WO2025041082A1 - Materials and methods for transmetallation-activated ring-opening metathesis polymerization (romp) - Google Patents

Abstract

A method for additive manufacturing of an object includes depositing layers of material, the depositing including, for at least some layers of material, and depositing a first fluid material, the first fluid material including an activator and a monomer, depositing a second fluid material including a pre-catalyst for reacting with the activator of the deposited first fluid material. The depositing causes the second fluid material to disperse through the first fluid material, causing the pre-catalyst in the deposited second fluid material to react with the activator in the deposited first fluid material to form a polymerization catalyst with a concentration determined from a concentration of the activator in the deposited first fluid material, initiating a polymerization reaction.

Description

MATERIALS AND METHODS FOR TRANSMETALLATION-ACTIVATED

RING-OPENING METATHESIS POLYMERIZATION (ROMP)

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to, and the benefit of, U.S. Provisional Application No. 63/534,166, filed August 23, 2023, and U.S. Provisional Application No. 63/685,756, filed August 22, 2024, the contents of each of which are incorporated by reference in their entireties for all purposes.

BACKGROUND OF THE INVENTION

[0002] This invention relates to additive manufacturing.

[0003] Additive manufacturing, sometimes referred to as 3D printing, is a manufacturing process that builds three-dimensional objects layer by layer using computer-aided design (CAD) specifications of the objects. Unlike traditional subtractive methods, which involve removing material from a solid block, additive manufacturing adds material precisely where it is needed, resulting in minimal waste and increased design freedom. There is a wide variety of techniques for additive manufacturing, including fused deposition modeling, stereolithography, selective laser sintering, and inkjet-based additive manufacturing. Applications of additive manufacturing span various industries, including aerospace, automotive, healthcare, and consumer products, where additive manufacturing offers the potential for customization, rapid prototyping, and on-demand production.

SUMMARY OF THE INVENTION

[0004] Some inkjet-based additive manufacturing systems build objects by repeatedly depositing layers of build material and/or support material in liquid form. For high print quality, each deposited layer should become sufficiently solid (e.g., cooled or cured) before a subsequent layer is deposited thereon. The speed at which an object can be fabricated depends on the speed at which deposited layers of the object become sufficiently solid.

[0005] Waxes are often used as support material, where the wax is deposited in a molten form and solidifies by cooling. One common type of build material is a photopolymer that solidifies by a curing process initiated using UV radiation. Other types of materials solidify by curing processes other than photo-initiated curing. For example, some polymer build materials solidify by a polymerization reaction caused by the mixing of a monomer fluid with a catalyst fluid (where the catalyst may be formed by combining an activator with a pre-catalyst). Traditionally, these types of polymer materials have been limited to applications where they can be mixed in bulk and poured into a mold shortly after mixing, where solidification occurs. Use of these types of materials in inkjet-based additive manufacturing systems is challenging for at least the reason that depositing a homogenous mixture of the catalyst and monomer through an inkjet system is difficult — if the components are mixed prior to deposition, polymerization will occur in the printhead or storage tank before it can be deposited as a liquid.

[0006] Aspects described herein relate to an inkjet-based additive manufacturing system and process for forming layers of polymer by depositing a precatalyst fluid and a liquid mixture of a monomer (e.g., a ROMP precursor) and activator (e.g., a transition metal activator) from separate inkjet nozzles. The precatalyst (e.g., a ROMP pre-catalyst) is designed to disperse through the deposited monomer/activator, where it interacts with the activator to form a polymerization catalyst. The polymerization catalyst then reacts with the monomer to form a polymer by a polymerization reaction.

[0007] A concentration of the polymerization catalyst generated in a layer is determined by a concentration of the activator in the deposited monomer/activator. In some examples, the precatalyst fluid (e.g., a Type B fluid material as described herein, comprising a ROMP pre-catalyst as described herein) is deposited in an amount such that the precatalyst (e.g., a ROMP pre-catalyst) is always in stoichiometric excess of the activator (e.g., a transition metal activator as described herein). In some examples, a concentration of the activator is chosen to ensure the precatalyst (a liberal amount of which is deposited) is able to fully disperse through the monomer/activator while also ensuring that enough (but not too much, i.e., a desired amount) catalyst is generated to form a layer of polymer that is sufficiently cured for deposition of a subsequent layer of material thereon. If a concentration of the activator is too high, too much catalyst will be produced as the precatalyst disperses through the monomer/activator, causing polymerization to occur too quickly, preventing the precatalyst from fully dispersing through the deposited monomer/activator mixture. This results in incomplete curing of the layer. If a concentration of the activator is too low, the amount of catalyst produced is insufficient to form a layer of polymer that is sufficiently cured in time for deposition of a subsequent layer of material thereon. [0008] In a general aspect, a method for additive manufacturing of an object includes depositing layers of material, the depositing including, for at least some layers of material, depositing a first fluid material (e.g., a Type A fluid material), the first fluid material including an activator and a monomer, depositing a second fluid material including a pre-catalyst for reacting with the activator of the deposited first fluid material. The depositing causes the second fluid material to disperse through the first fluid material, causing the pre-catalyst in the deposited second fluid material to react with the activator in the deposited first fluid material to form a polymerization catalyst with a concentration determined from a concentration of the activator in the deposited first fluid material, initiating a polymerization reaction.

[0009] It is understood that, as the terms are used herein, “first fluid material” has the same meaning as “Type A fluid material,” and the “second fluid material” has the same meaning as “Type B fluid material.” It is further understood that, in certain preferred embodiments, the “activator” described herein may be a “transition metal activator,” the “monomer” described herein may be a “ROMP precursor,” and the “pre-catalyst” or “precatalyst” described herein may be a “ROMP pre-catalyst.” [0010] Aspects may include one or more of the following features.

[0011] Initiating the polymerization reaction may include generating a polymerization catalyst by reaction of the pre-catalyst with the activator, where the polymerization catalyst reacts with the monomer to generate a polymer and a polymerization catalyst. The polymerization reaction may cause solidification of the deposited layer sufficient for deposition of a subsequent layer on the deposited layer. The second material may include a solvent. The second material may not include a monomer.

[0012] The dispersion of the second fluid material through the first fluid material may be due at least in part to diffusion. Depositing the layers of material may include depositing a support material prior to depositing the first fluid material and the second fluid material, depositing the second fluid material onto the support material, and depositing the first fluid material onto the second fluid material.

[0013] Depositing the support material may include depositing a plurality of layers of support material to form a well, depositing the second fluid material onto the support material may include coating an inner surface of the support material in the well with the second fluid material, and depositing the first fluid material onto the second fluid material may include depositing the first fluid material into the well. [0014] The pre-catalyst may be UltraLatMet, the activator may be the Cu Co-Cat C7 copper(II) coordination complex, and the monomer may be a blend of strained cyclic olefins 2-Ethylidene-l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8- dimethanonaphthalene and 5-decylbicyclo[2.2.1]hept-2-ene.

[0015] Among other advantages, aspects described herein are able to form layers of polymer from a combination of precatalyst, activator, and monomer, where the layers cure quickly enough to support a subsequent layer being deposited thereon in an inkjet printing process. This expands the types of materials that can be used in inkjet-based additive manufacturing beyond photopolymers.

[0016] Aspects described herein advantageously do not mix precatalyst with monomer prior to deposition because, without wishing to be bound by theory, doing so may result in at least a small amount of polymerization occurring in the mixture (e.g., in the printhead or material storage). The first time precatalyst encounters monomer is upon deposition.

[0017] Other features and advantages of the invention are apparent from the following description and from the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG. 1 is an inkjet-based additive manufacturing system.

[0019] FIG. 2 is a droplet of precatalyst fluid being deposited onto a liquid mixture of activator and monomer.

[0020] FIG. 3 shows the droplet of precatalyst fluid of FIG. 2 diffusing through the liquid mixture of activator and monomer.

[0021] FIG. 4 is a reaction for creating a polymerization catalyst from a precatalyst and activator.

[0022] FIG. 5 shows the formation of a section of monomer mixed with catalyst.

[0023] FIG. 6 shows a polymerization reaction.

[0024] FIG. 7 shows the formation of a section of polymer mixed with catalyst.

[0025] FIG. 8 shows the precatalyst diffusing through the mixture of activator and monomer, causing polymerization of the layer of material.

[0026] FIG. 9 shows the polymerized layer.

[0027] FIG. 10 shows a void formed by support material.

[0028] FIG. 11 shows the void of FIG. 10 with its interior surface coated with precatalyst. [0029] FIG. 12 shows a mixture of monomer and activator deposited in the void and onto the precatalyst coating of FIG. 11.

[0030] FIG. 13 shows a polymerization reaction occurring in the mixture of monomer, activator, and precatalyst of FIG. 12.

[0031] FIG. 14 shows a subsequent layer of a mixture of monomer and activator deposited into the void.

[0032] FIG. 15 shows a precatalyst deposited onto the layer of mixed monomer and activator of FIG. 14.

[0033] FIG. 16 shows a polymerization reaction occurring in layer of FIG. 15

[0034] FIG. 17 shows the layer of FIG. 15 after polymerization.

DETAILED DESCRIPTION

[0035] Referring to FIG. 1, an inkjet-based additive manufacturing system 100 receives an object specification 102 and fabricates a physical instance of the object 103 represented by the object specification. The system 100 includes a controller 104 that controls ejection of material droplets 105 (in liquid form) from one or more printheads 106 and the movement of a build platform 107 (via an actuator 108) according to the object specification 102 to cause layer-by-layer fabrication of the instance of the object 103 on the build platform 107. As is described in greater detail below, the system and materials are configured to deposit layers of material as liquid and to cause those layers to quickly solidify without requiring the use of UV or other radiation to initiate solidification.

[0036] The printheads 106 include jets 110, with each jet ejecting a different material or mixture of materials in a liquid form onto the platform or a partial fabrication of the instance of the object 103. In the simplified example of FIG. 1, the printhead 106 includes a first jet 110a and a second jet 110b. The first jet 110a ejects a liquid mixture 111 of monomer (e.g., a ROMP precursor as described herein) 112 (represented as a circle) and an activator (e.g., a transition metal activator as described herein) 114 (represented as a notched square). The second jet 110b ejects a precatalyst (e.g., a ROMP pre-catalyst as described herein) 116 (represented with a pointed protrusion conforming to the notch of the activator) mixed with a solvent (e.g., an inert solvent as described herein) (not shown) in liquid form.

[0037] The controller 104 causes the printheads 106 to fabricate the instance of the object 103 by repeatedly depositing layers of material as the build platform 107 moves. At least some layers of material are deposited as a combination of the monomer/activator mixture 111 and the precatalyst 116. In some examples, those layers are formed by causing the first jet 110a to deposit a layer 113 of the monomer/activator mixture 111 ahead of the second jet 110b depositing precatalyst fluid 116, such that the precatalyst fluid 116 is deposited onto the monomer/activator mixture 111. As is illustrated in the examples below, the precatalyst 116 diffuses through the deposited layer of the mixture 111, initiating a polymerization reaction and causing solidification of the layer by polymerization.

[0038] In general, the concentration of the activator 114 in the monomer/activator mixture I l l is carefully chosen to generate a corresponding concentration of polymerization catalyst in the deposited layer to (1) ensure that polymerization of the layer is quick enough that the layer is sufficiently solid in time for a next layer is deposited thereon and (2) ensure that polymerization does not occur so quickly that diffusion of the precatalyst 116 through the deposited layer of the mixture 111 is prevented or inhibited. In some embodiments, the precatalyst fluid (e.g., a Type B fluid material as described herein, comprising a ROMP pre-catalyst as described herein) is deposited in an amount such that the ROMP pre-catalyst is always in stoichiometric excess of the activator (e.g., a transition metal activator as described herein).

1 EXEMPLARY OPERATION

[0039] A detailed schematic view of region 115 of FIG. 1 is shown, with greatly exaggerated vertical scale, in FIGs. 2-9 to illustrate a series of events caused by depositing the precatalyst 116 onto the monomer/activator mixture 111. Referring to FIG. 2, a droplet 205 of precatalyst fluid 116 is approaching a previously deposited amount of monomer/activator mixture 111.

[0040] Referring to FIG. 3, when the droplet of precatalyst fluid 116 reaches the monomer/activator mixture 111, the precatalyst 116 begins diffusing through the monomer/activator mixture 111, resulting in a first region 220 where the monomer 112, activator 114, and precatalyst 116 are mixed (recognizing that the regions illustrated do not truly have as distinct boundaries as illustrated). Referring to FIG. 4, as a result of that mixing, a catalyst formation reaction 423 occurs in the first region 220, where the activator 114 and the precatalyst 116 combine to form a polymerization catalyst 422.

[0041] Referring to FIG. 5, a second region 524, including a mixture of monomer 112 and catalyst 422, is formed as a result of the activator 114 and precatalyst 116 reacting to form the polymerization catalyst 422. A liberal amount of precatalyst 116 is deposited, and any precatalyst 116 that didn’t react with the activator to form a catalyst 422 the second region 524 continues to diffuse through the monomer/ activator mixture 111, causing the first region 220 to expand.

[0042] Referring to FIG. 6, the polymerization catalyst 422 and the monomer 112 in the second region 524 undergo a polymerization reaction 625 to form polymer 626 and catalyst 422, which may be the same or different species depending on the type of polymerization reaction. Referring to FIG. 7, as the polymerization reaction 625 proceeds, a third, polymerized region 627 forms.

[0043] Referring to FIG. 8, the first region 220 including the precatalyst 116 continues to diffuse through the activator/monomer mixture 111, followed by the second region 524 and the third, polymerized region 627. Referring to FIG. 9, eventually the entire layer 113 is polymerized.

2 EXEMPLARY OPERATION WITH OFFSET PRINTING

[0044] Referring to FIGs. 10-17 (shown with greatly exaggerated vertical scale), in some examples an offset printing technique is used to fabricate a support material (e.g., wax) “well” that is subsequently filled with build material. In such examples, it may be preferable to deposit the precatalyst in a way that coats an interior surface of the well prior to depositing any of the activator/monomer mixture (e.g., due to undesirable interactions between the activator/monomer mixture and the support material).

[0045] Referring to FIG. 10, one or more layers of support material 1030 are deposited to form a well 1032. In FIG. 11, precatalyst fluid 116 is deposited to coat an interior surface 1034 of the well 1032. In FIG. 12, a first layer 1036 of activator/monomer mixture 111 is deposited in the coated well 1032. In FIG. 13, the precatalyst fluid 116 coating diffuses through the first layer 1036 of activator/monomer mixture 111, causing polymerization of a part of the first layer 1036.

[0046] In FIG. 14, the first layer 1036 of activator/monomer mixture 111 is polymerized (i.e., at least substantially polymerized or polymerized “enough” to support deposition of a subsequent layer) and a second layer 1038 of activator/monomer mixture 111 is deposited on the first layer 1036. In FIG. 15, the precatalyst fluid 116 coating diffuses into the sides of the second layer 1038, beginning polymerization of the second layer 1038. Precatalyst fluid 116 is deposited onto the second layer 1038. In FIG. 16, the precatalyst 116 deposited onto the second layer 1038 diffuses through the activator/monomer mixture 111 of the second layer 1038, continuing polymerization of the second layer 1038. Finally, in FIG. 17 polymerization of the second layer 1038 completes.

3 MATERIALS

[0047] Many different combinations of precatalyst, activator, and monomer are suitable to accomplish the printing processes described above. In one suitable example the pre-catalyst (e.g., the ROMP pre-catalyst) comprises Compound C-2 or a solvate thereof (in some embodiments, Compound C-2 is commercially available under the name UltraLatMet from Apeiron Synthesis, CAS: 2501978-79-4), the activator (e.g., the transition metal activator) is a copper(II) coordination complex comprising Compound A-l (in some embodiments, Compound A-l is commercially available under the name Cu Co-Cat C7 from Apeiron Synthesis). Without wishing to be bound by theory, the Compound A-l can activate Compound C-2 via a chemical transformation known as ligand exchange and sometimes known as transmetallation to generate the active catalyst (ROMP catalyst). In this example the monomers are a blend of the strained cyclic olefins (ROMP monomers) 2-Ethylidene- l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (CAS: 38233-76-0) and 5- decylbicyclo[2.2.1]hept-2-ene (CAS: 22094-85-5). The precatalyst UltraLatMet is dissolved in a mixture of biphenyl (CAS: 92-52-4) and diphenyl ether (CAS: 101-84- 8) to form the precatalyst fluid and the activator Cu Co-Cat C7 is dissolved in the ROMP monomers to form the monomer fluid. The resulting polymer poly(2- ethylidene-l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene-co-5- decylbicyclo[2.2.1]hept-2-ene) is a cyclic olefin polymer made via ROMP.

Definitions

[0048] Unless otherwise stated, the following terms used in the specification and claims have the following meanings set out below.

[0049] The articles "a" and "an" are used in this disclosure to refer to one or more than one (i.e., to at least one) of the grammatical object of the article. By way of example, "an element" means one element, at least one element, or more than one element.

