises a plurality of monomer molecules, a near-infrared dye, and an initiator, the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer, and the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm and less than or equal to 2500 nm; and (b) imidizing at least a portion of the precursor polymer to generate the poly(meth)acrylimide.
  • a method of preparing a poly(meth)acrylimide comprising: irradiating a material comprising a precursor polymer and a near-infrared dye with radiation comprising actinic radiation to imidize at least a portion of the precursor polymer to generate the poly(meth)acrylimide, wherein: the precursor polymer comprises an optionally substituted polyacrylate, an optionally substituted polyacrylamide, an optionally substituted polyacrylonitrile, an optionally substituted polyacrylic acid, and/or any copolymer thereof, and the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm and less than or equal to 2500 nm.
  • compositions according to the disclosure for producing precursor polymers (e.g., comprising one or more of poly(meth)acrylamide, poly(meth)acrylate, poly(meth)acrylonitrile) for poly(meth)acrylimide materials can include polymerizable mixtures (e.g., reaction mixtures).
  • the reaction mixtures or polymerizable mixtures may comprise a plurality of monomer molecules.
  • the plurality of monomer molecules comprises a plurality of monomer molecules each having the same chemical structure.
  • the plurality of monomer molecules comprises a plurality of monomer molecules each having the same chemical structure such that polymerizing the plurality of monomer molecules generates a homopolymer. In some embodiments, the plurality of monomer molecules comprises a plurality of monomer molecules having one or more chemical structures. In some embodiments, the plurality of monomer molecules comprises a plurality of monomer molecules having one or more chemical structures such that polymerizing the plurality of monomer molecules generates a copolymer.
  • the polymerizable mixtures may comprise at least one, or two or more, monomers, for example (meth)acrylic acid and (meth)acrylamide, optionally at least one polymerization initiator, and optionally a blowing agent for optional production of foam materials.
  • These compositions can be polymerized to generate precursor polymers, which upon thermal treatment may result in poly(meth)acrylimide materials, via a cyclization reaction, herein termed imidization.
  • Polymers and oligomers can comprise a plurality of repeat units.
  • a polymer comprises eleven or more repeat units.
  • an oligomer comprises two to ten repeat units.
  • a polymer is a homopolymer.
  • a polymer is a copolymer. In some embodiments, a polymer comprises a weight average molecular weight of at least 1,000 g/mol. In some embodiments, a polymer comprises a molecular weight of at least 2,000 g/mol. In some embodiments, a polymer comprises a molecular weight of at least 5,000 g/mol. In some embodiments, a polymer comprises a molecular weight of at least 10,000 g/mol. In some embodiments, a polymer comprises a molecular weight of at least 20,000 g/mol. In some embodiments, a polymer comprises a molecular weight of 1,000 g/mol to 5 x 10 6 g/mol.
  • a polymer comprises a weight average molecular weight of 2,000 g/mol to 5 x 10 6 g/mol. In some embodiments, a polymer comprises a molecular weight of 5,000 g/mol to 5 x 10 6 g/mol. In some embodiments, a polymer comprises a molecular weight of
  • a polymer comprises a molecular weight of 20,000 g/mol to 5 x 10 6 g/mol.
  • the weight average molecular weight of a polymer can be determined via gel permeation chromatography.
  • the formulation “poly(meth)acrylimide” as used herein describes both polymethacrylimides and polyacrylimides.
  • the formulation “(meth)acrylimide” as used herein describes both methacrylimides and acrylimides.
  • a poly(meth)acrylimide comprises a polymethacrylimide and/or a polyacrylimide.
  • a poly(meth)acrylimide is a polymethacrylimide. In some embodiments a poly(meth)acrylimide is a polyacrylimide. In some embodiments, the poly(meth)acrylimide is optionally substituted.
  • the poly(meth)acrylimide materials after thermal imidization may contain the repeat units according to formula (I): wherein: R1 and R2 are the same or different and are each a hydrogen (acrylate) or methyl group (methacrylate), R3 is hydrogen, optionally substituted acyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group.
  • R1 and R2 are the same or different and are each a hydrogen (acrylate) or methyl group (methacrylate)
  • R3 is hydrogen, optionally substituted acyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl
  • R1 and R2 are each methyl. In some embodiments, in at least one repeat unit, R 1 and R 2 are each hydrogen. In some embodiments, in at least one repeat unit, one of R1 and R2 is hydrogen and the other is methyl. In some embodiments, in at least one repeat unit, R1 is hydrogen and R2 is methyl. In some embodiments, in at least one repeat unit, R 1 is methyl and R 2 is hydrogen.
  • R3 is a hydrogen or optionally substituted alkyl, or optionally substituted aryl having up to 36 carbon atoms, or optionally substituted aliphatic, or optionally substituted heteroaliphatic, or optionally substituted aryl, or optionally substituted
  • heteroaryl (and possibly even also optionally substituted carbocyclyl and optionally substituted heterocyclyl), which may additionally contain oxygen, nitrogen, sulphur and/or phosphorous atoms in the form of typical organic functionalities, such as for example, an ether, alcohol, acid, ester, amide, imide, phosphonic acid, phosphonic ester, phosphoric acid, phosphoric ester, phosphinic acid, phosphinic ester, sulphonic acid, sulphonic ester, sulphinic acid and/or sulphinic ester function, silicon, aluminium and boron atoms and/or halogens, such as fluorine, chlorine, bromine and/or iodine.
  • typical organic functionalities such as for example, an ether, alcohol, acid, ester, amide, imide, phosphonic acid, phosphonic ester, phosphoric acid, phosphoric ester, phosphinic acid, phosphinic ester, sulphonic
  • R3 is hydrogen, optionally substituted alkyl, or a nitrogen protecting group. In some embodiments, in at least one repeat unit, R 3 is hydrogen or a nitrogen protecting group. In some embodiments, in at least one repeat unit, R 3 is hydrogen. In some embodiments, in at least one repeat unit, R 3 is a nitrogen protecting group. [0090] In some embodiments, in at least one repeat unit, R3 is optionally substituted acyl. [0091] In some embodiments, in at least one repeat unit, R 3 is hydrogen or optionally substituted alkyl. In some embodiments, in at least one repeat unit, R3 is hydrogen or optionally substituted C1-C36 alkyl.
  • R3 is hydrogen or optionally substituted C 1 -C 20 alkyl. In some embodiments, in at least one repeat unit, R3 is hydrogen or optionally substituted C1-C8 alkyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted alkyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C1-C36 alkyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C20 alkyl.
  • R3 is optionally substituted C 1 -C 8 alkyl.
  • the following may be mentioned as examples of R3, without being restricted to thereto: methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, hexyl, ethylhexyl, octyl, dodecyl, octadecyl.
  • R3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, or t-butyl optionally substituted with hydroxy or alkoxy.
  • R3 is methyl, ethyl, n- propyl, isopropyl, n-butyl, secbutyl, isobutyl, or t-butyl. In some embodiments, R3 is hydrogen, methyl, 2-hydroxyethyl, or isopropyl. In some embodiments, R 3 is methyl. In some embodiments, R 3 is 2-hydroxyethyl. In some embodiments, R 3 is isopropyl. [0092] In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C36 alkenyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C20 alkenyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C 1 -C 8
  • R 3 is optionally substituted C 1 -C 36 alkynyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C20 alkynyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C8 alkynyl. [0093] In some embodiments, in at least one repeat unit, R3 is optionally substituted heteroalkyl, optionally substituted heteroalkenyl, or optionally substituted heteroalkynyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted heteroalkyl.
  • R3 is optionally substituted C1-C36 heteroalkyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C20 heteroalkyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C 1 - C 8 heteroalkyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C1-C36 heteroalkenyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C20 heteroalkenyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C 1 -C 8 heteroalkenyl.
  • R3 is optionally substituted C1-C36 heteroalkynyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted C1-C20 heteroalkynyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C 1 -C 8 heteroalkynyl. [0094] In some embodiments, in at least one repeat unit, R3 is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted carbocyclyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C 3 -C 8 carbocyclyl.
  • R3 is optionally substituted C5-C6 carbocyclyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted heterocyclyl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted 3- to 8-membered heterocyclyl. [0095] In some embodiments, in at least one repeat unit, R3 is optionally substituted aryl or optionally substituted heteroaryl. In some embodiments, in at least one repeat unit, R3 is optionally substituted aryl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted C6-C10 aryl.
  • R3 is optionally substituted phenyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted heteroaryl. In some embodiments, in at least one repeat unit, R 3 is optionally substituted 5- to 10-membered heterocyclyl. In some embodiments, in at least one repeat unit, R3 is optionally substituted 5- to 6-membered heterocyclyl. [0096] In some embodiments, a monomer or co-monomer is a molecule capable of homopolymerizing and/or copolymerizing by radical addition and being incorporated into a
  • a monomer or co-monomer provided herein is optionally substituted.
  • Such comonomers may be, but not restricted to, acrylic acid or methacrylic acid, esters of acrylic or methacrylic acid, N-substituted (meth)acrylamides, vinyl ethers, styrenes, acrylamides, maleimides, vinyl esters, vinylpyrrolidone, vinylic cyclic structures such as, but not limited to, vinyl acetal, vinyl ethers, spiro-ortho-carbonates, spiro- ortho-esters, vinyl sulfones, allilyc sulfides, vinyl oxirane, ketene acetals, and thionolactones.
  • an acrylate monomer comprises a vinylic acid or ester moiety. In some embodiments, an acrylate monomer is optionally substituted. In some embodiments, an acrylate monomer is an unsubstituted acrylate monomer. In some embodiments, an acrylate monomer is a substituted acrylate monomer. In some embodiments, an acrylate monomer is an acrylic ester monomer optionally substituted at the ester position, a methacrylic ester monomer optionally substituted at the ester position, an acrylic acid monomer, a methacrylic acid monomer, a salt of an acrylic acid monomer, or a salt of a methacrylic acid monomer.
  • (meth)acrylate comprehends both acrylate monomers that are not substituted at the vinylic position to form methacrylates and methacrylate monomers.
  • (meth)acrylates can include unsubstituted acrylates, acrylates substituted at the vinylic position to form methacrylates, acrylates that are substituted at the ester position but not substituted at the vinylic position, and acrylates that are substituted at both the vinylic position and ester position.
  • acrylate monomers include, but are not limited to, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2- hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, 2- hydroxyethyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isobornyl methacrylate, isobornyl acrylate, glycidyl acrylate, glycidyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyl metahcrylate.
  • an acrylamide monomer comprises a vinylic amide moiety.
  • an acrylamide monomer is optionally substituted.
  • an acrylamide monomer is an unsubstituted acrylamide monomer.
  • an acrylamide monomer is a substituted acrylamide monomer.
  • an acrylamide monomer is an acrylamide monomer optionally substituted at the vinylic position or an acrylamide monomer optionally substituted at the amide nitrogen atom.
  • (meth)acrylamide comprehends both acrylamide monomers that are not substituted at the vinylic position to form methacrylamides and methacrylamide monomers.
  • (meth)acrylamides can include unsubstituted acrylamides, acrylamides substituted at the vinylic position to form methacrylamides, acrylamides that are substituted at the amide nitrogen atom but not substituted at the vinylic position, and acrylamides that are substituted at both the vinylic position and the amide nitrogen atom.