[0050] As used herein, the term “ring-opening metathesis polymerization” or “ROMP” refers to a form of chain-growth polymerization in which the terminus of a polymer chain repeatedly reacts with a cyclic alkene monomer by olefin metathesis to form a longer polymer.

[0051] As used herein, the term “curing” refers to a process of converting a material by forming polymers and/or linking existing polymers in the material, thereby producing a cured material. In some embodiments, the conversion is initiated by the reaction of an activator (e.g., a transition metal activator) and a pre-catalyst (e.g., a ROMP pre-catalyst) to product a catalyst (e.g., a ROMP catalyst).

[0052] As used herein, the term “about” refers to a range covering any normal fluctuations appreciated by one of ordinary skill in the relevant art. In some embodiments, the term “about” refers to a range of values that fall within 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less in either direction (greater than or less than) of the stated reference value unless otherwise stated or otherwise evident from the context (except where such number would exceed 100% of a possible value).

[0053] As used herein, the term “derivative” refers to compounds that have a common core structure as compared to the referenced compound and/or share one or more property with the referenced compound. In some embodiments, the derivatives are substituted with various groups as described herein as compared to the referenced compound.

[0054] Without wishing to be limited by this statement, it is understood that, while various options for variables are described herein, the disclosure intends to encompass operable embodiments having combinations of the options. The disclosure may be interpreted as excluding the non-operable embodiments caused by certain combinations of the options.

[0055] The term “alkyl”, as used herein, refers to saturated, straight-chain or branched hydrocarbon radicals containing, in certain embodiments, between one and twenty, including between one and ten, or between one and six, carbon atoms. Branched means that one or more lower Ci-Ce alkyl groups such as methyl, ethyl or propyl are attached to a linear alkyl chain. Exemplary alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, and 3-pentyl. Examples of Ci-Ce alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, neopentyl, n-hexyl radicals; and examples of Ci-Cs alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, neopentyl, n-hexyl, heptyl, octyl radicals. Examples of C1-C20 alkyl radicals include but are not limited to hexadecamethyl, hexadecaethyl, hexadecapropyl, octadecamethyl, octadecaethyl, octadecapropyl and the like. In some embodiments, a straight chain or branched alkyl has six or fewer carbon atoms (e.g, Ci-Ce for straight chain, C3-C6 for branched chain), and in another embodiment, a straight chain or branched alkyl has four or fewer carbon atoms.

[0056] As used herein, the term “alkenyl” includes unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but that contain at least one double bond. For example, the term “alkenyl” includes straight chain alkenyl groups (e.g., ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl), and branched alkenyl groups. In certain embodiments, a straight chain or branched alkenyl group has six or fewer carbon atoms in its backbone (e.g., C2-C6 for straight chain, C3-C6 for branched chain). The term “C2-C6” includes alkenyl groups containing two to six carbon atoms. The term “C3-C6” includes alkenyl groups containing three to six carbon atoms.

[0057] As used herein, the term “alkynyl” includes unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but which contain at least one triple bond. For example, “alkynyl” includes straight chain alkynyl groups (e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl), and branched alkynyl groups. In certain embodiments, a straight chain or branched alkynyl group has six or fewer carbon atoms in its backbone (e.g, C2-C6 for straight chain, C3-C6 for branched chain). The term “C2-C6” includes alkynyl groups containing two to six carbon atoms. The term “C3-C6” includes alkynyl groups containing three to six carbon atoms.

[0058] As used herein, the term “cycloalkyl” refers to a saturated or partially unsaturated hydrocarbon monocyclic or polycyclic (e.g., fused, bridged, or spiro rings) system having 3 to 30 carbon atoms (e.g., C3-C12, C3-C10, or C3-Cs). Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, 1,2,3,4-tetrahydronaphthalenyl, and adamantyl. In the case of polycyclic cycloalkyl, only one of the rings in the cycloalkyl needs to be non-aromatic.

[0059] As used herein, the term “heterocycloalkyl” refers to a saturated or partially unsaturated 3-8 membered monocyclic, 7-12 membered bicyclic (fused, bridged, or spiro rings), or 11-14 membered tricyclic ring system (fused, bridged, or spiro rings) having one or more heteroatoms (such as O, N, S, P, or Se), e.g., 1 or 1-2 or 1-3 or 1-4 or 1-5 or 1-6 heteroatoms, or e.g._s 1, 2, 3, 4, 5, or 6 heteroatoms, independently selected from the group consisting of nitrogen, oxygen and sulfur, unless specified otherwise. Examples of heterocycloalkyl groups include, but are not limited to, piperidinyl, piperazinyl, pyrrolidinyl, dioxanyl, tetrahydrofuranyl, isoindolinyl, indolinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, isoxazolidinyl, triazolidinyl, oxiranyl, azetidinyl, oxetanyl, thietanyl, 1,2,3,6-tetrahydropyridinyl, tetrahydropyranyl, dihydropyranyl, pyranyl, morpholinyl, tetrahydrothiopyranyl, 1,4- diazepanyl, 1,4-oxazepanyl, 2-oxa-5-azabicyclo[2.2.1]heptanyl, 2,5- diazabicyclo[2.2.1]heptanyl, DABCO (l,4-diazabicyclo[2.2.2]octane); 2-oxa-6- azaspiro[3.3]heptanyl, 2,6-diazaspiro[3.3]heptanyl, l,4-dioxa-8-azaspiro[4.5]decanyl, l,4-dioxaspiro[4.5]decanyl, l-oxaspiro[4.5]decanyl, l-azaspiro[4.5]decanyl, 3'H- spirofcyclohexane- 1 , 1 '-isobenzofuran]-yl, 7'H-spiro[cyclohexane- 1 , 5'-furo[3 ,4- b]pyridin]-yl, 3'H-spiro[cyclohexane-l,l'-furo[3,4-c]pyridin]-yl, 3- azabicyclo[3.1.0]hexanyl, 3-azabicyclo[3.1.0]hexan-3-yl, 1, 4,5,6- tetrahydropyrrolo[3,4-c]pyrazolyl, 3,4,5,6,7,8-hexahydropyrido[4,3-d]pyrimidinyl, 4,5,6,7-tetrahydro-lH-pyrazolo[3,4-c]pyridinyl, 5,6,7,8-tetrahydropyrido[4,3- d]pyrimidinyl, 2-azaspiro[3.3]heptanyl, 2-methyl-2-azaspiro[3.3]heptanyl, 2- azaspiro[3.5]nonanyl, 2-methyl-2-azaspiro[3.5]nonanyl, 2-azaspiro[4.5]decanyl, 2- methyl-2-azaspiro[4.5]decanyl, 2-oxa-azaspiro[3.4]octanyl, 2-oxa-azaspiro[3.4]octan- 6-yl, 5,6-dihydro-4H-cyclopenta[b]thiophenyl, and the like. In the case of multicyclic heterocycloalkyl, only one of the rings in the heterocycloalkyl needs to be nonaromatic (e.g., 4,5,6,7-tetrahydrobenzo[c]isoxazolyl).

[0060] As used herein, the term “aryl” includes groups with aromaticity, including “conjugated,” or multicyclic systems with one or more aromatic rings and do not contain any heteroatom in the ring structure. The term aryl includes both monovalent species and divalent species. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl and the like. Conveniently, an aryl is phenyl.

[0061] As used herein, the term “heteroaryl” is intended to include a stable 5-, 6-, or 7-membered monocyclic or 7-, 8-, 9-, 10-, 11- or 12-membered bicyclic aromatic heterocyclic ring which consists of carbon atoms and one or more heteroatoms, e.g., 1 or 1-2 or 1-3 or 1-4 or 1-5 or 1-6 heteroatoms, or e.g._t 1, 2, 3, 4, 5, or 6 heteroatoms, independently selected from the group consisting of nitrogen, oxygen and sulfur. The nitrogen atom may be substituted or unsubstituted (i.e., N or NR wherein R is H or other substituents, as defined). The nitrogen and sulfur heteroatoms may optionally be oxidized (z.e., N^O and S(O)_P, where p = 1 or 2). It is to be noted that total number of S and O atoms in the aromatic heterocycle is not more than 1. Examples of heteroaryl groups include pyrrole, furan, thiophene, thiazole, isothiazole, imidazole, triazole, tetrazole, pyrazole, oxazole, isoxazole, pyridine, pyrazine, pyridazine, pyrimidine, and the like. Heteroaryl groups can also be fused or bridged with alicyclic or heterocyclic rings, which are not aromatic so as to form a multi cyclic system (e.g., 4,5,6,7-tetrahydrobenzo[c]isoxazolyl). In some embodiments, the heteroaryl is thiophenyl or benzothiophenyl. In some embodiments, the heteroaryl is thiophenyl. In some embodiments, the heteroaryl benzothiophenyl.

[0062] Furthermore, the terms “aryl” and “heteroaryl” include multicyclic aryl and heteroaryl groups, e.g., tricyclic, bicyclic, e.g., naphthalene, benzoxazole, benzodioxazole, benzothiazole, benzoimidazole, benzothiophene, quinoline, isoquinoline, naphthrydine, indole, benzofuran, purine, benzofuran, deazapurine, indolizine.

[0063] The cycloalkyl, heterocycloalkyl, aryl, or heteroaryl ring can be substituted at one or more ring positions (e.g., the ring-forming carbon or heteroatom such as N) with such substituents as described above, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkoxy, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkylaminocarbonyl, aralkylaminocarbonyl, alkenylaminocarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkenylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphonato, phosphinato, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety. Aryl and heteroaryl groups can also be fused or bridged with alicyclic or heterocyclic rings, which are not aromatic so as to form a multicyclic system.

[0064] As used herein, the term “substituted” means that any one or more hydrogen atoms on the designated atom is replaced with a selection from the indicated groups, provided that the designated atom’s normal valency is not exceeded, and that the substitution results in a stable compound. When a substituent is oxo or keto (ie., =0), then 2 hydrogen atoms on the atom are replaced. Keto substituents are not present on aromatic moieties. Ring double bonds, as used herein, are double bonds that are formed between two adjacent ring atoms (e.g., C=C, C=N or N=N). “Stable compound” and “stable structure” are meant to indicate a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture, and formulation into an efficacious polymeric material.

[0065] As used herein, the term “inert” refers to a moiety which is not chemically reactive, i.e., it does not react with other moieties or reagents. The person skilled in the art understands that the term “inert” does not per se exclude the presence of functional groups, but understands that the functional groups potentially present in an inert moiety are not reactive with functional groups of moieties/reagents brought in contact with the inert moiety.

[0066] As used herein, the term “inert atmosphere” refers to a substantially oxygen free environment and primarily consists of non-reactive gases. Exemplary inert atmospheres include a nitrogen atmosphere or an argon atmosphere.

[0067] When a bond to a substituent is shown to cross a bond connecting two atoms in a ring, then such substituent may be bonded to any atom in the ring. When a substituent is listed without indicating the atom via which such substituent is bonded to the rest of the compound of a given formula, then such substituent may be bonded via any atom in such formula. Combinations of substituents and/or variables are permissible, but only if such combinations result in stable compounds.

[0068] When any variable (e.g., R) occurs more than one time in any constituent or formula for a compound, its definition at each occurrence is independent of its definition at every other occurrence. Thus, for example, if a group is shown to be substituted with 0-2 R moieties, then the group may optionally be substituted with up to two R moieties and R at each occurrence is selected independently from the definition of R. Also, combinations of substituents and/or variables are permissible, but only if such combinations result in stable compounds.

[0069] As used herein, the term “hydroxy” or “hydroxyl” includes groups with an -OH or -O’.

[0070] As used herein, the term “halo” or “halogen” refers to fluoro, chloro, bromo and iodo.

[0071] As used herein, the term “alkoxy” or “alkoxyl” includes substituted and unsubstituted alkyl, alkenyl and alkynyl groups covalently linked to an oxygen atom. Examples of alkoxy groups or alkoxyl radicals include, but are not limited to, methoxy, ethoxy, isopropyloxy, propoxy, butoxy and pentoxy groups. Examples of substituted alkoxy groups include halogenated alkoxy groups. The alkoxy groups can be substituted with groups such as alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moi eties. Examples of halogen substituted alkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy and trichloromethoxy.

[0072] As used herein, the expressions “one or more of A, B, or C,” “one or more A, B, or C,” “one or more of A, B, and C,” “one or more A, B, and C,” “selected from the group consisting of A, B, and C”, “selected from A, B, and C”, and the like are used interchangeably and all refer to a selection from a group consisting of A, B, and/or C, i.e., one or more As, one or more Bs, one or more Cs, or any combination thereof, unless indicated otherwise.

[0073] As used herein, the term “pigment” refers to a colored, black, white, or fluorescent particulate organic or inorganic solid. In some embodiments, the pigment insoluble in, and essentially physically and chemically unaffected by, the vehicle or substrate in which it is incorporated. In some embodiments, the pigment alters appearance by selective absorption and/or by scattering of light. In some embodiments, the pigment is dispersed in vehicles or substrates for application, as for instance in the manufacture or inks or other polymeric materials. In some embodiments, the pigment retains a crystal or particulate structure throughout the coloration process.

[0074] As used herein, the term “dye” refers to an intensely colored or fluorescent organic substances which imparts color to a substrate by selective absorption of light. In some embodiments, the dye is soluble and/or goes through an application process which, at least temporarily, destroys any crystal structure by absorption, solution, and mechanical retention, or by ionic or covalent chemical bonds.

[0075] As used herein, the term “viscosity” refers to the ability of a composition (e.g., the formulation of the present disclosure) to resist deformation at a given rate. [0076] As used herein, the term “elongation at break” refers to the ratio between increased length and initial length after breakage of the tested specimen at a controlled temperature. In some embodiments, the elongation at break is measured according to ASTM D412, ASTM D624, or ASTM D638.

[0077] As used herein, the term “Young’s modulus” refers to a mechanical property that measures the stiffness of a solid material. Young’s modulus is associated with the relationship between stress (force per unit area) and strain (proportional deformation) in a material in the linear elasticity regime of a uniaxial deformation. In some embodiments, the Young’s modulus is measured according to ASTM D412, ASTM D624, or ASTM D638.

[0078] As used herein, the term “notched Izod impact strength” refers to a mechanical property that measures the impact resistance of a solid material. In some embodiments, it is measured by a method in which a pivoting arm is raised to a specific height (constant potential energy) and then released. The arm swings down hitting a notched sample, breaking the specimen. The energy absorbed by the sample is calculated from the height the arm swings to after hitting the sample. A notched sample is generally used to determine impact energy and notch sensitivity. Notched Izod impact strength is associated with the energy lost per unit cross-sectional area (e.g., J/m²) at the notch. In some embodiments, the notched Izod impact strength is measured according to ASTM D256. In some embodiments, the notched Izod impact strength is measured according to ISO 180/B.

[0079] It is to be understood that, throughout the description, where compositions are described as having, including, or comprising specific components, it is contemplated that compositions may also consist essentially of, or consist of, the recited components. Similarly, where methods or processes are described as having, including, or comprising specific process steps, the processes also consist essentially of, or consist of, the recited processing steps. Further, it should be understood that the order of steps or order for performing certain actions is immaterial so long as the invention remains operable. Moreover, two or more steps or actions can be conducted simultaneously. [0080] It is to be understood that compounds of the present disclosure can be prepared in a variety of ways using commercially available starting materials, compounds known in the literature, or from readily prepared intermediates, by employing standard synthetic methods and procedures either known to those skilled in the art, or which will be apparent to the skilled artisan in light of the teachings herein. Standard synthetic methods and procedures for the preparation of organic molecules and functional group transformations and manipulations can be obtained from the relevant scientific literature or from standard textbooks in the field. Although not limited to any one or several sources, classic texts such as Smith, M. B., March, J., March ’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5^th edition, John Wiley & Sons: New York, 2001; Greene, T.W., Wuts, P.G. M., Protective Groups in Organic Synthesis, 3^rd edition, John Wiley & Sons: New York, 1999; R. Larock, Comprehensive Organic Transformations, VCH Publishers (1989);

L. Fieser and M. Fieser, Fieser andFieser ’s Reagents for Organic Synthesis, John Wiley and Sons (1994); and L. Paquette, ed., Encyclopedia of Reagents for Organic Synthesis, John Wiley and Sons (1995), incorporated by reference herein, are useful and recognized reference textbooks of organic synthesis known to those in the art.

[0081] One of ordinary skill in the art will note that, during the reaction sequences and synthetic schemes described herein, the order of certain steps may be changed, such as the introduction and removal of protecting groups. One of ordinary skill in the art will recognize that certain groups may require protection from the reaction conditions via the use of protecting groups. Protecting groups may also be used to differentiate similar functional groups in molecules. A list of protecting groups and how to introduce and remove these groups can be found in Greene, T.W., Wuts, P.G.

M., Protective Groups in Organic Synthesis, 3^rd edition, John Wiley & Sons: New York, 1999.

[0082] All percentages and ratios used herein, unless otherwise indicated, are by weight.