  • acrylamide monomers include, but are not limited to, acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N- diethylacrylamide, N-butylacrylamide, N-[3-(dimethylamino)propyl]acrylamide, 4- acryloylmorpholine, N-[2-(dimethylamino)ethyl]acrylamide, N-[2- (diethylamino)ethyl]acrylamide, diacetone acrylamide, N-(2-hydroxyethyl)acrylamide, N- isopropylacrylamide, N-propylacrylamide, N-(2-amino-2-oxoethyl)acrylamide, N-tert- butylacrylamide, N-(hydroxymethyl)acrylamide, and 3-acryloyl-2-oxazolidinone.
  • an acrylonitrile monomer comprises a vinylic nitrile moiety. In some embodiments, an acrylonitrile monomer is optionally substituted. In some embodiments, an acrylonitrile monomer is an unsubstituted acrylonitrile monomer. In some embodiments, an acrylonitrile monomer is a substituted acrylonitrile monomer. In some embodiments, an acrylonitrile monomer is an acrylonitrile monomer optionally substituted at the vinylic position. As used herein, the term (meth)acrylonitrile comprehends both acrylonitrile monomers and methacrylonitrile monomers.
  • Methods for forming the structural moieties displayed in formula (I) in the polymer may involve neighboring repeat units able to undergo a cyclization reaction.
  • Such repeat units may be introduced in the polymer by polymerizing monomers according to one or more of formulae (A), (B), or (C): wherein: each instance of R 1 is independently a hydrogen or methyl group, R3 and R4 are each independently hydrogen, optionally substituted acyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted
  • At least one instance of R1 is methyl. In some embodiments, at least one instance of R1 is hydrogen. In some embodiments, each instance of R1 is methyl. In some embodiments, each instance of R 1 is hydrogen.
  • R3 and R4 are the same or different and are each a hydrogen or optionally substituted substituted alkyl or optionally substituted aryl having up to 36 carbon atoms, which may additionally contain oxygen, nitrogen, sulphur and/or phosphorous atoms in the form of typical organic functionalities, such as for example, an ether, alcohol, acid, ester, amide, imide, phosphonic acid, phosphonic ester, phosphoric acid, phosphoric ester, phosphinic acid, phosphinic ester, sulphonic acid, sulphonic ester, sulphinic acid and/or sulphinic ester function, silicon, aluminium and/or boron atoms or halogens, such as fluorine, chlorine, bromine and/or iodine.
  • typical organic functionalities such as for example, an ether, alcohol, acid, ester, amide, imide, phosphonic acid, phosphonic ester, phosphoric acid, phosphoric ester, phos
  • R3 The following may be mentioned as examples of R3, without being restricted to thereto: methyl, ethyl, propyl, 2-propyl, butyl, tert-butyl, hexyl, ethylhexyl, octyl, dodecyl, octadecyl.
  • R3 is hydrogen, optionally substituted acyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or a nitrogen protecting group when attached to a nitrogen atom.
  • R 3 is hydrogen, optionally substituted alkyl, or a nitrogen protecting group. In some embodiments, R3 is hydrogen or a nitrogen protecting group. In some embodiments, R3 is hydrogen.
  • R3 is a nitrogen protecting group. [00107] In some embodiments, R 3 is optionally substituted acyl. [00108] In some embodiments, R3 is hydrogen or optionally substituted alkyl. In some embodiments, R3 is hydrogen or optionally substituted C1-C36 alkyl. In some embodiments, R 3 is hydrogen or optionally substituted C 1 -C 20 alkyl. In some embodiments, R 3 is hydrogen or optionally substituted C 1 -C 8 alkyl. In some embodiments, R 3 is optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In some embodiments, R3 is optionally substituted alkyl. In some embodiments, R3 is optionally substituted C1-C36 alkyl. In some embodiments, R 3 is optionally substituted C 1 -C 20 alkyl. In some embodiments,
  • R 3 is optionally substituted C 1 -C 8 alkyl.
  • R 3 is methyl, ethyl, propyl, 2- propyl, butyl, tert-butyl, hexyl, ethylhexyl, octyl, dodecyl, octadecyl.
  • R3 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, or t-butyl optionally substituted with hydroxy or alkoxy.
  • R 3 is methyl, ethyl, n- propyl, isopropyl, n-butyl, secbutyl, isobutyl, or t-butyl.
  • R3 is hydrogen, methyl, 2-hydroxyethyl, or isopropyl.
  • R3 is methyl.
  • R 3 is 2-hydroxyethyl.
  • R 3 is isopropyl.
  • R3 is optionally substituted C1-C36 alkenyl. In some embodiments, R3 is optionally substituted C1-C20 alkenyl.
  • R3 is optionally substituted C 1 -C 8 alkenyl. In some embodiments, R 3 is optionally substituted C 1 - C 36 alkynyl. In some embodiments, R 3 is optionally substituted C 1 -C 20 alkynyl. In some embodiments, R3 is optionally substituted C1-C8 alkynyl. [00110] In some embodiments, R3 is optionally substituted heteroalkyl, optionally substituted heteroalkenyl, or optionally substituted heteroalkynyl. In some embodiments, R 3 is optionally substituted heteroalkyl. In some embodiments, R3 is optionally substituted C1-C36 heteroalkyl.
  • R3 is optionally substituted C1-C20 heteroalkyl. In some embodiments, R 3 is optionally substituted C 1 -C 8 heteroalkyl. In some embodiments, R 3 is optionally substituted C1-C36 heteroalkenyl. In some embodiments, R3 is optionally substituted C1-C20 heteroalkenyl. In some embodiments, R3 is optionally substituted C1-C8 heteroalkenyl. In some embodiments, R 3 is optionally substituted C 1 -C 36 heteroalkynyl. In some embodiments, R 3 is optionally substituted C 1 -C 20 heteroalkynyl. In some embodiments, R 3 is optionally substituted C1-C8 heteroalkynyl.
  • R3 is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In some embodiments, R 3 is optionally substituted carbocyclyl. In some embodiments, R3 is optionally substituted C3-C8 carbocyclyl. In some embodiments, R3 is optionally substituted C5-C6 carbocyclyl. In some embodiments, R3 is optionally substituted heterocyclyl. In some embodiments, R 3 is optionally substituted 3- to 8-membered heterocyclyl. [00112] In some embodiments, R3 is optionally substituted aryl or optionally substituted heteroaryl. In some embodiments, R 3 is optionally substituted aryl.
  • R 3 is optionally substituted C 6 -C 10 aryl. In some embodiments, R 3 is optionally substituted phenyl. In some embodiments, R3 is optionally substituted heteroaryl. In some embodiments, R3 is optionally substituted 5- to 10-membered heterocyclyl. In some embodiments, R3 is optionally substituted 5- to 6-membered heterocyclyl.
  • R 4 is hydrogen, optionally substituted acyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or an oxygen protecting group when attached to an oxygen atom.
  • R 4 is hydrogen, optionally substituted alkyl, or an oxygen protecting group. In some embodiments, R4 is hydrogen or an oxygen protecting group. In some embodiments, R4 is hydrogen.
  • R4 is an oxygen protecting group. [00115] In some embodiments, R 4 is optionally substituted acyl. [00116] In some embodiments, R 4 is hydrogen or optionally substituted alkyl. In some embodiments, R4 is hydrogen or optionally substituted C1-C36 alkyl. In some embodiments, R4 is hydrogen or optionally substituted C1-C20 alkyl. In some embodiments, R4 is hydrogen or optionally substituted C 1 -C 8 alkyl. In some embodiments, R 4 is optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In some embodiments, R4 is optionally substituted alkyl.
  • R4 is optionally substituted C1-C36 alkyl. In some embodiments, R 4 is optionally substituted C 1 -C 20 alkyl. In some embodiments, R4 is optionally substituted C1-C8 alkyl. In some embodiments, R4 is methyl, ethyl, propyl, 2- propyl, butyl, tert-butyl, hexyl, ethylhexyl, octyl, dodecyl, octadecyl.
  • R 4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, or t-butyl optionally substituted with hydroxy or alkoxy.
  • R 4 is methyl, ethyl, n- propyl, isopropyl, n-butyl, secbutyl, isobutyl, or t-butyl.
  • R4 is hydrogen, methyl, 2-hydroxyethyl, or isopropyl.
  • R4 is methyl.
  • R 4 is 2-hydroxyethyl.
  • R 4 is isopropyl.
  • R4 is optionally substituted C1-C36 alkenyl. In some embodiments, R4 is optionally substituted C1-C20 alkenyl. In some embodiments, R4 is optionally substituted C 1 -C 8 alkenyl. In some embodiments, R 4 is optionally substituted C 1 - C36 alkynyl. In some embodiments, R4 is optionally substituted C1-C20 alkynyl. In some embodiments, R4 is optionally substituted C1-C8 alkynyl. [00118] In some embodiments, R 4 is optionally substituted heteroalkyl, optionally substituted heteroalkenyl, or optionally substituted heteroalkynyl.
  • R 4 is optionally substituted heteroalkyl. In some embodiments, R4 is optionally substituted C1-C36 heteroalkyl. In some embodiments, R4 is optionally substituted C1-C20 heteroalkyl. In some embodiments, R 4 is optionally substituted C 1 -C 8 heteroalkyl. In some embodiments, R 4 is optionally
  • R 4 is optionally substituted C 1 -C 20 heteroalkenyl. In some embodiments, R4 is optionally substituted C1-C8 heteroalkenyl. In some embodiments, R4 is optionally substituted C1-C36 heteroalkynyl. In some embodiments, R 4 is optionally substituted C 1 -C 20 heteroalkynyl. In some embodiments, R 4 is optionally substituted C1-C8 heteroalkynyl. [00119] In some embodiments, R4 is optionally substituted carbocyclyl or optionally substituted heterocyclyl. In some embodiments, R 4 is optionally substituted carbocyclyl.
  • R4 is optionally substituted C3-C8 carbocyclyl. In some embodiments, R4 is optionally substituted C5-C6 carbocyclyl. In some embodiments, R4 is optionally substituted heterocyclyl. In some embodiments, R 4 is optionally substituted 3- to 8-membered heterocyclyl. [00120] In some embodiments, R4 is optionally substituted aryl or optionally substituted heteroaryl. In some embodiments, R4 is optionally substituted aryl. In some embodiments, R4 is optionally substituted C 6 -C 10 aryl. In some embodiments, R 4 is optionally substituted phenyl. In some embodiments, R4 is optionally substituted heteroaryl.
  • R4 is optionally substituted 5- to 10-membered heterocyclyl. In some embodiments, R4 is optionally substituted 5- to 6-membered heterocyclyl.
  • Monomer A represents (meth)acrylic acid and/or (meth)acrylate esters
  • monomer B represents (meth)acrylamides
  • monomer C represents (meth)acrylonitriles. Monomers may be used in variable molar ratios. In some embodiments, to facilitate imidization, monomer A is combined with monomer B or C, or a combination of both B and C. In some embodiments, monomer B is used alone, or in combination with monomer A. In some embodiments, monomer C is combined with monomer A.
  • the first step in producing resins is the production of monomer mixtures containing a (meth)acrylic acid or (meth)acrylic ester, or combination thereof, with a (meth)acrylamide or (meth)acrylonitrile, or combination thereof.
  • the plurality of monomer molecules comprises an optionally substituted acrylate monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted acrylonitrile monomer.
  • the plurality of monomer molecules comprises an optionally substituted acrylic ester monomer, an optionally substituted methacrylic ester monomer, an acrylic acid monomer, a methacrylic acid monomer, an optionally substituted acrylamide monomer, an optionally substituted methacrylamide monomer, an acrylonitrile monomer, and/or a methacrylonitrile monomer. In some embodiments, the plurality of monomer molecules comprises an optionally substituted acrylic ester monomer, an optionally substituted methacrylic ester monomer, an acrylic acid monomer, a methacrylic acid monomer, an optionally substituted acrylamide monomer, an optionally substituted methacrylamide monomer, an acrylonitrile monomer, and/or a methacrylonitrile monomer. In some embodiments, the plurality of monomer molecules comprises an optionally substituted
  • the plurality of monomer molecules comprises acrylonitrile and acrylic acid. In some embodiments, the plurality of monomer molecules comprises methacrylonitrile and acrylic acid. In some embodiments, the plurality of monomer molecules comprises acrylonitrile and methacrylic acid. In some embodiments, the plurality of monomer molecules comprises methacrylonitrile and methacrylic acid. In some embodiments, the plurality of monomer molecules comprises an optionally substituted acrylonitrile and an optionally substituted acrylic ester. In some embodiments, the plurality of monomer molecules comprises acrylonitrile and an optionally substituted acrylic ester.
  • the plurality of monomer molecules comprises methacrylonitrile and an optionally substituted acrylic ester.
  • the plurality of monomer molecules comprises an optionally substituted acrylamide monomer, an optionally substituted acrylic ester monomer, and/or an optionally substituted acrylic acid monomer.
  • the plurality of monomer molecules comprises an optionally substituted acrylic ester monomer, an optionally substituted methacrylic ester monomer, an acrylic acid monomer, a methacrylic acid monomer, an optionally substituted acrylamide monomer, and/or an optionally substituted methacrylamide monomer.
  • the plurality of monomer molecules comprises an optionally substituted acrylate monomer and an optionally substituted acrylamide monomer.
  • the plurality of monomer molecules comprises an optionally substituted acrylamide and an optionally substituted acrylic ester.
  • the plurality of monomer molecules comprises an optionally substituted acrylamide and an optionally substituted acrylic acid.
  • the plurality of monomer molecules comprises methacrylic acid and methacrylamide.
  • the molar ratio of an optionally substituted acrylate monomer to an optionally substituted acrylamide monomer is between 10:90 and 90:10. In some embodiments, the molar ratio of an optionally substituted acrylate monomer to an optionally substituted acrylamide monomer is between 20:80 and 80:20. In some embodiments, the molar ratio of an optionally substituted acrylate monomer to an optionally substituted acrylamide monomer is between 40:60 and 60:40. In some embodiments, the molar ratio of
  • an optionally substituted acrylate monomer to an optionally substituted acrylamide monomer is between 45:55 and 55:45.
  • the molar ratio of an optionally substituted acrylate monomer to an optionally substituted acrylamide monomer is between 49:51 and 51:49.
  • the molar ratio of (meth)acrylic acid monomer to (meth)acrylamide as main constituents is between 20:80 and 80:20.
  • the molar ratio of (meth)acrylic acid monomer to (meth)acrylamide as main constituents is between 40:60 and 60:40.
  • the molar ratio of (meth)acrylic acid monomer to (meth)acrylamide as main constituents is between 51:49 to 49:51. In one embodiment, the molar ratio of (meth)acrylic ester monomer to (meth)acrylamide as main constituents is between 20:80 and 80:20. In some embodiments, the molar ratio of (meth)acrylic ester monomer to (meth)acrylamide as main constituents is between 40:60 and 60:40. In some embodiments, the molar ratio of (meth)acrylic ester monomer to (meth)acrylamide as main constituents is between 51:49 to 49:51.
  • Additional suitable comonomers may be used be used such as esters of acrylic or methacrylic acid, N-substituted (meth)acrylamides vinyl ethers, styrenes, acrylamides, maleimides, vinyl esters, vinylpyrrolidone, vinylic cyclic structures such as but not limited to vinyl acetal, vinyl ethers, spiro-ortho-carbonates, spiro-ortho-esters, vinyl sulfones, allylic sulfides, vinyl oxirane, ketene acetals, thionolactones. These comonomers are intended as examples and are not limiting.
  • the proportion of comonomers does not amount to more than 50% by weight of the two main constituents. In some embodiments, the proportion of comonomers does not amount to more than 40% by weight of the two main constituents. In some embodiments, the proportion of comonomers does not amount to more than 35% by weight of the two main constituents. In some embodiments, the proportion of comonomers does not amount to more than 20% by weight of the two main constituents. In some embodiments, the proportion of comonomers does not amount to more than 10% by weight of the two main constituents. In some embodiments, the additional comonomers comprise less than 50 mol% of the reaction mixture.
  • the additional comonomers comprise less than 35 mol% of the reaction mixture. In some embodiments, the additional comonomers comprise less than 20 mol% of the reaction mixture. In some embodiments, the additional comonomers comprise less than 10 mol% of the reaction mixture. In some embodiments, the additional comonomers comprise less than 5 mol% of the reaction mixture. In some embodiments, the additional comonomers comprise 1 mol% to 50 mol% of the reaction mixture. In some embodiments, the additional comonomers comprise 1 mol% to 35 mol% of the reaction mixture. In some embodiments, the additional comonomers
  • 43/96 G1035.70000WO00 comprise 1 mol% to 20 mol% of the reaction mixture.
  • the additional comonomers comprise 1 mol% to 10 mol% of the reaction mixture.
  • the additional comonomers comprise 1 mol% to 5 mol% of the reaction mixture.
  • the additional comonomers comprise 5 mol% to 50 mol% of the reaction mixture.
  • the additional comonomers comprise 5 mol% to 35 mol% of the reaction mixture.
  • the additional comonomers comprise 5 mol% to 20 mol% of the reaction mixture.
  • the additional comonomers comprise 5 mol% to 10 mol% of the reaction mixture.
  • the reaction mixture further comprises one or more cross- linkers.
  • a cross-linker links one polymer chain to at least one other polymer chain, e.g., via one or more covalent bonds.
  • a cross-linker comprises two or more functional groups that may react to link one polymer chain to at least one other polymer chain.
  • a cross-linker is a comonomer comprising two or more polymerizable moieties.
  • a cross-linker comprises two or more vinylic moieties.
  • a cross-linker comprises two or more acylate, acrylamide, and/or acrylonitrile moieties.
  • cross-linker “crosslinking monomer,” “crosslinking molecule,” and “crosslinking agent” are used interchangeably herein.
  • Small amounts of crosslinking unsaturated monomers can be used, having at least two 2 polymerizable functionalities in the molecule.
  • the cross-linker comprises at least two polymerizable functionalities in the molecule (e.g., at least two vinylic groups).
  • the cross-liner comprises two, three, or four polymerizable functionalities in the molecule.
  • the cross-linker comprises the same polymerizable functionalities as the plurality of monomer molecules.
  • the cross-linker comprises two or more polymerizable functionalities selected from an optionally substituted acrylate, an optionally substituted acrylamide, and/or an optionally substituted acrylonitrile. In some embodiments, the cross-linker comprises two or more polymerizable functionalities selected from an optionally substituted acrylate or an optionally substituted acrylamide.
  • cross-linkers include, but are not limited to, butanediol di(meth)acrylate, triallylisocyanurate, triacrylate isocyanurates (IGM Photomer 4356), pentaerythritol triacrylate, ethylene glycol acrylate, ethylene glycol methacrylate, triethylene glycol diacrylate, and triethylene glycol dimethacrylate.
  • Unsaturated polymerizable oligomers or polymers having at least two 2 polymerizable functionalities may be used, for example but not limited to aliphatic urethane diacrylate or dimethacrylate oligomer (IGM
  • the one or more cross-linkers comprise ethylene glycol dimethacrylate, CN9009, or Photomer 4356.
  • the one or more cross-linkers comprise N- methacryloylmethacrylamide or N-acryloylacrylamide.
  • the amounts of crosslinking molecules used is 0 to 20% by weight. In some embodiments, the amounts of crosslinking molecules used is 0 to 10% by weight. In some embodiments, the amounts of crosslinking molecules used is 0.05% to 5.0% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0% to 50% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0% to 40% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0% to 30% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0% to 20% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0% to 15% by weight.
  • the reaction mixture comprises cross-linker in an amount of 0% to 10% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0% to 5% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0.5% to 50% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0.5% to 40% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0.5% to 30% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0.5% to 20% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0.5% to 15% by weight.
  • the reaction mixture comprises cross-linker in an amount of 0.5% to 10% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 0.5% to 5% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 1% to 50% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 1% to 40% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 1% to 30% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 1% to 20% by weight. In some embodiments, the reaction mixture comprises cross-linker in an amount of 1% to 15% by weight. In some embodiments, the reaction mixture comprises
  • the reaction mixture comprises cross-linker in an amount of 1% to 5% by weight.
  • the percent conversion is the percentage of reactant that has been converted to product. For example, in the context of polymerization, percent conversion is the percentage of monomers or co-monomers that have been converted to polymer.
  • the reaction mixture at the start of the irradiation, has a percent conversion of less than 40%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 35%.
  • the reaction mixture has a percent conversion of less than 30%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 25%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 20%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 15%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 10%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 5%.
  • the reaction mixture has a percent conversion of less than 2%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of less than 1%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of 1% to 10%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of 5% to 15%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of 10% to 20%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of 15% to 25%.
  • the reaction mixture has a percent conversion of 20% to 30%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of 25% to 35%. In some embodiments, at the start of the irradiation, the reaction mixture has a percent conversion of 30% to 40%.
  • Further additional substances which are different from the stated monomers, crosslinker, blowing agents, solvents, assisting polymers/oligomers (e.g., homogenizers) or initiators can be admixed in the formulations (e.g., dispersed therein). Suitable amounts of additives can be for instance between 0% and 20% wt.
  • Additives can include, but are not limited to, antioxidants, dyes, thickeners, lubricants, fillers, UV absorbers, plasticizers, organic phosphorous compounds, release agents, flame retardants, graphite, graphene, fumed silica, glass beads or spheres, aluminum particles, and piezo electric-responsive fillers.
  • the additive is present in an amount between 0 wt% and 50 wt%. In some embodiments, the additive is present in an amount between 0 wt% and 40 wt%. In some embodiments, the additive is present in an amount between 0 wt% and 30 wt%. In some embodiments, the additive is present in an amount between 0 wt% and 20 wt%. In some embodiments, the additive is present in an amount between 0 wt% and 15 wt%. In some embodiments, the additive is present in an amount between 0 wt% and 10 wt%.
  • the additive is present in an amount between 0 wt% and 5 wt%. In some embodiments, the additive is present in an amount between 0.5 wt% and 50 wt%. In some embodiments, the additive is present in an amount between 0.5 wt% and 40 wt%. In some embodiments, the additive is present in an amount between 0.5 wt% and 30 wt%. In some embodiments, the additive is present in an amount between 0.5 wt% and 20 wt%. In some embodiments, the additive is present in an amount between 0.5 wt% and 15 wt%. In some embodiments, the additive is present in an amount between 0.5 wt% and 10 wt%.