[0083] Other features and advantages of the present disclosure are apparent from the different examples. The provided examples illustrate different components and methodology useful in practicing the present disclosure. The examples do not limit the claimed disclosure. Based on the present disclosure the skilled artisan can identify and employ other components and methodology useful for practicing the present disclosure. [0084] All publications and patent documents cited herein are incorporated herein by reference as if each such publication or document was specifically and individually indicated to be incorporated herein by reference. Citation of publications and patent documents is not intended as an admission that any is pertinent prior art, nor does it constitute any admission as to the contents or date of the same. The invention having now been described by way of written description, those of skill in the art will recognize that the invention can be practiced in a variety of embodiments and that the foregoing description and examples below are for purposes of illustration but not limitation.

Combinations, Materials, Kits, and Systems of the Present Disclosure [0085] In some aspects, the present disclosure provides a combination comprising:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator;

(iii) a ROMP pre-catalyst; and

(iv) optionally, an activator protecting agent.

[0086] As used herein, the term “combination” refers to any association between two or among more items (e.g., two or more of items (i)-(iv)). The term “combination” does not necessarily require that all of the recited elements be present in the same solution, composition, or fluid material. The items recited in a combination described herein may be present in a single composition (e.g. a solution, build material, fluid material, etc.) or may be divided among two or more different compositions.

[0087] In some aspects, the present disclosure provides a build material comprising a combination disclosed herein.

[0088] In some aspects, the present disclosure provides a kit comprising a combination disclosed herein.

[0089] In some aspects, the present disclosure provides a kit comprising a Type A fluid material and a Type B fluid material, wherein: the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator; and the Type B fluid material comprises:

(iii) a ROMP pre-catalyst. [0090] In some aspects, the present disclosure provides a kit comprising a Type A fluid material, a Type B fluid material, and a support material, wherein: the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator; and the Type B fluid material comprises:

(iii) a ROMP pre-catalyst.

[0091] In some aspects, the present disclosure provides a kit comprising one or more Type A fluid materials and one or more Type B fluid material, wherein: the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator; and the Type B fluid material comprises:

(iii) a ROMP pre-catalyst.

[0092] In some aspects, the present disclosure provides a kit comprising one or more Type A fluid materials, one or more Type B fluid material, and one or more support materials, wherein: the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator; and the Type B fluid material comprises:

(iii) a ROMP pre-catalyst.

[0093] In some aspects, the present disclosure provides a Type A fluid material comprising:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii)a transition metal activator; wherein the Type A fluid material does not comprise a ROMP pre-catalyst.

[0094] In some aspects, the present disclosure provides a Type B fluid material comprising:

(iii)a ROMP pre-catalyst; wherein the Type B fluid material does not comprise a transition metal activator.

[0095] In some embodiments, the Type A fluid material further comprises an activator protecting agent. [0096] In some embodiments, the Type A fluid material further comprises an antioxidant. In some embodiments, the Type A fluid material further comprises an antioxidant that is not an activator protecting agent.

[0097] In some embodiments, the Type B fluid material further comprises an antioxidant. In some embodiments, the Type B fluid material further comprises an antioxidant that is not an activator protecting agent.

[0098] In some embodiments the Type A fluid material further comprises an organic acid.

[0099] In some embodiments, the Type A fluid material further comprises a catalyst inhibitor.

[0100] In some embodiments, the Type A fluid material further comprises one or more additives independently selected from a reinforcing agent, an impact modifier, a dye, a pigment, and a flame retardant.

[0101] In some embodiments, the Type B fluid material further comprises an inert solvent.

[0102] In some embodiments, the Type B fluid material further comprises a catalyst inhibitor.

[0103] In some embodiments, the Type B fluid material further comprises one or more additives independently selected from a reinforcing agent, an impact modifier, a dye, a pigment, and a flame retardant.

[0104] In some embodiments, the Type B fluid material further comprises a ROMP precursor.

[0105] In a preferred embodiment, the Type B fluid material does not further comprise a ROMP precursor.

ROMP Precursors

[0106] In some embodiments, the ROMP precursor is a compound of Formula (S- II):

wherein: q-S is 0, 1 or 2; R³ and R⁵ are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2- C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R^S-1A, -O-C(=O)- R^S-1A, C6-C14 aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A; R⁴ and R⁶ are each independently hydrogen, halogen, C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)- R^S-1A, -O- C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷), wherein the C₁-₁₆ alkyl, C₂-C₁₆ alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A; or R⁴ and R⁶, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl; each R^S-1A is independently halogen, C₁-C₆ alkyl, or C₁-C₁₆ alkoxy; Z is a bond, -(CR^S-2AR^S-3A)_a-, -O(CR^S-2AR^S-3A)_a-, -(CR^S-2AR^S-3A)_aO-, -(CR^S-2AR^S-3A)a-O-(CR^S-2AR^S-3A)b-, -(CR^S-2AR^S-3A)a-O-(SiR^S-2AR^S-3A)b-, -(CR^S-2AR^S-3A)a- (C=O)O-(CR^S-2AR^S-3A)_b-, -(CR^S-2AR^S-3A)-O(C=O)-(CR^S-2AR^S-3A)_b-, -(CR^S-2AR^S-3A)_a- (C=O)-(CR^S-2AR^S-3A)_b-; Each R^S-2A and R^S-3A is independently hydrogen, C1-C6 alkyl, C1-C6 alkoxy, - O-C(=O)-C₁-C₆ alkyl, -C(=O)-(C₁-C₆ alkyl), phenyl, or -O-phenyl; R⁷ is phenyl optionally substituted with one or more R^S-7A; Each R^S-7A is independently selected from C1-C6 alkyl, C1-C6 alkoxy, - O-C(=O)-C1-C6 alkyl, -C(=O)-(C1-C6 alkyl), phenyl, or -O-phenyl; and each a and b is independently an integer between 1 and 12; is a single bond or a double bond, wherein when is a double bond, R³ and R⁵ are both absent. [0107] In some embodiments, q-S is 0, 1 or 2. In some embodiments, q-S is 0 or 1. In some embodiments, q-S is 0. In some embodiments, q-S is 1. [0108] In some embodiments, R³ and R⁵ are each independently absent, hydrogen, halogen, C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₃-C₁₄ cycloalkyl, C₁-C₁₆ alkoxy, -C(=O)-R^S-1A, -O-C(=O)- R^S-1A, C6-C14 aryl, -O-C6-C14 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A. In some embodiments, R³ and R⁵ are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C₁-C₁₆ alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷). In some embodiments, R³ and R⁵ are each independently absent, hydrogen, halogen, C₁-C₁₆ alkyl, or C₂-C₁₆ alkenyl. In some embodiments, R³ and R⁵ are each independently C₈ alkyl, C₁₀ alkyl, or C₂ alkenyl. [0109] In some embodiments, one of R³ and R⁵ is C1-C16 alkyl. In some embodiments, one of R³ and R⁵ is C2-C16 alkenyl. In some embodiments, one of R³ and R⁵ is C₃-C₁₄ cycloalkyl. In some embodiments, one of R³ and R⁵ is C₁-C₁₆ alkoxy. In some embodiments, one of R³ and R⁵ is -C(=O)- R^S-1A. In some embodiments, one of R³ and R⁵ is -O-C(=O)- R^S-1A. In some embodiments, one of R³ and R⁵ is C6-C14 aryl. In some embodiments, one of R³ and R⁵ is -O-C₆-C₁₄ aryl. In some embodiments, one of R³ and R⁵ is 3- to 14-membered heterocycloalkyl. In some embodiments, one of R³ and R⁵ is 5- to 14-membered heteroaryl. In some embodiments, one of R³ and R⁵ is -Si(R^S-1A)₃. In some embodiments, one of R³ and R⁵ is -Z-(R⁷). In some embodiments, one of R³ and R⁵ is C₈ alkyl, C₁₀ alkyl, or C₂ alkenyl. [0110] In some embodiments, R³ is absent, hydrogen, halogen, C₁-C₁₆ alkyl, C₂- C₁₆ alkenyl, C₃-C₁₄ cycloalkyl, C₁-C₁₆ alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆- C14 aryl, -O-C6-C14 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C₃-C₁₄ cycloalkenyl, C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A. In some embodiments, R³ is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3- C₁₄ cycloalkyl, C₁-C₁₆ alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆- C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R³ is C1-16 alkyl substituted with one or more F, C2-C16 alkenyl substituted with one or more F, C3-C14 cycloalkyl substituted with one or more F, C3-C14 cycloalkenyl substituted with one or more F, C6-C14 aryl substituted with one or more F, 3- to 14- membered heterocycloalkyl substituted with one or more F, or 5- to 14-membered heteroaryl substituted with one or more F. In some embodiments, R³ is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, - C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷). In some embodiments, R³ is C8 alkyl, C10 alkyl, or C2 alkenyl. [0111] In some embodiments, R³ is absent. In some embodiments, R³ is hydrogen. In some embodiments, R³ is C₁-C₁₆ alkyl. In some embodiments, R³ is C₂-C₁₆ alkenyl. In some embodiments, R³ is C3-C14 cycloalkyl. In some embodiments, R³ is C1-C16 alkoxy. In some embodiments, R³ is -C(=O)- R^S-1A. In some embodiments, R³ is -O- C(=O)- R^S-1A. In some embodiments, R³ is C₆-C₁₄ aryl. In some embodiments, R³ is - O-C6-C14 aryl. In some embodiments, R³ is 3- to 14-membered heterocycloalkyl. In some embodiments, R³ is 5- to 14-membered heteroaryl. In some embodiments, R³ is -Si(R^S-1A)₃. In some embodiments, R³ is -Z-(R⁷). In some embodiments, R³ is C₈ alkyl. In some embodiments, R³ is C₁₀ alkyl. In some embodiments, R³ is C₂ alkenyl. [0112] In some embodiments, R⁵ is absent, hydrogen, halogen, C1-C16 alkyl, C2- C₁₆ alkenyl, C₃-C₁₄ cycloalkyl, C₁-C₁₆ alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆- C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C₃-C₁₄ cycloalkenyl, C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A. In some embodiments, R⁵ is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3- C14 cycloalkyl, C1-C16 alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C6-C14 aryl, -O-C6- C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R⁵ is C₁-₁₆ alkyl substituted with one or more F, C₂-C₁₆ alkenyl substituted with one or more F, C3-C14 cycloalkyl substituted with one or more F, C3-C14 cycloalkenyl substituted with one or more F, C₆-C₁₄ aryl substituted with one or more F, 3- to 14- membered heterocycloalkyl substituted with one or more F, or 5- to 14-membered heteroaryl substituted with one or more F. In some embodiments, R⁵ is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, - C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C6-C14 aryl, -O-C6-C14 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷). In some embodiments, R⁵ is C8 alkyl, C10 alkyl, or C2 alkenyl. [0113] In some embodiments, R⁵ is absent. In some embodiments, R⁵ is hydrogen. In some embodiments, R⁵ is C₁-C₁₆ alkyl. In some embodiments, R⁵ is C₂-C₁₆ alkenyl. In some embodiments, R⁵ is C₃-C₁₄ cycloalkyl. In some embodiments, R⁵ is C₁-C₁₆ alkoxy. In some embodiments, R⁵ is -C(=O)- R^S-1A. In some embodiments, R⁵ is -O- C(=O)- R^S-1A. In some embodiments, R⁵ is C₆-C₁₄ aryl. In some embodiments, R⁵ is - O-C₆-C₁₄ aryl. In some embodiments, R⁵ is 3- to 14-membered heterocycloalkyl. In some embodiments, R⁵ is 5- to 14-membered heteroaryl. In some embodiments, R⁵ is -Si(R^S-1A)3. In some embodiments, R⁵ is -Z-(R⁷). In some embodiments, R⁵ is C8 alkyl. In some embodiments, R⁵ is C₁₀ alkyl. In some embodiments, R⁵ is C₂ alkenyl. [0114] In some embodiments, R⁴ and R⁶ are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14- membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6- C₁₄ aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A. In some embodiments, R⁴ and R⁶ are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C₃-C₁₄ cycloalkenyl, C₁-C₁₆ alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆- C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷). In some embodiments, one of R⁴ and R⁶ is C1-C16 alkyl. In some embodiments, one of R⁴ and R⁶ is C2-C16 alkenyl. In some embodiments, one of R⁴ and R⁶ is C₈ alkyl, C₁₀ alkyl, or C₂ alkenyl. [0115] In some embodiments, one of R⁴ and R⁶ is C1-C16 alkyl. In some embodiments, one of R⁴ and R⁶ is C6-C16 alkyl. In some embodiments, one of R⁴ and R⁶ is C₈-C₁₀ alkyl. In some embodiments, one of R⁴ and R⁶ is C₈ alkyl. In some embodiments, one of R⁴ and R⁶ is C₁₀ alkyl. [0116] In some embodiments, one of R⁴ and R⁶ is C2-C6 alkenyl. In some embodiments, one of R⁴ and R⁶ is C₂-C₃ alkenyl. In some embodiments, one of R⁴ and R⁶ is C2 alkenyl. In some embodiments, R³ is absent and R⁴ is

. [0117] In some embodiments, R⁴ is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)- R^S-1A, -O- C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A. In some embodiments, R⁴ is hydrogen, halogen, C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)- R^S-1A, -O- C(=O)- R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷), wherein the C₁-₁₆ alkyl, C₂-C₁₆ alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R⁴ is C₁-₁₆ alkyl substituted with one or more F, C₂- C16 alkenyl substituted with one or more F, C3-C14 cycloalkyl substituted with one or more F, C3-C14 cycloalkenyl substituted with one or more F, C6-C14 aryl substituted with one or more F, 3- to 14-membered heterocycloalkyl substituted with one or more F, or 5- to 14-membered heteroaryl substituted with one or more F. In some embodiments, R⁴ is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C₃-C₁₄ cycloalkenyl, C₁-C₁₆ alkoxy, -C(=O)- R^S-1A, -O-C(=O)- R^S-1A, C₆- C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷). In some embodiments, R⁴ is C1-C16 alkyl. In some embodiments, R⁴ is C₂-C₁₆ alkenyl. In some embodiments, R⁴ is C₈ alkyl, C₁₀ alkyl, or C₂ alkenyl. [0118] In some embodiments, R⁴ is hydrogen. In some embodiments, R⁴ is halogen. In some embodiments, R⁴ is C1-C16 alkyl. In some embodiments, R⁴ is C2- C₁₆ alkenyl. In some embodiments, R⁴ is C₃-C₁₄ cycloalkyl. In some embodiments, R⁴ is C3-C14 cycloalkenyl. In some embodiments, R⁴ is C1-C16 alkoxy. In some embodiments, R⁴ is -C(=O)-R^S-1A. In some embodiments, R⁴ is -O-C(=O)-R^S-1A. In some embodiments, R⁴ is C₆-C₁₄ aryl. In some embodiments, R⁴ is -O-C₆-C₁₄ aryl. In some embodiments, R⁴ is 3- to 14-membered heterocycloalkyl. In some embodiments, R⁴ is 5- to 14-membered heteroaryl. In some embodiments, R⁴ is -Si(R^S-1A)3. In some embodiments, R⁴ is -Z-(R⁷). [0119] In some embodiments, R⁶ is C1-C16 alkyl. In some embodiments, R⁶ is C6- C16 alkyl. In some embodiments, R⁶ is C8-C10 alkyl. In some embodiments, R⁶ is C80 alkyl. In some embodiments, R⁶ is C₁₀ alkyl. [0120] In some embodiments, R⁶ is C2-C6 alkenyl. In some embodiments, R⁶ is C2-C3 alkenyl. In some embodiments, R⁶ is C2 alkenyl. In some embodiments, R⁵ is absent