  • the additive is present in an amount between 0.5 wt% and 5 wt%. In some embodiments, the additive is present in an amount between 5 wt% and 10 wt%. In some embodiments, the additive is present in an amount between 10 wt% and 15 wt%. In some embodiments, the additive is present in an amount between 15 wt% and 20 wt%. In some embodiments, the additive is present in an amount between 20 wt% and 30 wt%. In some embodiments, the additive is present in an amount between 30 wt% and 40 wt%. In some embodiments, the additive is present in an amount between 40 wt% and 50 wt%.
  • the reaction mixture further comprises one or more solvents.
  • the composition may optionally contain a solvent. Some solvents may enhance the homogeneity of the mixture at ambient temperature.
  • suitable solvents include those which are capable of volatilization during subsequent processing steps and which do not negatively affect the monomer copolymerization.
  • suitable solvents include water, which is believed to not negatively affect the safety profile of the mixture.
  • the one or more solvents comprises a polar solvent.
  • the one or more solvents comprises a polar protic solvent.
  • the one or more solvents comprises a polar aprotic solvent.
  • the one or more solvents comprise water.
  • the one or more solvents comprises glycerol. In some embodiments, the one or more solvents comprises a non-polar solvent. In some embodiments, the one or more solvents comprises toluene, benzene, cyclohexane, heptane, hexane, or pentane. In some embodiments, the one or more solvents comprises toluene, cyclohexane, or heptane.
  • the one or more solvents comprise 0% to 35% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 0.1% to 35% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 1% to 35% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 5% to 35% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 1% to 20% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 5% to 20% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 1% to 5% of the reaction mixture by weight.
  • the one or more solvents comprise 5% to 10% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 8% to 20% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 8% to 15% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 8% to 12% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 10% to 20% of the reaction mixture by weight. In some embodiments, the one or more solvents comprise 20% to 35% of the reaction mixture by weight. [00136] In some embodiments, the reaction mixture further comprises one or more blowing agents. In some embodiments, the layer of the precursor polymer further comprises one or more blowing agents.
  • a blowing agent comprises a compound which is capable of producing a cellular structure via a foaming process in a variety of materials that undergo hardening or phase transition.
  • the blowing agent is a substance that forms gas during the hardening or phase transition.
  • the blowing agent causes foaming through a physical process.
  • the blowing agent is a volatile substance that forms gas when heated.
  • the blowing agent is added to a reaction mixture and/or a polymer (e.g., a precursor polymer) as an exogenous liquid or gaseous compound.
  • the one or more blowing agents is added to the reaction mixture as an exogenous liquid or gaseous compound.
  • the one or more blowing agents is added to the precursor polymer as an exogenous liquid or gaseous compound.
  • the blowing agent is an expandable bead (e.g., a microsphere encapsulating a gas).
  • the blowing agent is added to a reaction mixture and/or a polymer (e.g., a precursor polymer) as an expandable bead.
  • the one or more blowing agents is added to the reaction mixture as an expandable bead.
  • the one or more blowing agents is added to the precursor polymer as an
  • Expandable beads include, but are not limited to, acrylic shells or micro- balloons (e.g., Advancell Expandable Microspheres) and thermoplastic microspheres (e.g., Expancel® microspheres).
  • the blowing agent causes foaming through a chemical process.
  • the blowing agents causes foaming through a chemical reaction that produces a small molecule (e.g., a volatile small molecule).
  • the blowing agent is generated during imidization of a precursor polymer described herein.
  • a mixture for the copolymerisation further contains blowing agents which either decompose or vaporise at temperatures of about 120 °C to 250 °C, forming a gas phase in the process.
  • the blowing agent decomposes or vaporizes at a temperature below the imidization temperature.
  • the blowing agent decomposes or vaporizes at a temperature below 170 °C.
  • the blowing agent decomposes or vaporizes at a temperature below 160 °C.
  • the blowing agent decomposes or vaporizes at a temperature below 150 °C.
  • the blowing agent decomposes or vaporizes at a temperature below 150 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature below 140 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature below 130 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above the imidization temperature. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 130 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 140 °C.
  • the blowing agent decomposes or vaporizes at a temperature above 150 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 160 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 170 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 180 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 190 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 290 °C.
  • the blowing agent decomposes or vaporizes at a temperature above 225 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above 250 °C. In some embodiments, the blowing agent decomposes or vaporizes at a temperature above glass transition temperature (Tg) of the precursor polymer.
  • Tg glass transition temperature
  • the one or more blowing agents comprise urea, monomethylurea, N,N’-dimethylurea, formamide, monomethylformamide, formic acid, water, an alcohol, a low molecular weight hydrocarbon, a low molecular weight halohydrocarbon, an organic carboxylic acid, liquid carbon dioxide, azodicarbonamide, and/or hydrazine.
  • suitable blowing agents include, but are not limited to, the following compounds, or mixtures thereof: nitrogenous compounds, urea, monomethylurea or N,N'-dimethylurea, formamide or monomethylformamide.
  • nitrogen-free blowing agents include formic acid, water or mono hydric aliphatic alcohols particularly those of three to eight carbon atoms, for example propan-1-ol, propan-2-ol, butan-2-ol, tert- butanol and isobutanol.
  • Organic carboxylic acids may include oxalic acid, maleic acid, citric acid, itaconic acid, hydroxyisobutyric acid, malonic acid.
  • the one or more blowing agents comprise urea.
  • the blowing agent is generated during imidization of the precursor polymer.
  • the blowing agent is generated during imidization of the precursor polymer by liberation of a small molecule byproduct of imidization.
  • Blowing agents in the form of unsaturated copolymerisable monomers such as tert-butyl(meth)acrylate, sec-butyl(meth)acrylate and isopropyl(meth)acrylate may also be used.
  • the blowing agents may be used in amounts of 0% to 20% by weight based on the monomers used and the desired density of the PMI material.
  • the reaction mixture comprises blowing agent in an amount of 0% to 20% by weight relative to the plurality of monomer molecules.
  • the reaction mixture comprises blowing agent in an amount of 0% to 15% by weight relative to the plurality of monomer molecules.
  • the reaction mixture comprises blowing agent in an amount of 0% to 10% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0% to 5% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 20% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 15% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 10% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 5% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 5% by weight relative to the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 5% to 10% by weight of the plurality of monomer molecules. In
  • the reaction mixture comprises blowing agent in an amount of 10% to 15% by weight of the plurality of monomer molecules. In some embodiments, the reaction mixture comprises blowing agent in an amount of 15% to 20% by weight of the plurality of monomer molecules. [00142] In some embodiments, the reaction mixture comprises blowing agent in an amount of 0% to 80% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0% to 60% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0% to 40% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0% to 20% by volume.
  • the reaction mixture comprises blowing agent in an amount of 0.5% to 80% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 60% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 40% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 0.5% to 20% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 5% to 80% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 5% to 60% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 5% to 40% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 5% to 20% by volume.
  • the reaction mixture comprises blowing agent in an amount of 20% to 40% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 40% to 60% by volume. In some embodiments, the reaction mixture comprises blowing agent in an amount of 60% to 80% by volume.
  • the reaction mixture is homogenous (e.g., a uniform blend of its constituents, such as a uniform blend as determined by light scattering, e.g., dynamic light scattering). In some embodiments, the reaction mixture is homogenous prior to the addition of an additive. In some embodiments, the reaction mixture is homogenous prior to the addition of a filler. In some embodiments, the reaction mixture is a single phase.
  • the reaction mixture does not include a precipitate or includes precipitates in a relatively small amount (e.g., less than or equal to 5 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, less than or equal to 0.5 wt%, less than or equal to 0.2 wt%, less than or equal to 0.1 wt%, and, e.g., greater than or equal to 0 wt%).
  • a homogenizer comprises an oligomer, polymer, or copolymer which helps in
  • the monomer compositions may include oligomeric and/or polymeric resins of suitable molecular weights to assist in the formation of PMI resins and foams. These include, for example, PMMA (polymethylmethacrylate) and/or PMMI (poly-N- methylmethacrylimide). Such polymers are believed to have good incorporability.
  • the syrup phase resulting from addition of PMMA can be realized by means of high molecular weight PMMA, which may be prepared by emulsion or solution polymerization.
  • the product Degalan BT 310 produced by Röhm may serve for this purpose.
  • the amount of dissolved PMMA is between 0.005 and 0.10 gram of PMMA per gram of monomer mixture which acts as a solvent.
  • the reaction mixture further comprises an oligomer, polymer, or copolymer.
  • the reaction mixture further comprises one or more of PMMA, PMMI, Degalan BT 310, or Elvacite.
  • the reaction mixture further comprises a vinylic copolymer.
  • the reaction mixture further comprises a polyvinylbutyrate.
  • the reaction mixture further comprises an oligomer or polymer in an amount of 0.001 g to 0.60 g per gram of monomer mixture. In some embodiments, the reaction mixture further comprises an oligomer or polymer in an amount of 0.001 g to 0.50 g per gram of monomer mixture. In some embodiments, the reaction mixture further comprises an oligomer or polymer in an amount of 0.001 g to 0.20 g per gram of monomer mixture. In some embodiments, the reaction mixture further comprises an oligomer or polymer in an amount of 0.005 g to 0.10 g per gram of monomer mixture.
  • the reaction mixture further comprises an oligomer or polymer in an amount of 0.005 g to 0.01 g per gram of monomer mixture. In some embodiments, the reaction mixture further comprises an oligomer or polymer in an amount of 0.01 g to 0.05 g per gram of monomer mixture. In some embodiments, the reaction mixture further comprises an oligomer or polymer in an amount of 0.05 g to 0.10 g per gram of monomer mixture.
  • co-polymers of (meth)acrylamides and (meth)acrylic acid esters are used in combination with amine-generating blowing agents. Such species may react and turn the copolymer additives into P(M)I during the foaming process.
  • these homogenizers can, in some instances, prevent phase segregation during polymerization and/or assist and promote the foaming process.
  • the number average molecular weight for these homogenizers can be up to 4 x 10 6 g/mol.
  • an initiator is a substance or molecule that initiates a reaction, such as in polymerization. Typically, the initiator decomposes to form radical, anionic, or cationic species that serve as reactive sites for propagation of polymerization. In some embodiments, the initiator initiates free radical polymerization. [00149] In some embodiments, the initiator is a photoinitiator. In some embodiments, a photoinitiator generates a reactive species when exposed to radiation (e.g., actinic radiation, electromagnetic radiation, electron beam radiation). In some embodiments, the photoinitiator is a molecule that generates a free radical species when exposed to radiation.
  • radiation e.g., actinic radiation, electromagnetic radiation, electron beam radiation.
  • the free radical species formed from the photoinitiator initiates polymerization of one or more monomers or comonomers.
  • the initiator is a thermal intiator.
  • a thermal initiator generates a reactive species when exposed to thermal energy.
  • the thermal initiator generates a free radical species when exposed to radiation.
  • the free radical species formed from the thermal initiator initiates polymerization of one or more monomers or comonomers.
  • the thermal initiator is one or more of tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1’- azobis(cyclohexanecarbonitrile), 2,2’-azobisisobutyronitrile, benzoyl peroxide, 2,2-bis(tert- butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5- dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1- methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl hydro
  • the reaction mixture further comprises one or more photoinitiators.
  • the monomer compositions may include one or more photoinitiators.
  • the one or more photoinitiators comprise a benzoin ether, a benzil ketal, an ⁇ -dialkoxy-acetophenone, an ⁇ -hydroxy-alkylphenone, an ⁇ -amino alkylphenone, an acyl phosphine oxide, a benzophenone, a thioxanthone, and/or a metallocene.
  • the one or more photoinitiators comprise acetophenone, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, benzene tricarbonylchromium, benzil, benzoin, benzoin ethyl ether, benzoin methyl ether, benzophenone, 1-hydroxycyclohexyl phenyl ketone, 3,3’,4,4’-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2- benzyl-2-(dimethylamino)-4’-morpholinobutyrophenone, 4,4’-
  • the one or more photoinitiators comprise bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2,4,6-trimethylbenzoylphenyl phosphinate, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, dipheny1(2,4,6-trimethylbenzoyl)phosphine oxide, alpha- hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methy
  • the one or more photoinitiators comprise diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and combinations of two or more thereof. In some embodiments, the one or more photoinitiators comprise diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
  • the initiator is a salt. In some embodiments, the initiator is an onium salt. In some embodiments, the initiator is an iodonium salt or a sulfonium salt.
  • the initiator is an iodonium salt or a sulfonium salt of formula (RA)2I + XA ⁇ or (RA)3S + XA ⁇ ; wherein each instance of RA is independently optionally substituted C 6-10 aryl or optionally substituted C 1-10 alkyl; and X A – is a counter ion.
  • the initiator is bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-bromophenyl)iodonium trifluoromethanesulfonate, bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, (3- bromophenyl)(mesityl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium
  • the reaction mixture further comprises a reducing agent.
  • the reducing agent is a phosphine-based reducing agent or an amine- based reducing agent.
  • the reducing agent is 4- (diphenylphosphino)benzoic acid, 2-diphenylphosphinobenzoic acid, bis(2- diphenylphosphinophenyl)-ether, triomethoxyphenylphosphine, DPBP bidentate phosphine, 4-dimethylaminophenyldiphenylphosphine, (R,R) dach phenyl trost, triphenylphosphine, ethyl 4-dimethylaminobenzoate, 4-(dimethylamino)phenylacetic acid, triphenylamine, N,N- dibutylaniline, N-Ethyl-N-isopropylaniline, or 3-(dimethylamino)benzy
  • one or more materials may be irradiated with actinic radiation.
  • the actinic radiation may be capable of initiating chemical reactions by formation of radical or ionic species.
  • actinic radiation types may include electromagnetic radiation or particle radiation such as electrons.
  • polymerization of the monomer formulations is carried out under photoinitiated conditions by the use of radiation (e.g., actinic radiation), with the option of using additive manufacturing techniques.
  • the radiation comprises actinic radiation.
  • the actinic radiation comprises electromagnetic radiation.
  • the actinic radiation comprises UV, visible, and/or infrared electromagnetic radiation.
  • initiation includes short wavelength and long wavelength ultraviolet light irradiation. Suitable short wavelength ultraviolet light irradiation includes UV-C or UV-B irradiation. In one embodiment, the short wavelength ultraviolet light irradiation is UV-C light.
  • Suitable longwave ultraviolet light irradiation includes UV-A irradiation. In one embodiment visible light is used.
  • the actinic radiation comprises electromagnetic radiation having a wavelength greater than 100 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength greater than 200 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength greater than 300 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength greater than 400 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength greater than 500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength greater than 750 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 100 nm to less than 1 mm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 100 nm to less than 0.5 mm. [00157] In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 100 nm to less than 750 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 100 nm to less than 280 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 280 nm to less than 315 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 315 nm to less than 400 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 1000 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 750 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 500 nm. In some embodiments, the actinic radiation
  • 56/96 G1035.70000WO00 comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 450 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 440 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 430 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 420 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than 400 nm to less than 410 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm to less than 1 mm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm to less than 4500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm to less than 2500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm to less than 1500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 750 nm to less than 1000 nm.
  • the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 1000 nm to less than 1500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 1500 nm to less than 2500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 2500 nm to less than 4500 nm. In some embodiments, the actinic radiation comprises electromagnetic radiation having a wavelength of greater than or equal to 4500 nm to less than 1 mm. [00159] In some embodiments, the actinic radiation does not comprise gamma radiation.
  • the actinic radiation comprises electromagnetic radiation having an irradiance of 0.1 mW /cm 2 to 10 W/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 0.1 mW/cm 2 to 5 W/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 0.1 mW/cm 2 to 2 W/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 0.1 mW/cm 2 to 1 W/cm 2 .
  • the actinic radiation comprises electromagnetic radiation having an irradiance of 1 mW/cm 2 to 100 mW/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 100 mW/cm 2 to 1 mW/cm 2 . In
  • the actinic radiation comprises electromagnetic radiation having an irradiance of 1 W/cm 2 to 10 W/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 1 mW/cm 2 to 100 mW/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 1 mW/cm 2 to 50 mW/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 1 mW/cm 2 to 10 mW/cm 2 .
  • the actinic radiation comprises electromagnetic radiation having an irradiance of 20 mW/cm 2 to 60 mW/cm 2 . In some embodiments, the actinic radiation comprises electromagnetic radiation having an irradiance of 30 mW/cm 2 to 45 mW/cm 2 .
  • the actinic radiation comprises electron beam radiation. Additionally, Electron Beam (EB) irradiation may be utilized to induce curing of the composition.
  • the duration of the irradiation is up to 300 minutes. In some embodiments, the duration of the irradiation is up to 180 minutes. In some embodiments, the duration of the irradiation is up to 120 minutes.
  • the duration of the irradiation is up to 60 minutes. In some embodiments, the duration of the irradiation is up to 30 minutes. In some embodiments, the duration of the irradiation is up to 20 minutes. In some embodiments, the duration of the irradiation is up to 15 minutes. In some embodiments, the duration of the irradiation is up to 10 minutes. In some embodiments, the duration of the irradiation is up to 5 minutes. In some embodiments, the duration of the irradiation is up to 2 minutes. In some embodiments, the duration of the irradiation is up to 1 minute. In some embodiments, the duration of the irradiation is up to 45 seconds.
  • the duration of the irradiation is up to 30 seconds. In some embodiments, the duration of the irradiation is up to 20 seconds. In some embodiments, the duration of the irradiation is up to 10 seconds. In some embodiments, the duration of the irradiation is up to 5 seconds. In some embodiments, the duration of the irradiation is up to 2 seconds. In some embodiments, the duration of the irradiation is up to 1 second. In some embodiments, the duration of the irradiation is up to 0.5 seconds. In some embodiments, the duration of the irradiation is 0.1 second to 300 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 180 minutes.
  • the duration of the irradiation is 0.1 second to 120 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 60 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 30 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 20 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 15 minutes. In some
  • the duration of the irradiation is 0.1 second to 10 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 5 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 2 minutes. In some embodiments, the duration of the irradiation is 0.1 second to 1 minute. In some embodiments, the duration of the irradiation is 0.1 second to 45 seconds. In some embodiments, the duration of the irradiation is 0.1 second to 30 seconds. In some embodiments, the duration of the irradiation is 0.1 second to 20 seconds. In some embodiments, the duration of the irradiation is 0.1 second to 10 seconds.
  • the duration of the irradiation is 0.1 second to 5 seconds. In some embodiments, the duration of the irradiation is 0.1 second to 2 seconds. In some embodiments, the duration of the irradiation is 0.1 second to 1 second. In some embodiments, the duration of the irradiation is 0.1 second to 0.5 seconds. In some embodiments, the duration of the irradiation is 0.5 second to 2 seconds. In some embodiments, the duration of the irradiation is 2 seconds to 5 seconds. In some embodiments, the duration of the irradiation is 5 seconds to 10 seconds. In some embodiments, the duration of the irradiation is 10 seconds to 20 seconds.
  • the duration of the irradiation is 20 seconds to 30 seconds. In some embodiments, the duration of the irradiation is 30 seconds to 2 minutes. In some embodiments, the duration of the irradiation is 2 minutes to 5 minutes. In some embodiments, the duration of the irradiation is 5 minutes to 10 minutes. In some embodiments, the duration of the irradiation is 10 minutes to 30 minutes. In some embodiments, the duration of the irradiation is 30 minutes to 60 minutes. In some embodiments, the duration of the irradiation is 60 minutes to 120 minutes. In some embodiments, the duration of the irradiation is 120 minutes to 180 minutes. In some embodiments, the duration of the irradiation is 180 minutes to 300 minutes.
  • the duration of the irradiation is adjust based on the amount of the layer of the precursor polymer. In some embodiments, the duration of the irradiation is adjust based on the thickness of the layer of the precursor polymer. [00164] In some embodiments, each side or face of a precursor polymer layer described herein is irradiated. In some embodiments, each side or face of a precursor polymer layer described herein is irradiated for a similar duration of time. In some embodiments, each side or face of a precursor polymer layer described herein is irradiated prior to imidization.
  • each side or face of a precursor polymer layer described herein is irradiated for a similar duration of time prior to imidization.
  • the irradiation of a reaction mixture is performed at a temperature less than 100 °C. In some embodiments, the irradiation of a reaction mixture is
  • the irradiation of a reaction mixture is performed at a temperature less than 90 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 80 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 70 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 60 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 50 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 40 °C.
  • the irradiation of a reaction mixture is performed at a temperature less than 35 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 30 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature less than 25 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 10 °C to 100 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 10 °C to 90 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 10 °C to 80 °C.
  • the irradiation of a reaction mixture is performed at a temperature of 10 °C to 70 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 10 °C to 60 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 10 °C to 50 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 10 °C to 40 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 15 °C to 100 °C.
  • the irradiation of a reaction mixture is performed at a temperature of 15 °C to 90 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 15 °C to 80 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 15 °C to 70 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 15 °C to 60 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 15 °C to 50 °C.
  • the irradiation of a reaction mixture is performed at a temperature of 15 °C to 40 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 15 °C to 30 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 20 °C to 50 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 20 °C to 40 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 20 °C to 30 °C. In some embodiments, the irradiation of a reaction mixture is performed at a temperature of 20 °C to 25 °C.
  • the reaction mixture comprises liquid in an amount of less than 25%. In some embodiments, at the end of the irradiation, the reaction mixture comprises liquid in an amount of less than 20%. In some embodiments, at the end of the irradiation, the reaction mixture comprises liquid in an amount of less than 15%. In some embodiments, at the end of the irradiation, the reaction mixture comprises liquid in an amount of less than 10%. In some embodiments, at the end of the irradiation, the reaction mixture comprises liquid in an amount of less than 5%. In some embodiments, the liquid comprises a solvent. In some embodiments, the liquid comprises unreacted monomer.
  • a method for preparing a 3D article using any of the compositions described in any embodiment herein.
  • the method may include applying successive layers of one or more of the compositions described herein in any embodiment to fabricate a 3D article and/or irradiating the successive layers with UV irradiation.
  • Applying the composition to obtain the three-dimensional article may include depositing the composition.
  • the application may include depositing a first layer of the composition and second layer of the composition to the first layer and, potentially, successive layers thereafter to obtain a 3D article.
  • Such a depositing may include one or more methods, including but not limited to, UV inkjet printing, SLA, continuous liquid interface production (CLIP), and DLP.
  • the layer of the precursor polymer has a thickness of at least 0.5 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of at least 1 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of at least 2 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of at least 5 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of at least 10 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of up to 30 mm.