. [0121] In some embodiments, R⁶ is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C₃-C₁₄ cycloalkyl, C₃-C₁₄ cycloalkenyl, C₁-C₁₆ alkoxy, -C(=O)-R^S-1A, -O- C(=O)-R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S-1A. In some embodiments, R⁶ is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R^S-1A, -O- C(=O)-R^S-1A, C₆-C₁₄ aryl, -O-C₆-C₁₄ aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)_3, or -Z-(R⁷), wherein the C₁-₁₆ alkyl, C₂-C₁₆ alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R⁶ is C₁-₁₆ alkyl substituted with one or more F, C₂- C16 alkenyl substituted with one or more F, C3-C14 cycloalkyl substituted with one or more F, C₃-C₁₄ cycloalkenyl substituted with one or more F, C₆-C₁₄ aryl substituted with one or more F, 3- to 14-membered heterocycloalkyl substituted with one or more F, or 5- to 14-membered heteroaryl substituted with one or more F. In some embodiments, R⁶ is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C₃-C₁₄ cycloalkenyl, C₁-C₁₆ alkoxy, -C(=O)-R^S-1A, -O-C(=O)-R^S-1A, C₆- C14 aryl, -O-C6-C14 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^S-1A)3, or -Z-(R⁷). In some embodiments, R⁶ is C1-C16 alkyl. In some embodiments, R⁶ is C₂-C₁₆ alkenyl. In some embodiments, R⁶ is C₈ alkyl, C₁₀ alkyl, or C₂ alkenyl. [0122] In some embodiments, R⁶ is hydrogen. In some embodiments, R⁶ is halogen. In some embodiments, R⁶ is C₁-C₁₆ alkyl. In some embodiments, R⁶ is C₂- C₁₆ alkenyl. In some embodiments, R⁶ is C₃-C₁₄ cycloalkyl. In some embodiments, R⁶ is C3-C14 cycloalkenyl. In some embodiments, R⁶ is C1-C16 alkoxy. In some embodiments, R⁶ is -C(=O)-R^S-1A. In some embodiments, R⁶ is -O-C(=O)-R^S-1A. In some embodiments, R⁶ is C6-C14 aryl. In some embodiments, R⁶ is -O-C6-C14 aryl. In some embodiments, R⁶ is 3- to 14-membered heterocycloalkyl. In some embodiments, R⁶ is 5- to 14-membered heteroaryl. In some embodiments, R⁶ is -Si(R^S-1A)3. In some embodiments, R⁶ is or -Z-(R⁷). [0123] In some embodiments, R⁶ is C₁-C₁₆ alkyl. In some embodiments, R⁶ is C₆- C₁₆ alkyl. In some embodiments, R⁶ is C₈-C₁₀ alkyl. In some embodiments, R⁶ is C₈ alkyl. In some embodiments, R⁶ is C10 alkyl. [0124] In some embodiments, R⁶ is C₂-C₆ alkenyl. In some embodiments, R⁶ is C₂-C₃ alkenyl. In some embodiments, R⁶ is C₂ alkenyl. [0125] In some embodiments, R⁴ and R⁶, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl. In some embodiments, R⁴ and R⁶, together with the carbon atoms to which they are attached, form a C₅ cycloalkyl. In some embodiments, R⁴ and R⁶, together with the carbon atoms to which they are attached, form a C5 cycloalkenyl. [0126] In some embodiments, each R^S-1A is independently halogen, C₁-C₆ alkyl or C₁-C₁₆ alkoxy. In some embodiments, each R^S-1A is C₁-C₆ alkyl. In some embodiments, each R^S-1A is C1-C16 alkoxy. [0127] In some embodiments, Z is a bond, -(CR^S-2AR^S-3A)_a-, -O(CR^S-2AR^S-3A)_a-, - (CR^S-2AR^S-3A)_aO-, -(CR^S-2AR^S-3A)_a-O-(CR^S-2AR^S-3A)_b-, -(CR^S-2AR^S-3A)_a-O-(SiR^S-2AR^S-3A)b-, -(CR^S-2AR^S-3A)a-(C=O)O-(CR^S-2AR^S-3A)b-, -(CR^S-2AR^S-3A)-O(C=O)-(C R^S-2AR^S-3A)_b-, -(CR^S-2AR^S-3A)_a-(C=O)-(CR^S-2AR^S-3A)_b-. In some embodiments, Z is a bond. In some embodiments, Z is -(CR^S-2AR^S-3A)_a-. In some embodiments, Z is -O(CR^S-2AR^S-3A)a-. In some embodiments, Z is -(CR^S-2AR^S-3A)aO-. In some embodiments, Z is - (CR^S-2AR^S-3A)a-O-(CR^S-2AR^S-3A)b-. In some embodiments, Z is -(CR^S-2AR^S-3A)a-O- (SiR^S-2AR^S-3A)_b-. In some embodiments, Z is -(CR^S-2AR^S-3A)_a-(C=O)O-(CR^S-2AR^S-3A)_b-. In some embodiments, Z is -(CR^S-2AR^S-3A)-O(C=O)-(C R^S-2AR^S-3A)b-. In some embodiments, Z is -(CR^S-2AR^S-3A)a-(C=O)-(CR^S-2AR^S-3A)b-. [0128] In some embodiments, each R^S-2A and R^S-3A is independently hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, -O-C(=O)-C₁-C₆ alkyl, -C(=O)-(C₁-C₆ alkyl), phenyl, or - O-phenyl. In some embodiments, one of R^S-2A and R^S-3A is hydrogen. In some embodiments, one of R^S-2A and R^S-3A is C₁-C₆ alkyl. In some embodiments, one of R^S-2A and R^S-3A is C₁-C₆ alkoxy. In some embodiments, one of R^S-2A and R^S-3A is O- C(=O)-C1-C6 alkyl. In some embodiments, one of R^S-2A and R^S-3A is -C(=O)-(C1-C6 alkyl). In some embodiments, one of R^S-2A and R^S-3A is phenyl. In some embodiments, one of R^S-2A and R^S-3A is -O-phenyl. [0129] In some embodiments, each R^S-2A is hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, -O-C(=O)-C1-C6 alkyl, -C(=O)-(C1-C6 alkyl), phenyl, or -O-phenyl. In some embodiments, R^S-2A is hydrogen. In some embodiments, R^S-2A is C1-C6 alkyl. In some embodiments, R^S-2A is C₁-C₆ alkoxy. In some embodiments, R^S-2A is O-C(=O)-C₁-C₆ alkyl. In some embodiments, R^S-2A is -C(=O)-(C₁-C₆ alkyl). In some embodiments, R^S-2A is phenyl. In some embodiments, R^S-2A is -O-phenyl. [0130] In some embodiments, each R^S-3A is hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, -O-C(=O)-C₁-C₆ alkyl, -C(=O)-(C₁-C₆ alkyl), phenyl, or -O-phenyl. In some embodiments, R^S-3A is hydrogen. In some embodiments, R^S-3A is C1-C6 alkyl. In some embodiments, R^S-3A is C1-C6 alkoxy. In some embodiments, R^S-3A is O-C(=O)-C1-C6 alkyl. In some embodiments, R^S-3A is -C(=O)-(C₁-C₆ alkyl). In some embodiments, R^S-3A is phenyl. In some embodiments, R^S-3A is -O-phenyl. [0131] In some embodiments, each R^S-7A is independently selected from C1-C6 alkyl, C₁-C₆ alkoxy, -O-C(=O)-C₁-C₆ alkyl, -C(=O)-(C₁-C₆ alkyl), phenyl, or -O- phenyl. In some embodiments, R^S-7A is C₁-C₆ alkyl. In some embodiments, R^S-7A is C1-C6 alkoxy. In some embodiments, R^S-7A is O-C(=O)-C1-C6 alkyl. In some embodiments, R^S-7A is -C(=O)-(C₁-C₆ alkyl). In some embodiments, R^S-7A is phenyl. In some embodiments, R^S-7A is -O-phenyl. [0132] In some embodiments, each a and b is independently an integer between 1 and 12. In some embodiments, each a and b is independently an integer between 2 and 11. In some embodiments, each a and b is independently an integer between 3 and 10. In some embodiments, each a and b is independently an integer between 4 and 9. In some embodiments, each a and b is independently an integer between 5 and 8. In some embodiments, each a and b is independently an integer between 1 and 3. In some embodiments, each a and b is independently an integer between 1 and 6. [0133] In some embodiments, each a is an integer between 1 and 12. In some embodiments, each a is an integer between 2 and 11. In some embodiments, a is an integer between 3 and 10. In some embodiments, a is an integer between 4 and 9. In some embodiments, a is an integer between 5 and 8. In some embodiments, a is an integer between 1 and 3. In some embodiments, a is an integer between 1 and 6. [0134] In some embodiments, each b is an integer between 1 and 12. In some embodiments, each b is an integer between 2 and 11. In some embodiments, b is an integer between 3 and 10. In some embodiments, b is an integer between 4 and 9. In some embodiments, b is an integer between 5 and 8. In some embodiments, b is an integer between 1 and 3. In some embodiments, b is an integer between 1 and 6. [0135] In some embodiments, the ROMP precursor is a compound of Formula (S- IIa):

wherein R¹³ is C₁-C₁₆ alkyl. [0136] In some embodiments, R¹³ is C₁-C₁₆ alkyl. In some embodiments, R¹³ is C₈ alkyl. In some embodiments, R¹³ is n-octyl. [0137] In some embodiments, the ROMP precursor is a compound of Formula (S- III):

wherein: R⁹ and R¹⁰ are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O- C(=O)-C1-C16 alkyl, -C(=O)-(C1-C16 alkyl), C6-C14 aryl, or -O-(C6-C14 aryl); or R⁹ taken together with R¹⁰ and the carbon atoms to which they are attached to form a C₅-C₇ cycloalkyl; R¹¹ is hydrogen, halogen, OH, C1-C16 alkyl, C6-C16 aryl, -(C6-C14 aryl)-C1-C14 alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R¹², or -O(C=O)OR¹²; and R¹² is C₁-C₁₆ alkyl, C₆-C₁₄ aryl, or (C₆-C₁₄ aryl)-(C₁-C₁₆ alkyl). [0138] In some embodiments, the ROMP precursor is a compound of Formula (S- IIIa):

wherein R⁹, R¹⁰, and R¹¹ are as described herein. [0139] In some embodiments, the ROMP precursor is a compound of Formula (S- IIIb):

wherein R⁹, R¹⁰, and R¹¹ are as described herein. [0140] In some embodiments, R⁹ and R¹⁰ are each independently hydrogen, C₁- C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(C1-C16 alkyl), C6-C14 aryl, or -O-(C6-C14 aryl); or R⁹ taken together with R¹⁰ and the carbon atoms to which they are attached to form a C₅-C₇ cycloalkyl. In some embodiments, one of R⁹ and R¹⁰ is hydrogen. In some embodiments, one of R⁹ and R¹⁰ is C₁-C₁₆ alkyl. In some embodiments, one of R⁹ and R¹⁰ is C1-C16 alkoxy. In some embodiments, one of R⁹ and R¹⁰ is -O-C(=O)-C1-C16 alkyl. In some embodiments, one of R⁹ and R¹⁰ is - C(=O)-(C₁-C₁₆ alkyl). In some embodiments, one of R⁹ and R¹⁰ is C₆-C₁₄ aryl. In some embodiments, one of R⁹ and R¹⁰ is -O-(C6-C14 aryl). In some embodiments, R⁹ taken together with R¹⁰ and the carbon atoms to which they are attached to form a C5- C₇ cycloalkyl. [0141] In some embodiments, R⁹ is hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O- C(=O)-C1-C16 alkyl, -C(=O)-(C1-C16 alkyl), C6-C14 aryl, or -O-(C6-C14 aryl). In some embodiments, R⁹ is hydrogen. In some embodiments, R⁹ is C₁-C₁₆ alkyl. In some embodiments, R⁹ is C₁-C₁₆ alkoxy. In some embodiments, R⁹ is -O-C(=O)-C₁-C₁₆ alkyl. In some embodiments, R⁹ is -C(=O)-(C1-C16 alkyl). In some embodiments, R⁹ is C6-C14 aryl. In some embodiments, R⁹ is -O-(C6-C14 aryl). [0142] In some embodiments, R¹⁰ is hydrogen, C₁-C₁₆ alkyl, C₁-C₁₆ alkoxy, -O- C(=O)-C1-C16 alkyl, -C(=O)-(C1-C16 alkyl), C6-C14 aryl, or -O-(C6-C14 aryl). In some embodiments, R¹⁰ is hydrogen. In some embodiments, R¹⁰ is C1-C16 alkyl. In some embodiments, R¹⁰ is C₁-C₁₆ alkoxy. In some embodiments, R¹⁰ is -O-C(=O)-C₁-C₁₆ alkyl. In some embodiments, R¹⁰ is -C(=O)-(C1-C16 alkyl). In some embodiments, R¹⁰ is C6-C14 aryl. In some embodiments, R¹⁰ is -O-(C6-C14 aryl). [0143] In some embodiments, R¹¹ is hydrogen, halogen, OH, C₁-C₁₆ alkyl, C₆-C₁₆ aryl, -(C₆-C₁₄ aryl)-C₁-C₁₄ alkoxy, -C₁-C₁₆ alkoxy, -O-(C₆-C₁₄ aryl), -O(C=O)R¹², or - O(C=O)OR¹². In some embodiments, R¹¹ is hydrogen. In some embodiments, R¹¹ is halogen. In some embodiments, R¹¹ is OH. In some embodiments, R¹¹ is C₁-C₁₆ alkyl. In some embodiments, R¹¹ is C₆-C₁₆ aryl. In some embodiments, R¹¹ is -(C₆-C₁₄ aryl)- C1-C14 alkoxy. In some embodiments, R¹¹ is -C1-C16 alkoxy. In some embodiments, R¹¹ is -O-(C6-C14 aryl). In some embodiments, R¹¹ is -O(C=O)R¹². In some embodiments, R¹¹ is -O(C=O)OR¹². [0144] In some embodiments, R¹² is C₁-C₁₆ alkyl, C₆-C₁₄ aryl, or (C₆-C₁₄ aryl)- (C1-C16 alkyl).In some embodiments, R¹² is C1-C16 alkyl. In some embodiments, R¹² is C6-C14 aryl. In some embodiments, R¹² is (C6-C14 aryl)-(C1-C16 alkyl). [0145] In some embodiments, the ROMP precursor is a compound of any one of Formulae (S-IVa), (S-IVb), (S-IVc), and (S-IVd):

wherein: each Y is independently -CH2, -CH2-CH2-, -O-, or -S-; X¹ is -O-, -S-, -NR^a, -SiR^bR^c, -SiR^bR^cO(SiR^bR^cO)m1SiR^bR^c, -SiR^bR^c(C6-C10 aryl)SiR^bR^c, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, C₁- C18 alkyl, -CH=CH-, or -C≡C-; X² is -SiR^bR^c, -Si(R^bR^c)O(SiR^bR^cO)m1Si(R^bR^c), -Si(R^bR^c)(C6-C10 aryl)Si(R^bR^c), -C(=O)-, C₁-C₁₈ alkyl, -CH=CH-, or -C≡C-; R^a, R^b and R^c are each independently hydrogen, C₁-C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(C1-C3 alkyl)Si(CH3)2; and each n₁, n₂, n₃, and n₄ is independently an integer 0, 1, or 2; each b₁, b₂, and b₄ is independently an integer between 1 and 10; m1 is an integer between 0 and 10. [0146] In some embodiments, X¹ is -O-, -S-, -NR^a, -SiR^bR^c, - SiR^bR^cO(SiR^bR^cO)_m1SiR^bR^c, -SiR^bR^c(C₆-C₁₀ aryl)SiR^bR^c, -C(=O)-, -C(=O)O-, - OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, C1-C18 alkyl, -CH=CH-, or -C≡C-. In some embodiments, X¹ is -O-. In some embodiments, X¹ is -S-. In some embodiments, X¹ is -NR^a. In some embodiments, X¹ is -SiR^bR^c. In some embodiments, X¹ is -SiR^bR^cO(SiR^bR^cO)_m1SiR^bR^c. In some embodiments, X¹ is - SiR^bR^c(C6-C10 aryl)SiR^bR^c. In some embodiments, X¹ is -C(=O)-. In some embodiments, X¹ is -C(=O)O-. In some embodiments, X¹ is -OC(=O)-. In some embodiments, X¹ is -OC(=O)-O-. In some embodiments, X¹ is -SC(=O)-. In some embodiments, X¹ is -C(=O)-S-. In some embodiments, X¹ is C1-C18 alkyl. In some embodiments, X¹ is -CH=CH-. In some embodiments, X¹ is -C≡C-. [0147] In some embodiments, X² is -SiR^bR^c, -Si(R^bR^c)O(SiR^bR^cO)_m1Si(R^bR^c), - Si(R^bR^c)(C6-C10 aryl)Si(R^bR^c), -C(=O)-, C1-C18 alkyl, -CH=CH-, or -C≡C-. In some embodiments, X² is -SiR^bR^c. In some embodiments, X² is - Si(R^bR^c)O(SiR^bR^cO)_m1Si(R^bR^c). In some embodiments, X² is -Si(R^bR^c)(C₆-C₁₀ aryl)Si(R^bR^c). In some embodiments, X² is -C(=O)-. In some embodiments, X² is C₁- C18 alkyl. In some embodiments, X² is -CH=CH-. In some embodiments, X² is -C≡C-. [0148] In some embodiments, R^a, R^b and R^c are each independently hydrogen, C₁- C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C₃-C₁₂ cycloalkenyl, or (C₅-C₁₂ cycloalkyl)-(C₁- C3alkyl)Si(CH3)2. In some embodiments, at least one of R^a, R^b and R^c is hydrogen. In some embodiments, at least one of R^a, R^b and R^c is C₁-C₁₂ alkyl. In some embodiments, at least one of R^a, R^b and R^c is C₃ -C₁₂ cycloalkyl. In some embodiments, at least one of R^a, R^b and R^c is C3-C12 cycloalkenyl. In some embodiments, at least one of R^a, R^b and R^c is (C5-C12 cycloalkyl)-(C1- C₃alkyl)Si(CH₃)₂. [0149] In some embodiments, R^a is hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(C1-C3alkyl)Si(CH3)2. In some embodiments, R^a is hydrogen. In some embodiments, R^a is C₁-C₁₂ alkyl. In some embodiments, R^a is C₃ -C₁₂ cycloalkyl. In some embodiments, R^a is C₃-C₁₂ cycloalkenyl. In some embodiments, R^a is (C5-C12 cycloalkyl)-(C1-C3alkyl)Si(CH3)2. [0150] In some embodiments, R^b is hydrogen, C₁-C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C₃-C₁₂ cycloalkenyl, or (C₅-C₁₂ cycloalkyl)-(C₁-C₃alkyl)Si(CH₃)₂. In some embodiments, R^b is hydrogen. In some embodiments, R^b is C1-C12 alkyl. In some embodiments, R^b is C3 -C12 cycloalkyl. In some embodiments, R^b is C3-C12 cycloalkenyl. In some embodiments, R^b is (C5-C12 cycloalkyl)-(C1-C3alkyl)Si(CH3)2. [0151] In some embodiments, R^c is hydrogen, C₁-C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(C1-C3alkyl)Si(CH3)2. In some embodiments, R^c is hydrogen. In some embodiments, R^c is C1-C12 alkyl. In some embodiments, R^c is C₃ -C₁₂ cycloalkyl. In some embodiments, R^c is C₃-C₁₂ cycloalkenyl. In some embodiments, R^c is (C₅-C₁₂ cycloalkyl)-(C₁-C₃alkyl)Si(CH₃)₂. [0152] In some embodiments, each n1, n2, n3, and n4 is independently 0, 1, or 2. In some embodiments, each n₁, n₂, n₃, and n₄ is independently 0 or 1. In some embodiments, each n₁, n₂, n₃, and n₄ is independently 1 or 2. [0153] In some embodiments, n1 is 0, 1, or 2. In some embodiments, n2 is 0, 1, or 2. In some embodiments, n3 is 0, 1, or 2. In some embodiments, n4 is 0, 1, or 2. [0154] In some embodiments, each b₁, b₂, and b₄ is independently an integer between 1 and 10. In some embodiments, each b1, b2, and b4 is independently an integer between 1 and 5. In some embodiments, each b1, b2, and b4 is independently an integer between 1 and 3. [0155] In some embodiments, b₁ is an integer between 1 and 10. In some embodiments, b2 is an integer between 1 and 10. In some embodiments, b3 is an integer between 1 and 10. In some embodiments, b₄ is an integer between 1 and 10. [0156] In some embodiments, m₁ is an integer between 0 and 10. In some embodiments, m1 is an integer between 0 and 5. In some embodiments, m1 is an integer between 0 and 3. [0157] In some embodiments, the ROMP precursor is a compound of Formula (M-I):

or a salt thereof, wherein: Z^M is CH₂ or O; each R^M-1 independently: (a) is H, halogen, cyano, -OR^M-1A, -SR^M-1A, -C(=O)-R^M-1A, -C(=O)-OR^M-1A, - O-C(=O)-R^M-1A, -C(=O)-N(R^M-1A)₂, -C(=O)-NHR^M-1A, -NH-C(=O)-R^M-1A, -N(R^M-1A)₂, -Si(R^M-1A)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A; or (b) together with another R^M-1 and the atoms to which they attach, form a bond, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A; each R^M-1A independently: (a) is H, halogen, cyano, -OR^M-1B, -SR^M-1B, -C(=O)-R^M-1B, -C(=O)-OR^M-1B, - O-C(=O)-R^M-1B, -C(=O)-N(R^M-1B)2, -C(=O)-NHR^M-1B, -NH-C(=O)-R^M-1B, -N(R^M-1B)2, -Si(R^M-1B)₃, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1B; or (b) together with another R^M-1A and the atoms to which they attach, form a bond, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1B; each R^M-1B independently is H, halogen, cyano, -OR^M-1C, -SR^M-1C, -C(=O)-R^M-1C, -C(=O)-OR^M-1C, -O-C(=O)-R^M-1C, -C(=O)-N(R^M-1C)2, -C(=O)-NHR^M-1C, -NH- C(=O)-R^M-1C, -N(R^M-1C)2, -Si(R^M-1C)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3- C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl is optionally substituted with one or more R^M-1C; each R^M-1C independently is H, halogen, cyano, -OR^M-1D, -SR^M-1D, -C(=O)-R^M-1D, -C(=O)-OR^M-1D, -O-C(=O)-R^M-1D, -C(=O)-N(R^M-1D)2, -C(=O)-NHR^M-1D, -NH- C(=O)-R^M-1D, -N(R^M-1D)₂, -Si(R^M-1D)₃, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3- C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl is optionally substituted with one or more R^M-1D; and each R^M-1D independently is H, halogen, cyano, -OH, -NH₂, C₁-C₂₀ alkyl, C₂- C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl. Variable Z^M [0158] In some embodiments, Z^M is CH₂. [0159] In some embodiments, Z^M is O. Variable R^M-1 [0160] In some embodiments, at least one R^M-1 is H, halogen, cyano, -OR^M-1A, - R^M-1A, -C(=O)-R^M-1A, -C(=O)-OR^M-1A, -O-C(=O)-R^M-1A, -C(=O)-N(R^M-1A)2, -C(=O)- NHR^M-1A, -NH-C(=O)-R^M-1A, -N(R^M-1A)2, -Si(R^M-1A)3, C1-C20 alkyl, C2-C20 alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A. [0161] In some embodiments, at least one R^M-1 is H. [0162] In some embodiments, at least one R^M-1 is halogen, cyano, -OR^M-1A, -SR^M-1A, -C(=O)-R^M-1A, -C(=O)-OR^M-1A, -O-C(=O)-R^M-1A, -C(=O)-N(R^M-1A)₂, -C(=O)- NHR^M-1A, -NH-C(=O)-R^M-1A, -N(R^M-1A)₂, -Si(R^M-1A)₃, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A. [0163] In some embodiments, at least one R^M-1 is halogen. [0164] In some embodiments, at least one R^M-1 is cyano. [0165] In some embodiments, at least one R^M-1 is -OR^M-1A. [0166] In some embodiments, at least one R^M-1 is -SR^M-1A. [0167] In some embodiments, at least one R^M-1 is -C(=O)-R^M-1A. [0168] In some embodiments, at least one R^M-1 is -C(=O)-OR^M-1A. [0169] In some embodiments, at least one R^M-1 is -O-C(=O)-R^M-1A. [0170] In some embodiments, at least one R^M-1 is -C(=O)-N(R^M-1A)₂. [0171] In some embodiments, at least one R^M-1 is -C(=O)-NHR^M-1A. [0172] In some embodiments, at least one R^M-1 is -NH-C(=O)-R^M-1A. [0173] In some embodiments, at least one R^M-1 is -N(R^M-1A)2. [0174] In some embodiments, at least one R^M-1 is -Si(R^M-1A)3. [0175] In some embodiments, at least one R^M-1 is C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A. [0176] In some embodiments, at least one R^M-1 is C1-C20 alkyl optionally substituted with one or more R^M-1A. [0177] In some embodiments, at least one R^M-1 is C₂-C₂₀ alkenyl optionally substituted with one or more R^M-1A. [0178] In some embodiments, at least one R^M-1 is C2-C20 alkynyl optionally substituted with one or more R^M-1A. [0179] In some embodiments, at least one R^M-1 is C3-C20 cycloalkyl optionally substituted with one or more R^M-1A. [0180] In some embodiments, at least one R^M-1 is C₆-C₂₀ aryl (e.g., phenyl) optionally substituted with one or more R^M-1A. [0181] In some embodiments, at least one R^M-1 is 3- to 20-membered heterocycloalkyl optionally substituted with one or more R^M-1A. [0182] In some embodiments, at least one R^M-1 is 5- to 20-membered heteroaryl optionally substituted with one or more R^M-1A. [0183] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form a bond, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C3-C20 cycloalkyl, C6- C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A. [0184] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form a bond. [0185] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A. [0186] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form C3-C20 cycloalkyl optionally substituted with one or more R^M'^1A.

[0187] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form C6-C20 aryl (e.g., phenyl) optionally substituted with one or more

[0188] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form 3- to 20-membered heterocycloalkyl optionally substituted with one or more R^M'^1A.

[0189] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form 5- to 20-membered heteroaryl optionally substituted with one or more R^M'^1A.

Variable R^M'^U

[0190] In some embodiments, at least one R^M'^1A is H.

[0191] In some embodiments, at least one R^M'^1A is halogen, cyano, -OR^M'^1B, -

SR^M-^1B, -C(=O)-R^M'^1B, -C(=O)-OR^M'^1B, -O-C(=O)-R^M'^1B, -C(=O)-N(R^M'^1B)2, -C(=O)- NHR^M'^1B, -NH-C(=O)-R^M'^1B, -N(R^M'^1B)2, -Si(R^M'^1B)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1B.

[0192] In some embodiments, at least one R^M'^1A is halogen.

[0193] In some embodiments, at least one R^M'^1A is cyano.

[0194] In some embodiments, at least one R^M'^1A is -OR^M'^1B.

[0195] In some embodiments, at least one R^M'^1A is -SR^M'^1B.

[0196] In some embodiments, at least one R^M'^1A is -C(=O)-R^M'^1B.

[0197] In some embodiments, at least one R^M'^1A is -C(=O)-OR^M'^1B.

[0198] In some embodiments, at least one R^M'^1A is -O-C(=O)-R^M'^1B.

[0199] In some embodiments, at least one R^M'^1A is -C(=O)-N(R^M'^1B)2.

[0200] In some embodiments, at least one R^M'^1A is -C(=O)-NHR^M'^1B.

[0201] In some embodiments, at least one R^M'^1A is -NH-C(=O)-R^M'^1B.

[0202] In some embodiments, at least one R^M'^1A is -N(R^M'^1B)2.

[0203] In some embodiments, at least one R^M'^1A is -Si(R^M'^1B)3.

[0204] In some embodiments, at least one R^M'^1A is C1-C20 alkyl, C2-C20 alkenyl,

C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1B.

[0205] In some embodiments, at least one R^M'^1A is C1-C20 alkyl optionally substituted with one or more R^M'^1B.

[0206] In some embodiments, at least one R^M'^1A is C2-C20 alkenyl optionally substituted with one or more R^M'^1B.

[0207] In some embodiments, at least one R^M'^1A is C2-C20 alkynyl optionally substituted with one or more R^M'^1B.

[0208] In some embodiments, at least one R^M'^1A is C3-C20 cycloalkyl optionally substituted with one or more R^M'^1B.

[0209] In some embodiments, at least one R^M'^1A is C6-C20 aryl (e.g., phenyl) optionally substituted with one or more R^M'^1B.

[0210] In some embodiments, at least one R^M'^1A is 3- to 20-membered heterocycloalkyl optionally substituted with one or more R^M'^1B.

[0211] In some embodiments, at least one R^M'^1A is 5- to 20-membered heteroaryl optionally substituted with one or more R^M'^1B.

[0212]

[0213] In some embodiments, at least two R^M'^1A, together with the atoms to which they attach, form a bond, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C3-C20 cycloalkyl, Ce- C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1B.

[0214] In some embodiments, at least two R^M-1, together with the atoms to which to which they attach, form a bond.

[0215] In some embodiments, at least two R^M-1, together with the atoms to which they attach, form C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1B.

[0216] In some embodiments, at least two R^M'^1A, together with the atoms to which they attach, form C3-C20 cycloalkyl optionally substituted with one or more R^M'^1B [0217] In some embodiments, at least two R^M'^1A, together with the atoms to which they attach, form C6-C20 aryl (e.g., phenyl) optionally substituted with one or more

[0218] In some embodiments, at least two R^M'^1A, together with the atoms to which they attach, form 3- to 20-membered heterocycloalkyl optionally substituted with one or more R^M'^1B.

[0219] In some embodiments, at least two R^M'^1A, together with the atoms to which they attach, form 5- to 20-membered heteroaryl optionally substituted with one or more R^M'^1B.

Variable R^M'^1B

[0220] In some embodiments, at least one R^M'^1B is halogen.

[0221] In some embodiments, at least one R^M'^1B is cyano.

[0222] In some embodiments, at least one R^M'^1B is -OR^M'^1C.

[0223] In some embodiments, at least one R^M'^1B is -SR^M'^1C.

[0224] In some embodiments, at least one R^M'^1B is -C(=O)-R^M'^1C.

[0225] In some embodiments, at least one R^M'^1B is -C(=O)-OR^M'^1C.

[0226] In some embodiments, at least one R^M'^1B is -O-C(=O)-R^M'^1C.

[0227] In some embodiments, at least one R^M'^1B is -C(=O)-N(R^M'^1C)2.

[0228] In some embodiments, at least one R^M'^1B is -C(=O)-NHR^M'^1C.

[0229] In some embodiments, at least one R^M'^1B is -NH-C(=O)-R^M'^1C.

[0230] In some embodiments, at least one R^M'^1B is -N(R^M'^1C)2.

[0231] In some embodiments, at least one R^M'^1B is -Si(R^M'^lc)3.

[0232] In some embodiments, at least one R^M'^1B is C1-C20 alkyl, C2-C20 alkenyl,

C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1C.

[0233] In some embodiments, at least one R^M'^1B is C1-C20 alkyl optionally substituted with one or more R^M'^1C.

[0234] In some embodiments, at least one R^M'^1B is C2-C20 alkenyl optionally substituted with one or more R^M'^1C.

[0235] In some embodiments, at least one R^M'^1B is C2-C20 alkynyl optionally substituted with one or more R^M'^1C. [0236] In some embodiments, at least one R^M'^1B is C3-C20 cycloalkyl optionally substituted with one or more R^M'^1C.

[0237] In some embodiments, at least one R^M'^1B is C6-C20 aryl (e.g., phenyl) optionally substituted with one or more R^M'^1C.

[0238] In some embodiments, at least one R^M'^1B is 3- to 20-membered heterocycloalkyl optionally substituted with one or more R^M'^1C.

[0239] In some embodiments, at least one R^M'^1B is 5- to 20-membered heteroaryl optionally substituted with one or more R^M'^1C.

Variable R^M'^1C

[0240] In some embodiments, at least one R^M'^1C is halogen.

[0241] In some embodiments, at least one R^M'^1C is cyano.

[0242] In some embodiments, at least one R^M'^1C is -OR^M'^1D.

[0243] In some embodiments, at least one R^M'^1C is -SR^M'^1D.

[0244] In some embodiments, at least one R^M'^1C is -C(=O)-R^M'^1D.

[0245] In some embodiments, at least one R^M'^1C is -C(=O)-OR^M'^1D.

[0246] In some embodiments, at least one R^M'^1C is -O-C(=O)-R^M'^1D.

[0247] In some embodiments, at least one R^M'^1C is -C(=O)-N(R^M'^1D)2.

[0248] In some embodiments, at least one R^M'^1C is -C(=O)-NHR^M'^1D.

[0249] In some embodiments, at least one R^M'^1C is -NH-C(=O)-R^M'^1D.

[0250] In some embodiments, at least one R^M'^1C is -N(R^M'^1D)2.

[0251] In some embodiments, at least one R^M'^1C is -Si(R^M'^1D)3.

[0252] In some embodiments, at least one R^M'^1C is C1-C20 alkyl, C2-C20 alkenyl,

C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1D.

[0253] In some embodiments, at least one R^M'^1C is C1-C20 alkyl optionally substituted with one or more R^M'^1D.

[0254] In some embodiments, at least one R^M'^1C is C2-C20 alkenyl optionally substituted with one or more R^M'^1D.

[0255] In some embodiments, at least one R^M'^1C is C2-C20 alkynyl optionally substituted with one or more R^M'^1D.

[0256] In some embodiments, at least one R^M'^1C is C3-C20 cycloalkyl optionally substituted with one or more R^M'^1D. [0257] In some embodiments, at least one R^M'^1C is C6-C20 aryl (e.g., phenyl) optionally substituted with one or more R^M'^1D.

[0258] In some embodiments, at least one R^M'^1C is 3- to 20-membered heterocycloalkyl optionally substituted with one or more R^M'^1D.

[0259] In some embodiments, at least one R^M'^1C is 5- to 20-membered heteroaryl optionally substituted with one or more R^M'^1D.

Variable R^M'^1D

[0260] In some embodiments, at least one R^M'^1D is H.

[0261] In some embodiments, at least one R^M'^1D is halogen, cyano, -OH, -NH2, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl.

[0262] In some embodiments, at least one R^M'^1D is halogen.

[0263] In some embodiments, at least one R^M'^1D is cyano.

[0264] In some embodiments, at least one R^M'^1D is -OH.

[0265] In some embodiments, at least one R^M'^1D is -NH2.

[0266] In some embodiments, at least one R^M'^1D is C1-C20 alkyl.

[0267] In some embodiments, at least one R^M'^1D is C2-C20 alkenyl.

[0268] In some embodiments, at least one R^M'^1D is C2-C20 alkynyl.

[0269] In some embodiments, at least one R^M'^1D is C3-C20 cycloalkyl.

[0270] In some embodiments, at least one R^M'^1D is C6-C20 aryl (e.g., phenyl).

[0271] In some embodiments, at least one R^M'^1D is 3- to 20-membered heterocycloalkyl.