  • the layer of the precursor polymer has a thickness of up to 40 mm. In some embodiments, the layer of the precursor polymer has a thickness of up to 50 mm. In some embodiments, the layer of the precursor polymer has a thickness of up to 1 cm. In some embodiments, the layer of the precursor polymer has a thickness of up to 2 cm. In some embodiments, the layer of the precursor polymer has a thickness of up to 5 cm. In some embodiments, the layer of the precursor polymer has a thickness of up to 10 cm. [00170] In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 10 cm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m
  • the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 40 mm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 30 mm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 20 mm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 0.5 mm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 5 mm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 1 mm.
  • the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 500 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 250 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 200 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 100 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 100 ⁇ m to 30 mm. In some embodiments, the layer of the precursor polymer has a thickness of 200 ⁇ m to 30 mm. In some embodiments, the layer of the precursor polymer has a thickness of 500 ⁇ m to 30 mm.
  • the layer of the precursor polymer has a thickness of 1 mm to 30 mm. In some embodiments, the layer of the precursor polymer has a thickness of 100 ⁇ m to 50 mm. In some embodiments, the layer of the precursor polymer has a thickness of 200 ⁇ m to 50 mm. In some embodiments, the layer of the precursor polymer has a thickness of 500 ⁇ m to 50 mm. In some embodiments, the layer of the precursor polymer has a thickness of 1 mm to 50 mm. In some embodiments, the layer of the precursor polymer has a thickness of 0.5 ⁇ m to 10 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 1 ⁇ m to 50 ⁇ m.
  • the layer of the precursor polymer has a thickness of 5 ⁇ m to 100 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 10 ⁇ m to 250 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 250 ⁇ m to 500 ⁇ m. In some embodiments, the layer of the precursor polymer has a thickness of 500 ⁇ m to 1 mm. In some embodiments, the layer of the precursor polymer has a thickness of 1 mm to 10 mm. In some embodiments, the layer of the precursor polymer has a thickness of 10 mm to 20 mm. In some embodiments, the layer of the precursor polymer has a thickness of 20 mm to 30 mm.
  • the layer of the precursor polymer has a thickness of 30 mm to 40 mm. In some embodiments, the layer of the precursor polymer has a thickness of 40 mm to 50 mm. In some embodiments, the layer of the precursor polymer has a thickness of 50 mm to 10 cm. [00171] In some embodiments, the precursor polymer is a solid. In some embodiments, the precursor polymer is a resin. In some embodiments, the precursor polymer is in the form of a
  • the precursor polymer is in the form of a solid layer.
  • the layer of the precursor polymer is a solid.
  • the precursor polymer is a solid having a stable shape.
  • the precursor polymer is a solid having a firm and stable shape.
  • the layer of the precursor polymer is a solid having a stable shape.
  • the layer of the precursor polymer is a solid having a firm and stable shape.
  • the layer of the precursor polymer has a percent conversion of at least 50%. In some embodiments, the layer of the precursor polymer has a percent conversion of at least 60%.
  • the layer of the precursor polymer has a percent conversion of at least 70%. In some embodiments, the layer of the precursor polymer has a percent conversion of at least 75%. In some embodiments, the layer of the precursor polymer has a percent conversion of at least 80%. In some embodiments, the layer of the precursor polymer has a percent conversion of at least 85%. In some embodiments, the layer of the precursor polymer has a percent conversion of at least 90%. In some embodiments, the layer of the precursor polymer has a percent conversion of at least 95%. [00173] Other applications for the compositions include, but are not limited to, other coating and ink applications for automotive, aerospace, and electronics.
  • Some methods described herein include contacting the layers of the composition with ultraviolet light irradiation to induce curing of the composition.
  • the contacting may include short wavelength and/or long wavelength ultraviolet light irradiation.
  • Suitable short wavelength ultraviolet light irradiation includes UV-C or UV-B irradiation.
  • the short wavelength ultraviolet light irradiation is UV-C light.
  • Suitable longwave ultraviolet light irradiation includes UV-A irradiation.
  • Electron Beam (EB) irradiation may be utilized to induce curing of the composition.
  • the methods described herein may include repeating the deposition of layers of the composition and exposure to UV irradiation to obtain the 3D article.
  • the repeating may occur sequentially wherein depositing the layers of composition is repeated to obtain the 3D article prior to exposure to UV irradiation. In any embodiments, the repeating may occur subsequently wherein the depositing the layers of composition and exposure to UV irradiation are repeated after both steps. In some embodiments, the depositing is performed via UV inkjet printing, stereolithography, continuous liquid interface production, or digital light processing.
  • a 3D article that includes UV cured successive layers of any of the compositions as described herein.
  • the composition may have been cast, inkjet, SLA, or DLP deposited.
  • the layer is formed via vat polymerization, material jetting, binder jetting, powder bed fusion, extrusion, directed energy deposition, sheet lamination, extrusion, and/or layer casting.
  • the layer is formed via UV inkjet printing, stereolithography, continuous liquid interface production, or digital light processing.
  • the layer is formed via 3D printing.
  • a method provided herein further comprises a step of forming one or more additional layers of the precursor polymer.
  • the one or more additional layers of the precursor polymer are formed prior to the imidizing step.
  • the one or more additional layers of the precursor polymer are formed subsequent to the imidizing step.
  • the one or more additional layers of the precursor polymer undergo imidization.
  • the one or more additional layers are formed by repeating step (a) provided herein.
  • the one or more additional layers are formed by repeating steps (a) and (b) provided herein.
  • an imidizing step e.g., imidization described herein occurs without foaming.
  • a method provided herein further comprises a step of foaming the precursor polymer.
  • the imidizing step e.g., imidization
  • the imidizing step is performed prior to, concurrent with, or subsequent to the foaming step.
  • the imidizing step e.g., imidization
  • the imidizing step is performed prior to the foaming step.
  • the imidizing step is performed concurrently with the foaming step.
  • the imidizing step e.g., imidization
  • Methods for inducing imidization and foaming include but are not limited to, supplying heat using hot-air convection furnaces, microwave radiation, magnetic induction, infrared radiation, near-infrared radiation, optionally combined with near-infrared dyes such as but not limited to, cyanines, porphyrine dyes, squaraine dyes, phtalocyanines, squarylium salts, diimonium salts, and dithiolene complexes.
  • the imidizing step comprises irradiating the precursor polymer with actinic radiation.
  • the imidizing step comprises irradiating the precursor polymer with electromagnetic radiation. In some embodiments, the imidizing step (e.g., imidization) comprises irradiating the precursor polymer with electromagnetic radiation as provided herein (e.g., having a wavelength
  • the imidizing step comprises irradiating the precursor polymer with near-infrared radiation. In some embodiments, the imidizing step (e.g., imidization) comprises irradiating the precursor polymer with infrared radiation. [00182] In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer. In some embodiments, the heating causes the precursor polymer to undergo foaming. In some embodiments, the foaming step comprises heating the precursor polymer.
  • the foaming step comprises heating the precursor polymer below the T g of the precursor polymer.
  • the heat is supplied using conduction, convection, or radiation.
  • the heat is supplied using a hot- air convection furnace, microwave radiation, magnetic induction, infrared radiation, and/or near-infrared radiation.
  • the heat is supplied using a furnace, heating element, or water bath.
  • the heat is supplied using a hot-air convection furnace.
  • the imidizing step e.g., imidization
  • the foaming step is performed prior to the foaming step using a blowing agent that volatilizes or decomposes above the imidization temperature.
  • the imidizing step (e.g., imidization) is performed concurrently with the foaming step using a blowing agent that volatilizes or decomposes close to the imdization temperature.
  • the imidizing step (e.g., imidization) is performed concurrently with the foaming step when a blowing agent is generated during the imidizing step (e.g., imidization).
  • the heating during the imidizing step causes the precursor polymer to undergo foaming.
  • the imidizing step (e.g., imidization) is performed subsequent to the foaming step using a blowing agent that volatilizes or decomposes below the imidization temperature.
  • the imidizing step comprises heating the precursor polymer to at least 100 °C. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer to at least 120 °C. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer to at least 150 °C. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer to 100 °C to 250 °C. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer to 130 °C to 220 °C. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer to 140 °C to 210 °C. In some embodiments, the imidizing step (e.g., imidization) comprises
  • the imidizing step comprises heating the precursor polymer to 160 °C to 190 °C.
  • the imidizing step comprises heating the precursor polymer for 1 second to 4 hours.
  • the imidizing step comprises heating the precursor polymer for 1 minute to 4 hours.
  • the imidizing step comprises heating the precursor polymer for 5 minutes to 4 hours.
  • the imidizing step comprises heating the precursor polymer for 30 seconds to 2 minutes. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 1 minute to 5 minutes. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 5 minutes to 20 minutes. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 20 minutes to 1 hour. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 1 hour to 4 hours.
  • the imidizing step comprises heating the precursor polymer for 20 minutes to 3 hours. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 30 minutes to 2 hours. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 40 minutes to 80 minutes. In some embodiments, the imidizing step (e.g., imidization) comprises heating the precursor polymer for 80 minutes to 120 minutes. [00186] In some embodiments, at least a portion of the precursor polymer undergoes imidization. In some embodiments, at least 20% of the precursor polymer undergoes imidization.
  • At least 40% of the precursor polymer undergoes imidization. In some embodiments, at least 60% of the precursor polymer undergoes imidization. In some embodiments, at least 80% of the precursor polymer undergoes imidization. In some embodiments, at least 90% of the precursor polymer undergoes imidization. In some embodiments, at least 95% of the precursor polymer undergoes imidization. In some embodiments, 20%-100% of the precursor polymer undergoes imdization. In some embodiments, 40%-100% of the precursor polymer undergoes imdization. In some embodiments, 60%-100% of the precursor polymer undergoes imdization. In some embodiments, 80%-100% of the precursor polymer undergoes imdization.
  • the portion of the precursor polymer is a section (e.g., a section of a layer). [00187] In some embodiments, at least a section of the layer of the precursor polymer undergoes imidization. In some embodiments, the layer of the precursor polymer undergoes
  • at least a section of one or more layers of the precursor polymer undergo imdidization.
  • one or more layers of the precursor polymer undergo imdidization in their entirety.
  • at least a section of one or more layers of the precursor polymer undergo concurrent imdidization.
  • one or more layers of the precursor polymer undergo concurrent imdidization.
  • at least a section of one or more layers of the precursor polymer undergo sequential imdidization.
  • one or more layers of the precursor polymer undergo sequential imdidization.
  • a columetric section spanning one or more layers of the precursor undergoes imidization.
  • At least 20% of one or more layers of the precursor polymer undergoes imidization. In some embodiments, at least 40% of one or more layers of the precursor polymer undergoes imidization. In some embodiments, at least 60% of one or more layers of the precursor polymer undergoes imidization. In some embodiments, at least 80% of one or more layers of the precursor polymer undergoes imidization. In some embodiments, at least 90% of one or more layers of the precursor polymer undergoes imidization. In some embodiments, at least 95% of one or more layers of the precursor polymer undergoes imidization. In some embodiments, 20%-100% of one or more layers of the precursor polymer undergoes imdization.
  • the foaming step comprises heating the precursor polymer above the imidization temperature. In some embodiments, the foaming step comprises heating the precursor polymer above 150 °C. In some embodiments, the foaming step comprises heating the precursor polymer above 170 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 150 °C to 250 °C.