[0272] In some embodiments, at least one R^M'^1D is 5- to 20-membered heteroaryl.

[0273] It is understood that, for a compound of Formula (M-I), Z^M, R^M-1, R^M'^1A, RM-IB, R^M'^1C, and R^M'^1D can each be, where applicable, selected from the groups described herein, and any group described herein for any of Z^M, R^M-1, R^M'^1A, R^M'^1B, R^M-^1C,_and RM-ID_can b_{e com}bi_nec[, where applicable, with any group described herein for one or more of the remainder Z^M, R^M-1, R^M'^1A, R^M'^1B, R^M'^1C, and R^M'^1D.

Exemplary ROMP Precursors

In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0274] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0275] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0276] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0277] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0278] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0279] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0280] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof.

[0281] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof, wherein R^M'^1Fis H, halogen, cyano, -OH, NH2, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, and wherein R^M'^1E is

[0282] In some embodiments, the ROMP precursor is a compound of:

or a salt thereof, wherein R^M'^1E is as defined herein.

[0283] In some embodiments, the ROMP precursor is a compound of:

[0284] In some embodiments, the ROMP precursor is selected from the compounds described in Table 1 and salts thereof.

Table 1.

ĨDCPD). Transition Metal Activator

[0286] In some embodiments, the transition metal activator comprises a Cu(I) complex. In some embodiments, the transition metal activator comprises a Cu(II) complex.

[0287] In some embodiments, the transition metal activator the transition metal activator comprises a mixture of a Cu(I) complex and a Cu(II) complex.

[0288] In some embodiments, the transition metal activator comprises a compound of Formula (A-I) or Formula (A-II):

LmCu*Xn (A-I); L_qAu*X (A-II) wherein:

Cu* is Cu(I) or Cu(II);

Au* is Au(I); each X is independently an X-type ligand; each L is independently an L-type ligand; m is 0, 1, 2, 3, 4, or 5; q is 0, 1, 2, 3, 4, 5 or 6; and when Cu* is Cu(I), n is 1, and when Cu* is Cu(II), n is 2.

[0289] As used herein in its art-recognized sense, “X-type ligand” refers to an anionic ligand formally donating a single electron to the metal and is anionic when disassociated from the metal. Examples of X-type ligands include, e.g., halogens (e.g., fluoride, chloride, bromide, iodide), nitrate, and weakly coordinating anions (e.g., perchlorate, tetrafluorob orate, hexafluorophosphate, hexafluoroantimonate, or [Bar^F4]' )•

[0290] As used herein, [BAr^F4]’ refers to tetrakis[3,5-bis(trifluoromethyl)phenyl] borate).

[0291] As used herein in its art-recognized sense, “L-type ligand” refers to a neutral ligand formally donating a pair of electrons to the metal when datively bonded and is neutral when disassociated from the metal. Examples of L-type ligands include, e.g., water, phosphines (e.g., triphenyl phosphine), pyridines (e.g., bipyridine, DMAP), amines (e.g., ethylene diamaine, DABCO), N-heterocyclic carbenes (e.g. l,3-dimesityl-imidazol-4,5-dihydro-2-ylidene), and cyclooctadiene. One or more of the ROMP precursors described herein (e.g., a compound of Formulae (S-II), (S-IIa), (S-III), (S-IIIa), (S-IIIb), (S-IVa), (S-IVb), (S-IVc), (S-IVd), (M-I), and/or any of compounds 1-85) may also function as an L-type ligand. [0292] Ligands may be monodentate or polydentate (e.g., bidentate, tridentate, tetradentate, etc.). A polydentate ligand may function as multiple X-type ligands, multiple L-type ligands, or both. For example, in some embodiments, an X and an L may together form

X and two L may together form

[0293] In some embodiments, the activator comprises a compound of Formula (A-I) or Formula (A-II): L_mCu*X_n (A-I); L_qAu*X (A-II) wherein: Cu* is Cu(I) or Cu(II); Au* is Au(I); each X is independently F-, Cl-, Br-, I-, BF4-, ClO4-, NO3-, PF6-, HCO3-, F6Sb-, C6-20 aryl-O-, [BAr^F4]-, C1-20 alkyl-, (C1-18 alkyl)-C≡C-, HC≡C-, C1-20 alkyl-O-, (C_1-20 alkyl)-CO₂-, (C_1-20 alkyl)-CO₃-, (C_1-20 alkyl)-SO₃-, (C_1-20 alkyl)- NH-, (L^Ra)(L^Rb)NCO₂-; each L is independently the ROMP precursor, H2O, C3-14 cycloalkyl, C_2-20 alkenyl, C_2-20 alkynyl, PR^p₃, 5- to 14-membered heteroaryl, or 3- to 14- membered heterocyloalkyl; and an X and an L may together form

,

each R^p is independently C1-6 alkyl or phenyl; each R^s is independently H or C_1-6 alkyl; each R^x is independently H or C_1-6 alkyl; each R^y is independently H or C1-6 alkyl, optionally wherein two R^y, together with the atoms to which they are connected form a phenyl or cyclohexyl; each R^z is independently H or C1-6 alkyl; each L^Ra is independently H, C1-6 alkyl, or C6-10 aryl; each L^Rb is independently H, C_1-6 alkyl, or C_6-10 aryl; m is 0, 1, 2, 3, 4, or 5; q is 0, 1, 2, 3, 4, 5 or 6; when Cu* is Cu(I), n is 1, and when Cu* is Cu(II), n is 2; and

represents a point of attachment to Cu* or Au*. [0294] In some embodiments, each X is independently F-, Cl-, Br-, or I-. In some embodiments, X is Cl-. [0295] In some embodiments, the transition metal activator comprises a compound of Formula (A-I). In some embodiments, the transition metal activator comprises a compound of Formula (A-II). [0296] In some embodiments, the transition metal activator comprises a compound of Formula (A-I) wherein Cu* is Cu(I). In some embodiments, the transition metal activator comprises a compound of Formula (A-I) wherein Cu* is Cu(II).

[0297] In some embodiments, the transition metal activator comprises a compound of Formula (A-III) or (A-IV):

[0298] In some embodiments, the transition metal activator comprises a compound of Formula (A-V):

LmCu*Cl (A-V); wherein Cu* is Cu(I).

[0299] In some embodiments, the activator comprises Compound A-l :

or a solvate thereof.

[0300] In some embodiments, the activator comprises Compound A-l.

[0301] In some embodiments, the activator comprises Compound A-2:

or a solvate thereof. [0302] In some embodiments, the activator comprises Compound A-2. [0303] In some embodiments, the activator comprises Compound A-3: CuCl ^dicyclopentadiene complex (A-3), or a solvate thereof. [0304] In some embodiments, the activator comprises Compound A-3. [0305] In some embodiments the transition metal activator is present in the Type A fluid material in an amount between about 1 and about 100 ppm mol/mol. In a preferred embodiment, the transition metal activator is present in the Type A fluid material in an amount between about 10 and about 60 ppm mol/mol. ROMP Pre-catalyst [0306] In some embodiments, the ROMP pre-catalyst is a compound of Formula (C-I) or (C-II):

or a salt or a solvate thereof; wherein:

each R^x is independently Cl, Br, or I; each L^1-b is independently

represents either a single or double bond; each Ar^1-b is independently C₆-C₁₀ aryl or biphenyl; wherein the C₆-C₁₀ aryl or biphenyl is optionally substituted with one or more C₁-C₁₆ alkyl, C₁-C₆ alkoxy, or -N(C1-C6 alkyl)(C1-C6 alkyl); each R^1-a is independently H or C1-C6 alkyl; each R^1-b is independently C1-C6 alkyl, C6-C10 aryl, C1-C6 alkoxy, or - O(C6-C10 aryl); each R^2-b and R^3-b is independently C₁-C₆ alkyl, C₃-C₁₄ cycloalkyl, C₆- C10 aryl or biphenyl, wherein the C6-C10 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; or R^2-b and R^3-b, together with the carbon to which they are attached, form a C₃-C₁₄ cycloalkyl; each R^4-b is independently C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, C₆-C₁₄ aryl, 5- to 14-membered heteroaryl, or biphenyl, wherein the C₆-C₁₄ aryl or biphenyl is optionally substituted with one or more C₁-C₁₆ alkyl; R^6-b is absent, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, -O(C1-C10 aryl), - NHC=O(C₁-C₆ alkyl), -NHC=O(C₁-C₆ fluoroalkyl), -SO₂N(C₁-C₆ alkyl)₂, or - NO2; R^7-b is C1-C6 alkyl, cyclohexyl, or Ar^1-b; wherein the cyclohexyl, is optionally substituted with one or more C₁-C₁₆ alkyl, C₁-C₆ alkoxy, or -N(C₁- C₆ alkyl)(C₁-C₆ alkyl); R^11-b is absent, P(R^13-b)₃

, or a catalyst inhibitor as described herein; each R^13-b is independently C₁-C₁₆ alkyl, C₆-C₁₀ aryl, -O(C₁-C₆ alkyl), - O(C₆-C₁₀ aryl), or C₃-C₁₄ cycloalkyl; R^14-b is halogen, -N(C1-C6 alkyl)2, or –(C1-C16 alkyl)-(C6-C10 aryl); and z1 is 1 or 2. [0307] In some embodiments, the ROMP pre-catalyst is a compound of Formula (C-I). In some embodiments, the ROMP pre-catalyst is a compound of Formula (C- II).

[0308] In some embodiments, each L^1-b is independently . In some preferred embodiments, each L^1-b is independently

[0309] In some embodiments, each L^1-b is independently

[0310] In some embodiments, each L^1-b is . In some

embodiments, each L^1-b is . In some embodiments, each L^1-b is

[0311] In some preferred embodiments, each L^1-b is independently

[0312] In some preferred embodiments, each L^1-b is

some preferred embodiments, each L^1-b is . In some preferred embodiments, each

. In some preferred embodiments,

each L^1-b is . In some preferred embodiments, each L^1-b is

[0314] In some embodiments, each R^x is independently Cl, Br, or I.

[0315] In some embodiments, both R^x are the same, and both R^x are Cl, Br, or I.

In some embodiments, both R^x are the same, and both R^x are Cl. In some embodiments, both R^x are the same, and both R^x are Br. In some embodiments, both R^x are the same, and both R^x are I.

/=yR¹⁴’^b

-l-N

[0316] R^11-b is absent, P(R¹³'^b)3, or — J . In some embodiments R^11-bis

/=yR¹⁴’^b

-1-N "/) absent. R^11-bis P(R¹³'^b)3 or v — 'J . In some embodiments R^11-b is P(R¹³'^b)3. In some embodiments

o

[0318] In some embodiments, R^11-b is v — J . In some embodiments, R^11-b is

Br

m [0-3j i1o9i] T In some em kbod Ji-men₊t

some embodiments, R^11-b is . In some embodiments, R^11-b is^{J PCyj} . In some

embodiments, R^11-b is ^°^Pr\ In some embodiments, R^11-b is [0320] In some embodiments, the ROMP pre-catalyst comprises Compound C-2:

or a solvate thereof. In some embodiments, Compound C-2 is commercially available from Apeiron Synthesis under the name UltraLatMet.

ROMP Catalyst

[0321] In some embodiments, the ROMP catalyst is produced by the reaction of the transition metal activator and the ROMP pre-catalyst.

[0322] Without wishing to be bound by theory, in some embodiments, the ROMP catalyst can be produced by the reaction of the transition metal activator and the ROMP pre-catalyst as shown in the scheme below:

ROMP Pre-Catalyst (C-l) etal Activator (A-l)

Transmetalation

[0323] As illustrated in the scheme above, in some embodiments, the ROMP catalyst may catalyze the polymerization of ROMP precursors.

[0324] Although the scheme above refers specifically to transition metal activator (A-I), ROMP pre-catalyst (C-I), ROMP catalyst (C-III) and ROMP Precursor (M-I), a person skilled in the art will readily recognize that analogous reactions may be described for any of the transition metal activators, ROMP pre-catalysts, ROMP catalyst, and ROMP precursors described herein. [0325] In some embodiments, the ROMP catalyst comprises a compound of Formula (C-III) or (C-IV):

or a salt or a solvate thereof; wherein L⁵'^b, R^x, L^1-b, R⁶'^b, R^11-b, and zi are as described herein.

[0326] In some embodiments, the ROMP catalyst comprises a compound of Formula (C-III). In some embodiments, the ROMP catalyst comprises a compound of Formula (C-IV).

Inert Solvent

[0327] The term "inert solvent", as used herein, refers to a solvent that cannot participate in, or inhibit, a polymerization reaction as disclosed herein. A skilled artisan will recognize that, in the context of the materials and methods disclosed herein, an inert solvent may be a solvent that does not comprise any of the functional groups identified as a catalyst inhibitor herein. A skilled artisan will recognize that the status of “inert”, as applied to a solvent, depends on the specific compounds to be dissolved therein, and can readily ascertain, by conventional means, whether a given solvent is appropriately inert under the circumstances.

[0328] In preferred embodiments, an inert solvent described herein has suitable rheology to be jetted according to the methods disclosed herein. In some embodiments, the solvent has a viscosity of about 4-200 cP at room temperature, preferably about 8-50 cP, most preferably 8-15 cP.

[0329] Exemplary inert solvents can include, e.g. mineral oil (e.g., light white mineral oil, liquid paraffin, and/or paraffin oil), arenes (e.g., xylenes, diphenyl ether, mesitylene, and/or biphenyl), alkyl benzoates, and mixtures thereof.

[0330] In some embodiments, the inert solvent comprises an organic solvent.

[0331] In some embodiments, the inert solvent comprises a non-polar solvent.

[0332] In some embodiments, the inert solvent comprises a non-polar, organic solvent.

[0333] In some embodiments, the inert solvent comprises an aromatic ether.

[0334] In some embodiments, the inert solvent comprises biphenyl. [0335] In some embodiments, the inert solvent comprises at least one benzyl moiety.

[0336] In some embodiments, the inert solvent comprises a eutectic mixture of diphenyl ether and biphenyl.

[0337] In some embodiments, the inert solvent comprises a mixture of about 27 % (w/w) biphenyl and about 73 % (w/w) diphenyl ether, relative to the total amount of inert solvent.

Organic Acids

[0338] In some embodiments, a fluid material described herein (e.g., a Type A fluid material) may comprise an organic acid. Suitable organic may include fatty acids (e.g., stearic acid, palmitic acid) and sulfonic acids (e.g., para-toluenesulfonic acid and camphorsulfonic acid) , and mixtures thereof.

Catalyst Inhibitors

[0339] In some embodiments, the combination or build material further comprises a catalyst inhibitor. As used herein, a “a catalyst inhibitor” is a chemical species which retards or ceases catalyst (or pre-catalyst) initiation or propagation. Catalyst inhibitors may be desirable for, e.g., preventing the premature polymerization during the preparation, purification, transportation and storage of the combination or build material. Suitable catalyst inhibitors include, but are not limited to, amines (e.g., alkyl amines, e.g., triethylamine, diisopropyl methyl amine), azaheterocycles (e.g., DBU (l,8-Diazabicyclo[5.4.0]undec-7-ene), DBN (l,5-Diazabicyclo[4.3.0]non-5-ene), and DABCO (l,4-diazabicyclo[2.2.2]octane), phosphines (e.g., tricyclohexylphosphine, trialkyl phosphines, and triaryl phosphines), phosphites (e.g., trialkyl phosphites, triarylphosphites, and tribenzylphosphites), pyridines (e.g., 4-dimethylaminopyridine, 3 -chloropyridine, 3 -bromopyridine, 2-dimethylaminopyridine, 3,5-lutidine, 4-(3- phenylpropyle)pyridine, and 4-tert-butylpyridine), and organic superbases, e.g., (amidine, guanidene, and phosphazene super bases).

[0340] In some embodiments, the molar ratio of catalyst inhibitor to ROMP precatalyst is between about 0.1 : 1 and about 10:1, between about 0.5:1 and about 1.5: 1, between about 0.9: 1 and about 1.1 : 1, between about 0.95: 1 and about 1.05: 1, between about 0.99: 1 and about 1.01 : 1, or about 1 : 1 [0341] In some embodiments, the molar ratio of the catalyst inhibitor and the transition metal activator (e.g., in the Type A fluid material) is about 1 : 1.

[0342] In some embodiments, the molar ratio of the catalyst inhibitor and the transition metal activator in the Type A fluid material (e.g., in the Type A fluid material) is between about 0.8: 1 and about 1.2: 1, between about 0.9: 1 and about 1.1 : 1, between about 0.95: 1 and about 1.05: 1, or between about 0.99: 1 and about 1.01 : 1. [0343] It is understood that, in some embodiments, a catalyst inhibitor as described herein may be incorporated into a ROMP pre-catalyst (e.g., at position R^11-b in compounds of Formula (C-I) or (C-II)), or into a ROMP catalyst (e.g., at position R'^llb in compounds of Formula (C-III) or (C-IV)). It is further understood that, when amounts of a catalyst inhibitor are described, those amounts are inclusive of both the amount of catalyst inhibitor incorporated into a ROMP pre-catalyst or ROMP catalyst, as well as the amount of inhibitor otherwise present in the composition (e.g., the Type B fluid material), e.g., in solution.