  • the foaming step comprises heating the precursor polymer from 160 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 170 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 180 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 190 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 200 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 150 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 160 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 170 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 180 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 190 °C to
  • the foaming step comprises heating the precursor polymer from 170 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 180 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 190 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 200 °C to 250 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 150 °C to 200 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 160 °C to 200 °C.
  • the foaming step comprises heating the precursor polymer from 170 °C to 200 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 180 °C to 200 °C. In some embodiments, the foaming step comprises heating the precursor polymer from 190 °C to 200 °C. [00189] In some embodiments, the foaming step comprises heating the precursor polymer below the imidization temperature. In some embodiments, the foaming step comprises heating the precursor polymer up to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer up to 150 °C. In some embodiments, the foaming step comprises heating the precursor polymer up to 140 °C.
  • the foaming step comprises heating the precursor polymer up to 130 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 30 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 40 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 50 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 60 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 70 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 80 °C to 160 °C.
  • the foaming step comprises heating the precursor polymer to 90 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 100 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 110 °C to 160 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 30 °C to 140 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 40 °C to 140 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 50 °C to 140 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 60 °C to 140 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 70 °C to 140 °C. In some embodiments, the foaming step comprises heating the precursor polymer to 80 °C to 140 °C. In some embodiments, the foaming step comprises, the precursor polymer to 80 °C to 140 °C
  • 68/96 G1035.70000WO00 comprises heating the precursor polymer to 90 °C to 140 °C.
  • the foaming step comprises heating the precursor polymer to 100 °C to 140 °C.
  • the foaming step comprises heating the precursor polymer to 110 °C to 140 °C.
  • the foaming step comprises heating the precursor polymer for 5 minutes to 4 hours.
  • the foaming step comprises heating the precursor polymer for 20 minutes to 3 hours.
  • the foaming step comprises heating the precursor polymer for 30 minutes to 2 hours.
  • the foaming step comprises heating the precursor polymer for 40 minutes to 80 minutes.
  • the foaming step comprises heating the precursor polymer for 80 minutes to 120 minutes. In some embodiments, the foaming step comprises heating the precursor polymer for the duration of the imidizing step (e.g., imidization).
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes.
  • suitable near-infrared dyes include cyanine dyes, phtalocyanine dyes, porphyrine dyes, squaraine dyes, squarylium dyes, diimonium dyes, and dithiolene complexes.
  • the near-infrared dye is a cyanine dye, a phtalocyanine dye, a squarylium dye, a diimonium dye, or a dithiolene complex. In some embodiments, the near-infrared dye is a cyanine dye. In some embodiments, the cyanine dye is IR-813. In some embodiments, the cyanine dye is IR-783. In some embodiments, the near-infrared dye is a near-infrared borate dye or a near-infrared heat generating dye. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises a cyanine dye.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises IR-813, IR- 140, IR-780, IR-783, IR-1601, Indocyanine Green, IR-140, IR-780, S2425, S0507, S2544, S0991, S2025, camphorquinone, ethyldimethylaminobenzoate, SQ-1, SQ-2, SQ-3, BODIPY, or a salt thereof.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises IR-813, IR-813 borate, IR-783, IR-140 borate, IR-780 borate, IR-1601, Indocyanine Green, IR-140 perchlorate, IR- 780 iodide, S2425, S0507, S2544, S0991, S2025, camphorquinone, ethyldimethylaminobenzoate, SQ-1, SQ-2, SQ-3, or BODIPY.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises IR-813 or IR-783.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises a dye provided in U.S. patent number 11,384,167, which is incorporated herein by reference.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.01 wt% to 1 wt%. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.01 wt% to 0.5 wt%.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.01 wt% to 0.4 wt%. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.01 wt% to 0.3 wt%. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near- infrared dyes in an amount of 0.01 wt% to 0.2 wt%.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.01 wt% to 0.1 wt%. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.01 wt% to 0.05 wt%. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near- infrared dyes in an amount of 0.05 wt% to 0.1 wt%.
  • the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.1 wt% to 0.5 wt%. In some embodiments, the reaction mixture, a layer of the precursor polymer, and/or a material comprising a precursor polymer comprises one or more near-infrared dyes in an amount of 0.5 wt% to 1 wt%. [00193] In some embodiments, each side or face of a precursor polymer layer comprising one or more near-infrared dyes described herein is irradiated.
  • each side or face of a precursor polymer layer comprising one or more near-infrared dyes described herein is irradiated for a similar duration of time.
  • a precursor polymer comprises an optionally substituted polyacrylic ester, an optionally substituted polyacrylamide, an optionally substituted polyacrylic acid, an optionally substituted polyacrylonitrile, and/or any copolymer thereof.
  • a precursor polymer comprises an optionally substituted polyacrylic ester, an optionally substituted polyacrylamide, an optionally substituted polyacrylic acid, and/or any copolymer thereof.
  • a precursor polymer comprises an optionally substituted polyacrylic ester, an optionally substituted polyacrylamide, an optionally substituted polyacrylic acid, and/or any copolymer thereof.
  • a precursor polymer comprises an
  • a precursor polymer comprises an optionally substituted polyacrylic ester, an optionally substituted polyacrylamide, an optionally substituted polyacrylic acid, an optionally substituted polyacrylonitrile, and/or any copolymer thereof prepared according to a method provided herein.
  • poly(meth)acrylimides prepared according to any method provided herein.
  • the obtained PMI materials may be particularly suitable for high temperature applications in their dense and/or foamed states.
  • PMI foams can be obtained in densities ranging from 30 kg/m 3 to 600 kg/m 3 and/or may possess homogeneous microstructures.
  • the PMI foam has a density of 30 kg/m 3 to 600 kg/m 3 .
  • the PMI foam has a density of 30 kg/m 3 to 300 kg/m 3 .
  • the PMI foam has a density of 300 kg/m 3 to 600 kg/m 3 .
  • the PMI foam has a density of 30 kg/m 3 to 100 kg/m 3 .
  • the PMI foam has a density of 100 kg/m 3 to 200 kg/m 3 .
  • the PMI foam has a density of 200 kg/m 3 to 300 kg/m 3 . In some embodiments, the PMI foam has a density of 300 kg/m 3 to 400 kg/m 3 . In some embodiments, the PMI foam has a density of 400 kg/m 3 to 500 kg/m 3 . In some embodiments, the PMI foam has a density of 500 kg/m 3 to 600 kg/m 3 . [00198] In some embodiments, a PMI resin is obtained with a higher density than a PMI foam. In some embodiments, a PMI resin has a density of at least 600 kg/m 3 . In some embodiments, the PMI resin has a density of 600 kg/m 3 to 2500 kg/m 3 .
  • the PMI resin has a density of 600 kg/m 3 to 2000 kg/m 3 . In some embodiments, the PMI resin has a density of 600 kg/m 3 to 1500 kg/m 3 . In some embodiments, the PMI resin has a density of 600 kg/m 3 to 1000 kg/m 3 . In some embodiments, the PMI resin has a density of 1000 kg/m 3 to 1500 kg/m 3 . In some embodiments, the PMI resin has a density of 1500 kg/m 3 to 2000 kg/m 3 . In some embodiments, the PMI resin has a density of 600 kg/m 3 to 900 kg/m 3 . In some embodiments, the PMI resin has a density of 900 kg/m 3 to 1200 kg/m 3 .
  • the PMI resin has a density of 1200 kg/m 3 to 1500 kg/m 3 . In some embodiments, the PMI resin has a density of 1500 kg/m 3 to 2000 kg/m 3 . In some embodiments, the PMI resin has a density of 2000 kg/m 3 to 2500 kg/m 3 .
  • the PMI foam has a homogenous microstructure.
  • a homogenous microstructure is characterized by optical microscopy or electron microscopy.
  • a PMI foam having a homogenous microstructure has a pore size of 1 ⁇ m to 500 ⁇ m.
  • a PMI foam having a homogenous microstructure has a pore size of 1 ⁇ m to 250 ⁇ m.
  • a PMI foam having a homogenous microstructure has a pore size of 1 ⁇ m to 100 ⁇ m.
  • a PMI foam having a homogenous microstructure has a pore size of 1 ⁇ m to 50 ⁇ m. In some embodiments, a PMI foam having a homogenous microstructure has a pore size of 10 ⁇ m to 500 ⁇ m. In some embodiments, a PMI foam having a homogenous microstructure has a pore size of 25 ⁇ m to 500 ⁇ m. In some embodiments, a PMI foam having a homogenous microstructure has a pore size of 50 ⁇ m to 500 ⁇ m. In some embodiments, a PMI foam having a homogenous microstructure has a pore size of 100 ⁇ m to 500 ⁇ m.
  • a homogenous microstructure is characterized by nuclear magnetic resonance spectroscopy. In some embodiments, a homogenous microstructure is characterized by nuclear magnetic resonance spectroscopy by comparing relaxation times of solvent at a surface of a pore to those of solvent in the pore. In some embodiments, a homogenous microstructure is characterized by ultrasound. In some embodiments, a homogenous microstructure is characterized by tomography. [00200] In particular, for PMI materials produced by some additive manufacturing methods according to this disclosure, geometries are not constrained to rectangular blocks, and/or production times are cut to hours. [00201] Additionally, the thermomechanical properties of the PMI foams may be particularly improved above 160 °C.
  • the thermomechanical properties of the PMI foams are improved compared to industrial standards.
  • the PMI foam has a Tg of at least 160 °C. In some embodiments, the PMI foam has a Tg of at least 170 °C. In some embodiments, the PMI foam has a Tg of at least 180 °C. In some embodiments, the PMI foam has a T g of at least 190 °C. In some embodiments, the PMI foam has a T g of 160 °C to 250 °C. In some embodiments, the PMI foam has a Tg of 160 °C to 230 °C. In some embodiments, the PMI foam has a Tg of 160 °C to 220 °C.
  • the PMI foam has a T g of 160 °C to 210 °C. In some embodiments, the PMI foam has a T g of 160 °C to 200 °C. In some embodiments, the PMI foam has a T g of 160 °C to 170 °C. In some embodiments, the PMI has a Tg of 170 °C to 190 °C. In some embodiments, the PMI foam has a Tg of 190 °C to 210 °C. In some embodiments, the PMI foam has a Tg of 210 °C to 230
  • the PMI foam has a T g of 230 °C to 240 °C. In some embodiments, the PMI foam has a Tg of 240 °C to 250 °C.
  • a PMI resin has increased thermomechanical properties relative to a PMI foam. In some embodiments, the PMI resin has a T g of at least 160 °C. In some embodiments, the PMI resin has a Tg of at least 170 °C. In some embodiments, the PMI resin has a Tg of at least 180 °C. In some embodiments, the PMI resin has a Tg of at least 190 °C.
  • the PMI resin has a T g of at least 200 °C. In some embodiments, the PMI resin has a Tg of 160 °C to 280 °C. In some embodiments, the PMI resin has a Tg of 160 °C to 270 °C. In some embodiments, the PMI resin has a Tg of 160 °C to 260 °C. In some embodiments, the PMI resin has a T g of 160 °C to 250 °C. In some embodiments, the PMI resin has a T g of 160 °C to 240 °C. In some embodiments, the PMI resin has a T g of 160 °C to 200 °C.