Activator Protecting Agents

[0344] As used herein, the term “activator protecting agent” refers to a compound (e.g., an organic compound) capable reducing (in whole or in part) an amount of Cu(II) to Cu(I). A person skilled in the art understands that copper exists in multiple oxidation states, and that Cu(I) may be in equilibrium with Cu(II). An activator protecting agent can shift this equilibrium toward Cu(I).

[0345] Without wishing to be bound by theory, it has been observed that Cu(I) complexes can activate ROMP pre-catalysts faster than can Cu(II), however Cu(I) activators have also been observed to be oxidized to Cu(II) in the presence of dissolved atmospheric oxygen. Therefore, protecting Cu(I) from oxidation from dissolved atmospheric oxygen and shifting the equilibrium of Cu(I)/Cu(II) toward Cu(I) can increase the rate at which a ROMP pre-catalyst is converted to a ROMP catalyst, thereby reducing the cure time of polymerization reactions described herein. [0346] Activator protecting agents may be described as “strong activator protecting agents” or “moderate activator protecting agents.” As used herein, a strong activator protecting agent refers to a compound that has a reduction potential significantly larger than Cu(II), or alternatively, a compound that shifts the equilibrium of Cu(I)/Cu(II) such that Cu(I) is the predominant species. Suitable strong activator protecting agents may include, e.g., hydroquinone and its derivatives (e.g., alkylated derivatives of hydroquinone) ascorbic acid. [0347] As used herein, a moderate activator protecting agent refers to a compound that has similar reduction potential to Cu(I), or alternatively, a compound that shifts the equilibrium of Cu(I)/Cu(II) such Cu(I) and Cu(II) are both present in appreciable amounts. Suitable moderate activator protecting agents may include, e.g., catechol and its derivatives (e.g., 4-/c/7-butyl catechol and other alkylated derivatives of catechol).

[0348] A person skilled in the art can recognize suitable activator protecting agent by routine means known in the art. For example, suitable activator protecting agents (e.g., strong activator protecting agents and moderate activator protecting agents) may be identified by comparing the reduction potential of an organic compound to the reduction potential of Cu(I). Alternatively, without wishing to be bound by theory, Cu(II) solutions are often intensely colored (e.g., yellow, green, or brown), while Cu(I) solutions are often colorless. Accordingly, when a moderate activator protecting agent is added to a Cu(II) solution, the intensity of the solution color may become less intense but not disappear entirely, indicating that the equilibrium has shifted to a mix of Cu(I) and Cu(II). In contrast, when a strong activator protecting agent is added to a Cu(II) solution, the intensity of the solution color may disappear entirely, indicating that the equilibrium has shifted to predominantly Cu(I). Such color changes can in some instances be observed visually (e.g., without the assistance of an analytical instrument), and may in some instances also be observed with, e.g., a UV-Vis Spectrophotometer.

[0349] In some embodiments, the activator protecting agent is an organic molecule.

[0350] In some embodiments, the activator protecting agent is present in the Type A fluid material in an amount between about 20 and about 2000 ppm mol/mol relative to the amount of the Type A fluid material.

[0351] In some embodiments, the molar ratio of the activator protecting agent and the transition metal activator in the Type A fluid material is about 1 : 1.

[0352] In some embodiments, the molar ratio of the activator protecting agent and the transition metal activator in the Type A fluid material is greater than about 1.1 : 1, greater than about 1.2:1, greater than about 1.3: 1, greater than about 1.4: 1, greater than about 1.5: 1, greater than about 1.6: 1, greater than about 1.7: 1, greater than about 1.8: 1, greater than about 1.9: 1, greater than about 2: 1, greater than about 3: 1, greater than about 4: 1, greater than about 5 : 1 , or greater than about 10:1. Antioxidants

[0353] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material further comprises an antioxidant. Antioxidants may be classified as primary or secondary antioxidants depending on the method by which they prevent oxidation. Without wishing to be bound by theory, primary antioxidants may function by donating their reactive hydrogen to the peroxy free radical so that the propagation of subsequent free radicals does not occur. The antioxidant free radical is rendered stable by electron delocalization. Secondary antioxidants may retard oxidation by preventing the proliferation of alkoxy and hydroxyl radicals by decomposing hydroperoxides to yield nonreactive products. These materials may be used in a synergistic combination with primary antioxidants. [0354] Suitable antioxidants include, for example, organic phosphites such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t- butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4- hydroxyhydrocinnamate)]methane, or the like; benzene polyols, such as catechols or the like; butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3- methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as di stearylthiopropi onate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate or the like; amides of beta-(3,5-di-tert-butyl-4- hydroxyphenyl)-propionic acid or the like; hindered amine light stabilizers (HALS) (e.g., (bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, decanedioic acid, bis(2,2,6,6- tetramethyl-l-(octyloxy)-4-piperidinyl) ester, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis(2,2,6,6-tetramethyl-4-piperidyl) succinate)), or combinations comprising at least one of the foregoing antioxidants.

[0355] As used herein, the term “phenol” refers to compounds that comprise one or more hydroxyl groups directly bonded to a phenyl group. Examples of phenols include, e.g., butylated hydroxytoluene (BHT), 4-tert-butylcatechol, 1,8- dihydroxynaphthalene, or the like.

[0356] As used herein, the term “monophenol” refers to compounds that comprise one hydroxyl group that is directly bonded to a phenyl group. Examples of monophenols include, e.g., butylated hydroxytoluene (BHT) or the like.

[0357] As used herein, the term “polyphenol” refers to compounds that comprise two or more hydroxyl groups that are directly bonded to a phenyl group. Examples of polyphenols include, e.g., 2,3 -dihydroxynaphthalene, 1,8-dihydroxynaphthalene, or the like.

[0358] As used herein, the term “benzene polyol” refers to compounds that comprise at least one phenyl group that is directly bonded to two or more hydroxyl groups. Examples of benzene polyols include 2,3-dihydroxynaphthalene, 4-tert- butylcatechol, 3,5-di-tert-butylcatechol, octyl gallate, pyrocatechol, or the like. Benzene polyols may be alkylated (e.g., 4-tert-butylcatechol, 3,5-di-tert- butylcatechol, octyl gallate, or the like) or non-alkylated (e.g., 2,3- dihydroxynaphthalene, pyrocatechol, pyrogallol, or the like).

[0359] In some embodiments, the primary antioxidant is a hindered phenol, a secondary aryl amine, a benzene polyol (e.g., an alkylated benzene polyol or a nonalkylated benzene polyol), or a combination thereof. In some embodiments, the hindered phenol comprises one or more compounds selected from butylated hydroxytoluene (BHT), triethylene glycol bis[3-(3-t-butyl-5-methyl-4- hydroxyphenyl)propionate], l,6-hexanediolbis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylene bis(3,5-di-t-butyl-4- hydroxy-hydrocinnamamide), tetrakis(methylene 3,5-di-tert-butyl- hydroxycinnamate)methane, and octadecyl 3,5-di-tert-butylhydroxyhydrocinnamate. [0360] In some embodiments, the antioxidant is an antioxidant described in WO 2023/201307, the contents of which are incorporated by reference in their entireties for all purposes.

[0361] Without wishing to be bound by theory, a compound described herein as an antioxidant may also function as an activator protecting agent. In some embodiments, the antioxidant is not an activator protecting agent. [0362] In some embodiments, the antioxidant is present in the Type A fluid material in an amount between about 100 and about 10,000 ppm w/w, relative to the amount of the Type A fluid material. In some embodiments, the antioxidant is present in the Type A fluid material in an amount between about 200 and about 1,000 ppm w/w, relative to the amount of the Type A fluid material.

[0363] In some embodiments, the antioxidant is present in the Type B fluid material in an amount between about 100 and about 10,000 ppm w/w, relative to the amount of the Type B fluid material. In some embodiments, the antioxidant is present in the Type B fluid material in an amount between about 200 and about 1,000 ppm w/w, relative to the amount of the Type B fluid material.

Reinforcing Additives

[0364] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material described herein can include reinforcing additives. In some embodiments, the reinforcing additives can include carbon fiber, fiber glass, cellulose fiber, material fibers (wood, jute) Polymer fibers (nylon, PVC, aramids, polyolefins, polyesters, polyurethanes), mineral fibers (asbestos), and/or silica (e.g., fumed or colloidal silica, treated hydrophobic fumed or colloidal silica).

Impact Modifiers

[0365] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material disclosed herein further comprises an impact modifier.

[0366] In some embodiments, the impact modifier comprises EPDM rubber, hydrogenated styrene-ethylene-butadiene-styrene (SEBS) copolymer, hydrogenated styrene-ethylene-propylene-styrene (SEPS) copolymer, hydrogenated styrene- ethylene-ethylene-propylene-styrene (SEEPS) copolymer, or a combination thereof. In some embodiments, the impact modifier comprises EPDM rubber. In some embodiments, the impact modifier comprises a hydrogenated styrene-ethylene- ethylene-propylene-styrene (SEEPS) copolymer. In some embodiments, the impact modifier comprises hydrogenated styrene-ethylene-propylene-styrene (SEPS) copolymer.

[0367] In some embodiments, the impact modifier comprises a synthetic rubber. [0368] In some embodiments, the synthetic rubber comprises an ethylene propylene diene monomer (EPDM) rubber.

[0369] In some embodiments, the synthetic rubber comprises a liquid ethylene propylene diene monomer (EPDM) rubber.

[0370] In some embodiments, the impact modifier comprises an elastomeric polymer (e.g., methyl methacrylate butadiene styrene (MBS), acrylonitrile butadiene (NBR), styrene butadiene styrene (SBS), styrene butadiene methyl methacrylate (SBM), styrene ethylene butylene styrene (SEBS), styrene ethylene propylene styrene (SEPS), styrene ethylene ethylene propylene styrene (SEEPS), liquid isoprene rubber (LIR), liquid famesene butadiene rubber (LFBR), and/or a silicone copolymer).

[0371] In some embodiments, the impact modifier comprises a core-shell nanoparticle (e.g. a methyl-methacrylate butadiene styrene core-shell nanoparticle). In some embodiments, the core-shell nanoparticle is commercially available as Dow Paraloid, Arkema Clearstrength and/or Kaneka Kane Ace.

Dyes and Pigments

[0372] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material further comprises a pigment, a dye, or a combination thereof.

[0373] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material further comprises a pigment.

[0374] In some embodiments, the pigment is an organic pigment, an inorganic pigment, or a combination thereof.

[0375] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material further comprises a dye.

[0376] In some embodiments, the dye is an organic dye, an inorganic dye, or a combination thereof.

[0377] In some embodiments, the dye comprises a solvent dye (e.g., (Solvent Red 164, Solvent Yellow 85, Sudan Black B). In some embodiments, the dye comprises an optical brightener (e.g., 2,2’-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole)) [0378] In some embodiments, the pigment comprises carbon black, titanium dioxide, silica, and/or phthalocyanine blue.

[0379] Without wishing to be bound by theory, it is noted that the pigment or dye may enable the optical sensing (e.g., scanning) of the deposited material during printing. [0380] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material containing the pigment or dye is colored, thereby enabling the optical sensing (e.g., scanning) of the deposited material by its color. In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material containing the pigment or dye is colorless but fluorescent, thereby enabling the optical sensing (e.g., scanning) of the deposited material by its fluorescence.

Flame Retardants

[0381] In some embodiments, the combination, kit, method, system, Type A Fluid Material, or Type B Fluid Material described herein can include flame retardants. In some embodiments, the flame retardants can include organophosphorus materials, including phosphates (triphenyl phosphate, ammonium polyphosphate), phosphonates (dimethyl methyl phosphonate), and/or phosphinates (diethylphosphinate salts). In some embodiments, the flame retardants can include melamines (melamine, melamine cyanurate). In some embodiments, the flame retardants can include organohalogen materials, including chlorinated paraffins, chlorendic acid, organo bromines, decabrominated diphenyl ether, brominated polystyrene, hexabromocyclododecane, and/or tetrabrom ophisphenol A.

Support Materials

[0382] In some embodiments, the support material is deposited (e.g., jetted) under a support depositing condition (e.g., support jetting condition).

[0383] In some embodiments, the support material is cured under a support curing condition.

[0384] In some embodiments, the support material or the cured support material is removed under a support removal condition.

[0385] In some embodiments, the support material is a liquid under the support depositing condition (e.g., the support jetting condition).

[0386] In some preferred embodiments, the support material is a wax (e.g., a polyethylene wax, ester wax, fatty acid, amide wax, aliphatic alcohol, polyethylene glycol-based wax, and/or a silicone wax, or mixtures thereof).

[0387] In some embodiments, the support material has a melting point being the same or lower than the temperature of the support depositing condition.

[0388] In some embodiments, upon deposition, the support material is converted to a solid (e.g., via a phase change). [0389] In some embodiments, upon deposition, the support material is converted to a solid by cooling.

[0390] In some embodiments, upon deposition, the support material is converted to a solid by curing.

[0391] In some embodiments, the cured support material is substantially stable (e.g., chemically and/or physically) toward the build material.

[0392] In some embodiments, the cured support material is substantially stable (e.g., chemically and/or physically) under the build curing condition.

[0393] In some embodiments, the cured support material comprises a polymer.

[0394] In some embodiments, the support removal condition comprises adding a solvent, thereby dissolving the cured support material.

[0395] In some embodiments, the support removal condition comprises mechanically removing the cured support material.

In some embodiments, the support removal condition comprises converting the support material from a solid to a liquid (e.g., via a phase change).

4 ALTERNATIVES

[0396] Certain applications benefit from depositing the activator/monomer mixture first and later depositing the precatalyst fluid onto the activator/monomer mixture. Other applications benefit from depositing the precatalyst fluid first and later depositing the activator/monomer mixture onto the precatalyst fluid. Either order of deposition can be used, and a mixed order of deposition may also be used.

[0397] As is alluded to above, a liberal amount of precatalyst is deposited. What is important is that enough precatalyst is deposited to ensure that substantially all the activator in the activator/monomer mixture reacts with precatalyst to form polymerization catalyst. In some embodiments, the precatalyst fluid (e.g., a Type B fluid material as described herein, comprising a ROMP pre-catalyst as described herein) is deposited in an amount such that the ROMP pre-catalyst is always in stoichiometric excess of the activator (e.g., a transition metal activator as described herein).

[0398] One alternative approach is to deposit a mixture of activator and monomer from one jet and a mixture of precatalyst and monomer from another jet. But doing so may require including an inhibitor in the mixture of precatalyst and monomer to prevent a reaction of the precatalyst and monomer in the printhead or during material storage. Thus, it is preferable that the precatalyst is not mixed with a monomer prior to deposition. To the extent that the precatalyst is a solid, or that the volume of the precatalyst fluid needs to be increased for effective inkjet deposition, the precatalyst is mixed with a solvent.

[0399] Alternative chemical strategies for the activation of ruthenium -based ROMP precatalysts include acidic/basic and oxidative/reductive activators. To give examples, an acid-sensitive ruthenium based precatalyst (e.g. LatMet, Aperion Synthesis, CAS: 1407229-58-6) may be activated by an acid activator (e.g. hydrochloric acid) and an oxidation- or reduction-sensitive precatalyst may be activated by an oxidizing or reducing activator. The approach we describe could also be generalized to polymerization chemistries other than ROMP using alternative precatalyst-activator pairs and monomers. One notable example is olefin polymerization using metallocene precatalysts, methylaluminoxane as an activator, and olefins as monomers.

[0400] The catalyst fluid should be mixed with one or more monomer fluid at a small ratio; at minimum less than 10:90, preferably less than 2:98, and ideally less than 1 :99. When ratios are too large the solvent in the catalyst fluid may act as a plasticizer in the cured material, leading to poor thermal and mechanical properties. [0401] A number of embodiments of the invention have been described. Nevertheless, it is to be understood that the foregoing description is intended to illustrate and not to limit the scope of the invention, which is defined by the scope of the following claims. Accordingly, other embodiments are also within the scope of the following claims. For example, various modifications may be made without departing from the scope of the invention. Additionally, some of the steps described above may be order independent, and thus can be performed in an order different from that described.

[0402] The aspects of the present disclosure are further described with reference to the following numbered embodiments:

Al . A method for additive manufacturing of an object, the method comprising: depositing a plurality of layers of material, the depositing including, for at least some layers of the plurality of layers of material, depositing a first fluid material, the first fluid material including an activator and a monomer; depositing a second fluid material including a pre-catalyst for reacting with the activator of the deposited first fluid material; wherein the depositing causes the second fluid material to disperse through the first fluid material, causing the pre-catalyst in the deposited second fluid material to react with the activator in the deposited first fluid material to form a polymerization catalyst with a concentration determined from a concentration of the activator in the deposited first fluid material, initiating a polymerization reaction.