  • the PMI resin has a Tg of 160 °C to 170 °C. In some embodiments, the PMI resin has a Tg of 170 °C to 190 °C. In some embodiments, the PMI resin has a T g of 190 °C to 200 °C. In some embodiments, the PMI resin has a T g of 200 °C to 220 °C. In some embodiments, the PMI resin has a Tg of 220 °C to 240 °C. In some embodiments, the PMI resin has a Tg of 240 °C to 260 °C. In some embodiments, the PMI resin has a T g of 250 °C to 270 °C.
  • the PMI resin has a T g of 260 °C to 280 °C.
  • the compressive modulus of a PMI foam produced according to a method provided herein is at least 5 MPa. In some embodiments, the compressive modulus of a PMI foam produced according to a method provided herein is at least 10 MPa. In some embodiments, the compressive modulus of a PMI foam produced according to a method provided herein is at least 15 MPa. In some embodiments, the compressive modulus of a PMI foam produced according to a method provided herein is at least 20 MPa. In some embodiments, the compressive modulus of a PMI foam produced according to a method provided herein is at least 30 MPa.
  • the compressive modulus of a PMI foam produced according to a method provided herein is at least 40 MPa. In some embodiments, the compressive modulus of a PMI foam produced according to a method provided herein is at least 50 MPa. In some embodiments, the compressive modulus of a PMI foam produced according to a method provided herein is at least 75 MPa. [00204] In some embodiments, the flexural modulus of a PMI foam produced according to a method provided herein is at least 50 MPa. In some embodiments, the flexural modulus of a PMI foam produced according to a method provided herein is at least 60 MPa. In some embodiments, the flexural modulus of a PMI foam produced according to a method provided
  • the flexural modulus of a PMI foam produced according to a method provided herein is at least 100 MPa. In some embodiments, the flexural modulus of a PMI foam produced according to a method provided herein is at least 200 MPa. In some embodiments, the flexural modulus of a PMI foam produced according to a method provided herein is at least 500 MPa. In some embodiments, the flexural modulus of a PMI foam produced according to a method provided herein is at least 1 GPa. In some embodiments, the flexural modulus of a PMI foam produced according to a method provided herein is at least 5 GPa.
  • the temperature was then increased to 75 °C for 12 h, followed by tempering at 110 °C for 12 h.
  • the obtained rectangular copolymer block was subsequently imidized and foamed at 190 °C in a hot-air furnace for 2 h.
  • the density of the obtained foam was 50 kg/m 3 .
  • Compressive modulus measured by DMA at 25 °C was 17 MPa at 25 °C and 18 MPa at 180 °C.
  • Flexural modulus measured by DMA was 28 MPa at 25 °C and 23 at 180 °C.
  • Example 1 To a mixture of 5.50 g methacrylic acid, 5.55 g methacrylamide, 1.5 g water, and 0.11 g ethylene glycol dimethacrylate, 1.11 g of a homogenizer that is a copolymer of a (meth)acrylamide and a (meth)acrylic acid ester was added. The mixture was stirred until homogeneous, then 1.11 g urea and 0.33 g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide were added. The mixture was extruded in a silicone mold as a single layer and photocured with a LED lamp (405 nm,100 W) for 30 s on each side. The obtained copolymer block was subsequently imidized and foamed at 190 °C in a hot-air furnace for 1 h. The density of the
  • the mixture was stirred until homogeneous, 0.33 g diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide were added.
  • the mixture was extruded in a silicone mold as a single layer and photocured with a LED lamp (405 nm,100 W) for 30 s on each side.
  • the obtained copolymer block was subsequently imidized at 160 °C for 1 h, followed by thermal treatment at 180 °C for 2 h in a hot-air furnace.
  • the density of the obtained PMI polymer was 1324 kg/m 3 . Flexural modulus measured by DMA was 6.5 GPa at 25 °C.
  • the layer was photocured for 40 seconds with a 365 nm LED (40 mW/cm 2 ) on one side, then flipped and photocured again for 40 seconds on the other side.
  • the obtained transparent yellow rectangular copolymer was imidized and foamed at 180 °C for 1h in a hot-air furnace.
  • the obtained PMI foam had a density of 250 kg/m 3 and a T g of 172 °C.
  • Example 5 A mixture of 11.90 g methacrylic acid, 11.90 g methacrylamide, 4.40 g water, 1.00 g glycerol, 2.50 g N-methylurea and 0.10 g trimethylolpropane trimethacrylate (TMPTMA) was stirred at 40 °C until homogenous. 0.70 g Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) were added, and after cooling to room temperature, the clear solution was layer- casted in a rectangular silicone mold (100 mm x 10 mm x 10 mm) to form a 1 mm thick liquid layer.
  • TPO Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
  • Example 6 [00212] The same reaction mixture of Example 5 was loaded in a LCD 3D printer with a light source at 405 nm and irradiance of 2 mW/cm 2 .
  • a rectangular (60 mm x 10 mm x 5 mm) 3D article was printed by sequentially photocuring 50 ⁇ m thick layers with 10 seconds exposure.
  • the copolymer block was imidized and foamed at 180 °C for 1 h in a hot-air furnace.
  • the obtained PMI foam had a density of 150 kg/m 3 and a Tg of 170 °C.
  • Example 7 A mixture of 11.90 g methacrylic acid, 11.90 g methacrylamide, 4.40 g water, 1.00 g glycerol, 2.00 g urea, 0.20 g tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA) and 1.80 g urethane dimethacrylate (UDMA) was stirred at 40 °C until homogenous. 0.70 g Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) were added, and after cooling to room temperature, the clear solution was layer-casted in a rectangular silicone mold (100 mm x 10 mm x 10 mm) to form a 2 mm thick liquid layer.
  • TPO Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
  • the layer was photocured for 40 seconds with a 405 nm LED (32 mW/cm2) on one side, then flipped and photocured again for 40 seconds on the other side.
  • the obtained transparent yellow rectangular copolymer was imidized and foamed at 180 °C for 1 h in a hot-air furnace.
  • the obtained PMI foam had a density of 478 kg/m 3 and a T g of 165 °C.
  • Example 8 A mixture of 23.80 g methacrylic acid, 23.80 g methacrylamide, 8.80 g water, 2.00 g glycerol, 4.00 g urea and 0.20 g trimethylolpropane trimethacrylate (TMPTMA) was stirred at 40 °C until homogenous. 1.40 g Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) were added, and after cooling to room temperature, the clear solution was loaded in a LCD
  • Example 9 A mixture of 23.80 g methacrylic acid, 23.80 g methacrylamide, 8.80 g water, 2.00 g glycerol, 4.00 g urea, 0.30 g tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA) and 1.60 g urethane dimethacrylate (UDMA) was stirred at 40 °C until homogenous.
  • TEEICTA tris(2-hydroxyethyl)isocyanurate triacrylate
  • UDMA urethane dimethacrylate
  • TPO Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
  • Example 10 A mixture of 18.00 g methacrylic acid, 12.00 g methacrylamide, 3.00 g butylmethacrylate, 3.00 g water, 3.00 g urea, 0.30 g ethylene glycol dimethacrylate (EGDMA) was stirred at 40 °C until homogenous. 0.92 g Diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide (TPO) were added, and after cooling to room temperature, the clear solution was layer-casted in a rectangular silicone mold (100 mm x 10 mm x 10 mm) to form a 2 mm thick liquid layer.
  • EGDMA ethylene glycol dimethacrylate
  • TPO Diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide
  • the layer was photocured for 40 seconds with a 405 nm LED (32 mW/cm 2 ) on one side, then flipped and photocured again for 40 seconds on the other side.
  • the obtained transparent yellow rectangular copolymer was imidized and foamed at 180 °C for 1 h in a hot-air furnace.
  • the obtained PMI foam had a density of 220 kg/m 3 and a Tg of 170 °C.
  • Example 11 A mixture of 27.00 g methacrylic acid, 18.00 g methacrylamide, 4.50 g butylmethacrylate, 4.50 g water, 4.50 g urea, 0.40 g triethylene glycol dimethacrylate (TEGDMA) was stirred at 40 °C until homogenous. 1.38 g Diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide (TPO) were added, and after cooling to room temperature, the clear solution layer-casted in a rectangular silicone mold (100 mm x 10 mm x 10 mm) to form a 1 mm thick liquid layer. The layer was photocured for 40 seconds with a 365 nm LED
  • NIR near-infrared
  • Example 13 Temperature response in precursor polymers and poly(meth)acrylimides was measured over time upon exposure to near-infrared (NIR) irradiation with a 810 nm LED array operated at different irradiances (FIGs. 3-10). The temperature was measured on the irradiated surface of a polymer sample with an infrared camera. Polymer samples containing different %wt of NIR dyes were tested and compared to a control sample of the same polymer without dyes. NIR dyes tested were IR-813 (FIGs. 3-7) and IR-783 (FIGs. 8-10).
  • the present disclosure includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.
  • the present disclosure encompasses all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim.
  • any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim.
  • elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

La divulgation concerne un procédé de production de poly(méth)acrylimides par copolymérisation de (méth)acrylates, de (méth)acrylamides et/ou de (méth)acrylonitrile sous l'influence d'un rayonnement actinique. La résine polymère précurseur résultante peut être imidisée et/ou moussée par traitement thermique.
PCT/US2024/056301 2023-11-16 2024-11-15 Matériaux de poly(méth)acrylimide présentant des propriétés thermomécaniques améliorées Pending WO2025106936A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6206550B1 (en) * 1994-10-18 2001-03-27 Mitsubishi Rayon Company Ltd. Active energy ray-curable composition and lens sheet
US20120251831A1 (en) * 2009-12-16 2012-10-04 Japan Carlit Co., Ltd Near-infrared absorptive coloring matter and near-infrared absorptive composition
US20160159995A1 (en) * 2013-07-10 2016-06-09 Riken Technos Corporation Poly(meth)acrylimide film, easy-adhesion film using same, and method for manufacturing such films
US20160304752A1 (en) * 2013-11-18 2016-10-20 Riken Technos Corporation Blue light-blocking resin composition
EP3272518B1 (fr) * 2015-03-18 2022-05-11 Riken Technos Corporation Film de stratifié de revêtement dur et son procédé de production
WO2023012268A1 (fr) * 2021-08-04 2023-02-09 Röhm Gmbh Composition polymère à base de poly(méth)acrylimide pour des applications tribologiques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6206550B1 (en) * 1994-10-18 2001-03-27 Mitsubishi Rayon Company Ltd. Active energy ray-curable composition and lens sheet
US20120251831A1 (en) * 2009-12-16 2012-10-04 Japan Carlit Co., Ltd Near-infrared absorptive coloring matter and near-infrared absorptive composition
US20160159995A1 (en) * 2013-07-10 2016-06-09 Riken Technos Corporation Poly(meth)acrylimide film, easy-adhesion film using same, and method for manufacturing such films
US20160304752A1 (en) * 2013-11-18 2016-10-20 Riken Technos Corporation Blue light-blocking resin composition
EP3272518B1 (fr) * 2015-03-18 2022-05-11 Riken Technos Corporation Film de stratifié de revêtement dur et son procédé de production
WO2023012268A1 (fr) * 2021-08-04 2023-02-09 Röhm Gmbh Composition polymère à base de poly(méth)acrylimide pour des applications tribologiques

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