A2. The method of embodiment Al wherein the initiating of the polymerization reaction includes generating a polymerization catalyst by reaction of the pre-catalyst with the activator, where the polymerization catalyst reacts with the monomer to generate a polymer and a polymerization catalyst.

A3. The method of embodiment Al wherein the polymerization reaction causes solidification of the deposited layer sufficient for deposition of a subsequent layer on the deposited layer.

A4. The method of embodiment Al wherein the second material includes a solvent.

A5. The method of embodiment Al wherein the second material does not include a monomer.

A6. The method of embodiment Al wherein the dispersion of the second fluid material through the first fluid material is due at least in part to diffusion.

A7. The method of embodiment Al wherein depositing the plurality of layers of material further comprises depositing a support material prior to depositing the first fluid material and the second fluid material, depositing the second fluid material onto the support material, and depositing the first fluid material onto the second fluid material.

A8. The method of embodiment A7 wherein: depositing the support material includes depositing a plurality of layers of support material to form a well, depositing the second fluid material onto the support material includes coating an inner surface of the support material in the well with the second fluid material, and depositing the first fluid material onto the second fluid material includes depositing the first fluid material into the well.

A9. The method of embodiment Al wherein the pre-catalyst is UltraLatMet, the activator is the Cu Co-Cat C7 copper(II) coordination complex, and the monomer is a blend of strained cyclic olefins 2-Ethylidene-l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8- dimethanonaphthalene and 5-decylbicyclo[2.2.1]hept-2-ene.

1. A combination comprising:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator;

(iii) a ROMP pre-catalyst; and

(iv) optionally, an activator protecting agent.

2B. A kit comprising the combination of embodiment 1.

2. The kit of embodiment 2B, comprising a Type A fluid material and a Type B fluid material, wherein: the Type A fluid material comprises:

(i) the ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) the transition metal activator; and the Type B fluid material comprises:

(iii) the ROMP pre-catalyst.

3. The kit of embodiment 2, comprising two or more Type A fluid materials or two or more Type B fluid materials, wherein each Type A fluid material independently comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a transition metal activator; and each Type B fluid material independently comprises:

(iii) a ROMP pre-catalyst.

4. The kit of embodiment 2 or embodiment 3, further comprising a support material.

5. A system for additive manufacturing of an object, comprising

(a) a printer; and

(b) the combination or kit of any one of the preceding embodiments.

5B. A method for additive manufacturing of an object, the method comprising: depositing a combination comprising:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator;

(iii) a ROMP pre-catalyst; and

(iv) optionally, an Activator Protecting Agent, thereby forming a cured material.

5C. A method for additive manufacturing of an object, the method comprising: depositing a Type A fluid material, wherein the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor; and

(ii) a transition metal activator; and depositing a Type B fluid material, wherein the Type B fluid material comprises:

(iii) a ROMP pre-catalyst; thereby forming a cured material.

6. A method for additive manufacturing of an object, the method comprising: depositing a plurality of layers of material, the depositing including, for at least some layers of the plurality of layers of material, depositing a Type A fluid material, wherein the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor; and

(ii) a transition metal activator; and depositing a Type B fluid material, wherein the Type B fluid material comprises:

(iii) a ROMP pre-catalyst; wherein the depositing causes the Type B fluid material to disperse through the Type A fluid material, causing the ROMP pre-catalyst in the deposited Type B fluid material to react with the transition metal activator in the deposited Type A fluid material to form a ROMP catalyst.

6B. A method for additive manufacturing of an object, the method comprising: depositing a Type A fluid material, wherein the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor; and

(ii) a transition metal activator; and depositing a Type B fluid material, wherein the Type B fluid material comprises:

(iii) a ROMP pre-catalyst; thereby forming a cured material.

6C. The method of claim 6B, wherein the depositing causes the Type B fluid material to disperse through the Type A fluid material, causing the ROMP precatalyst in the deposited Type B fluid material to react with the transition metal activator in the deposited Type A fluid material to form a ROMP catalyst.

7. A method for additive manufacturing of an object, the method comprising: depositing a Type A fluid material, wherein the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a transition metal activator; and depositing a Type B fluid material, wherein the Type B fluid material comprises:

(iii) a ROMP pre-catalyst; wherein the ROMP pre-catalyst reacts with the transition metal activator to form a ROMP catalyst.

8. The method of any of embodiments 5B -7, wherein the method is not conducted under an inert atmosphere.

8B. The method of any of embodiments 5B -7, wherein the depositing is not conducted under an inert atmosphere.

9. The method of any of embodiments 5B -8, wherein the Type B fluid is deposited in an amount such that the ROMP pre-catalyst is always in stoichiometric excess of the transition metal activator.

10. The method of any of embodiments 5B -8, wherein the ROMP pre-catalyst is deposited in stoichiometric excess relative to the transition metal activator.

IOB. The method of any of embodiments 5B-8, wherein the Type A fluid material and the Type B fluid material are deposited at a ratio such that the deposited ROMP pre-catalyst is present at an equal or greater amount relative to the deposited transition metal activator.

IOC. A cured material prepared by the method of any one of embodiments 5B-10B.

11. A Type A fluid material comprising:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator; wherein the Type A fluid material does not comprise a ROMP pre-catalyst.

12. A Type B fluid material comprising:

(iii) a ROMP pre-catalyst; wherein the Type B fluid material does not comprise a transition metal activator.

13. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the ROMP precursor comprises a compound of Formula (S-II):

wherein: q-S is 0, 1 or 2;

R³ and R⁵ are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2- Ci6 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R^S'^1A, -O-C(=O)- R^S'^1A, C₆-Ci4 aryl, -O-Ce-Cu aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^s'^1A)3, or -Z-(R⁷), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cu aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S'^1A;

R⁴ and R⁶ are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)- R^S'^1A, -O- C(=O)- R^S'^1A, Ce-Cu aryl, -O-Ce-C 14 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R^s'^1A)3, or -Z-(R⁷), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cu aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R^S'^1A; or

R⁴ and R⁶, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl; each R^S'^1A is independently halogen, Ci-Ce alkyl, or C1-C16 alkoxy;

Z is a bond, -(CR^s'^2AR^s-^3A)_a-, -O(CR^s'^2AR^s-^3A)_a-, -(CR^s'^2AR^s-^3A)_aO-, -(CR^S‘^2AR^s-3A)_a-O-(CR^s-^2AR^s-^3A)b-, -(CR^s'^2AR^s'^3A)_a-O-(SiR^s'^2AR^s'^3A)b-, -(CR^s'^2AR^s-^3A)_a- (C=O)O-(CR^s'^2AR^s'^3A)b-, -(CR^s'^2AR^s'^3A)-O(C=O)-(CR^s'^2AR^s'^3A)b-, -(CR^s'^2AR^s-^3A)_a- (C=O)-(CR^s'^2AR^s'^3A)b-; Each R^S-2A and R^S-3A is independently hydrogen, C1-C6 alkyl, C1-C6 alkoxy, - O-C(=O)-C1-C6 alkyl, -C(=O)-(C1-C6 alkyl), phenyl, or -O-phenyl; R⁷ is phenyl optionally substituted with one or more R^S-7A; Each R^S-7A is independently selected from C1-C6 alkyl, C1-C6 alkoxy, - O-C(=O)-C1-C6 alkyl, -C(=O)-(C1-C6 alkyl), phenyl, or -O-phenyl; and each a and b is independently an integer between 1 and 12; is a single bond or a double bond, wherein when is a double bond, R³ and R⁵ are both absent. 14. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the ROMP precursor comprises a compound of any one of Formula (S-IVa), (S-IVb), (S-IVc), and (S-IVd):

wherein: each Y is independently -CH₂, -CH₂-CH₂-, -O-, or -S-; X¹ is -O-, -S-, -NR^a, -SiR^bR^c, -SiR^bR^cO(SiR^bR^cO)m1SiR^bR^c, -SiR^bR^c(C6-C10 aryl)SiR^bR^c, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, C₁- C₁₈ alkyl, -CH=CH-, or -C≡C-; X² is -SiR^bR^c, -Si(R^bR^c)O(SiR^bR^cO)m1Si(R^bR^c), -Si(R^bR^c)(C6-C10 aryl)Si(R^bR^c), -C(=O)-, C1-C18 alkyl, -CH=CH-, or -C≡C-; R^a, R^b and R^c are each independently hydrogen, C₁-C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(C1-C3alkyl)Si(CH3)2; and each n1, n2, n3, and n4 is independently an integer 0, 1, or 2; each b₁, b₂, and b₄ is independently an integer between 1 and 10; m₁ is an integer between 0 and 10. 15. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the ROMP precursor comprises a compound of Formula (M-I):

or a salt thereof, wherein: Z^M is CH2 or O; each R^M-1 independently: (a) is H, halogen, cyano, -OR^M-1A, -SR^M-1A, -C(=O)-R^M-1A, -C(=O)-OR^M-1A, - O-C(=O)-R^M-1A, -C(=O)-N(R^M-1A)₂, -C(=O)-NHR^M-1A, -NH-C(=O)-R^M-1A, -N(R^M-1A)₂, -Si(R^M-1A)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A; or (b) together with another R^M-1 and the atoms to which they attach, form a bond, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A; each R^M-1A independently: (a) is H, halogen, cyano, -OR^M'^1B, -SR^M'^1B, -C(=O)-R^M'^1B, -C(=O)-OR^M'^1B, - O-C(=O)-R^M'^1B, -C(=O)-N(R^M'^1B)₂, -C(=O)-NHR^M'^1B, -NH-C(=O)-R^M'^1B, -N(R^M'^1B)₂, -Si(R^M'^1B)₃, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1B; or

(b) together with another R^M'^1A and the atoms to which they attach, form a bond, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M'^1B; each R^M'^1B independently is H, halogen, cyano, -OR^M'^1C, -SR^M'^1C, -C(=O)-R^M"

^IC, -C(=O)-OR^M'^1C, -O-C(=O)-R^M'^1C, -C(=0)-N(R^M'^1C)2, -C(=O)-NHR^M'^1C, -NH- C(=O)-R^M'^1C, -N(R^M'^1C)2, -Si(R^M'^lc)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3- C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl is optionally substituted with one or more R^M'^1C; each R^M'^1C independently is H, halogen, cyano, -OR^M'^1D, -SR^M'^1D, -C(=O)-R^M"

^ID, -C(=O)-OR^M'^1D, -O-C(=O)-R^M'^1D, -C(=0)-N(R^M'^1D)2, -C(=O)-NHR^M'^1D, -NH- C(=O)-R^M'^1D, -N(R^M'^1D)2, -Si(R^M'^1D)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3- C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl is optionally substituted with one or more R^M'^1D; and each R^M'^1D independently is H, halogen, cyano, -OH, -NH2, C1-C20 alkyl, C2- C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl.

16. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator comprises a Cu(I) complex, and Cu(II) complex, or a mixture thereof. 17. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator comprises a Cu(I) complex. 18. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator comprises a Cu(II) complex. 19. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator comprises a mixture of a Cu(I) complex and a Cu(II) complex. 20. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator comprises an Au(I) complex. 21. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator comprises a compound of Formula (A-I) or (A-II): L_mCu*X_n (A-I); LqAu*X (A-II) wherein: Cu* is Cu(I) or Cu(II); Au* is Au(I); each X is independently an X-type ligand; each L is independently an L-type ligand; m is 0, 1, 2, 3, 4, or 5; q is 0, 1, 2, 3, 4, 5 or 6; and when Cu* is Cu(I), n is 1, and when Cu* is Cu(II), n is 2. 22. The combination, kit, method, system, or Type A fluid material of embodiment 21, wherein: each X is independently F-, Cl-, Br-, I-, BF₄-, ClO₄-, NO₃-, PF₆-, HCO₃-, F6Sb-, C6-20 aryl-O-, [BAr^F4]-, C1-20 alkyl-, (C1-18 alkyl)-C≡C-, HC≡C-, C1-20 alkyl-O-, (C1-20 alkyl)-CO2-, (C1-20 alkyl)-CO3-, (C1-20 alkyl)-SO3-, (C1-20 alkyl)- NH-, (L^Ra)(L^Rb)NCO2-; each L is independently the ROMP precursor, H₂O, C_3-14 cycloalkyl, C2-20 alkenyl, C2-20 alkynyl, PR^p3, 5- to 14-membered heteroaryl, or 3- to 14- membered heterocycloalkyl; and ,

two X and two L may together form

each R^p is independently C_1-6 alkyl or phenyl; each R^s is independently H or C1-6 alkyl; each R^x is independently H or C1-6 alkyl; each R^y is independently H or C_1-6 alkyl, optionally wherein two R^y, together with the atoms to which they are connected form a phenyl or cyclohexyl; each R^z is independently H or C_1-6 alkyl; each L^Ra is independently H, C_1-6 alkyl, or C_6-10 aryl; each L^Rb is independently H, C1-6 alkyl, or C6-10 aryl; and

represents a point of attachment to Cu* or Au*. 23. The combination, kit, method, system, or Type A fluid material of any one of embodiments 21 or 22, wherein the transition metal activator comprises a compound of Formula (A-I) wherein Cu* is Cu(I). 24. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the transition metal activator is present in the Type A fluid material in an amount between about 1 and about 100 ppm mol/mol, or between about 10 and about 60 ppm mol/mol, relative to the amount of the Type A fluid material.

25. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the Type A fluid material further comprises an activator protecting agent.

26. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the activator protecting agent comprises a strong activator protecting agent.

27. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the activator protecting agent comprises a moderate activator protecting agent.

28. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the activator protecting agent comprises catechol or a catechol derivative.

29. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the activator protecting agent comprises hydroquinone, ascorbic acid, catechol, 4-/c/7-butyl catechol, or a mixture thereof.

30. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the activator protecting agent comprises catechol.

31. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the activator protecting agent is present in the Type A fluid material in an amount between about 20 and about 2000 ppm mol/mol relative to the amount of the Type A fluid material. 32. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the molar ratio of the activator protecting agent and the transition metal activator in the Type A fluid material is about 1 : 1.

33. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the molar ratio of the activator protecting agent and the transition metal activator in the Type A fluid material is greater than about 1.1 : 1, greater than about 1.2:1, greater than about 1.3: 1, greater than about 1.4: 1, greater than about 1.5: 1, greater than about 1.6: 1, greater than about 1.7: 1, greater than about 1.8: 1, greater than about 1.9: 1, greater than about 2: 1, greater than about 3: 1, greater than about 4: 1, greater than about 5 : 1 , or greater than about 10:1.

34. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the Type A fluid material further comprises an antioxidant.

35. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the Type A fluid material further comprises an antioxidant that is not an activator protecting agent.

36. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the antioxidant is present in the Type A fluid material in an amount between about 100 and about 10,000 ppm w/w, or between about 200 and about 1,000 ppm w/w, relative to the amount of the Type A fluid material.

37. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the Type A fluid material further comprises an organic acid.

38. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the Type A fluid material further comprises a catalyst inhibitor. 39. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the catalyst inhibitor is present in the Type A fluid material in an amount between about 5 and about 1000 ppm mol/mol, or between about 5 and about 50 ppm mol/mol relative to the amount of the Type A fluid material.

39B. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the molar ratio of the catalyst inhibitor and the transition metal activator in the Type A fluid material is about 1 : 1.

39C. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the molar ratio of the catalyst inhibitor and the transition metal activator in the Type A fluid material is between about 0.8: 1 and about 1.2: 1, between about 0.9: 1 and about 1.1 : 1, between about 0.95: 1 and about 1.05: 1, or between about 0.99: 1 and about 1.01 : 1.

40. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the Type A fluid material further comprises one or more additives independently selected from a reinforcing agent, an impact modifier, a dye, a pigment, and a flame retardant.

41. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material further comprises an inert solvent.

42. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the ROMP pre-catalyst comprises a compound of

Formula (C-I) or (C-II):

or a salt or a solvate thereof; wherein:

each R^x is independently Cl, Br, or I; each L^1-b is independently

represents either a single or double bond; each Ar^1-b is independently C6-C10 aryl or biphenyl; wherein the C6-C10 aryl or biphenyl is optionally substituted with one or more C₁-C₁₆ alkyl, C₁-C₆ alkoxy, or -N(C1-C6 alkyl)(C1-C6 alkyl); each R^1-a is independently H or C1-C6 alkyl; each R^1-b is independently C₁-C₆ alkyl, C₆-C₁₀ aryl, C₁-C₆ alkoxy, or - O(C₆-C₁₀ aryl); each R^2-b and R^3-b is independently C1-C6 alkyl, C3-C14 cycloalkyl, C6- C10 aryl or biphenyl, wherein the C6-C10 aryl or biphenyl is optionally substituted with one or more C₁-C₁₆ alkyl; or R^2-b and R^3-b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl; each R^4-b is independently C₁-C₁₆ alkyl, C₃-C₁₄ cycloalkyl, C₂-C₁₆ alkenyl, C6-C14 aryl, 5- to 14-membered heteroaryl, or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; R^6-b is absent, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₆-C₁₀ aryl, -O(C₁-C₁₀ aryl), - NHC=O(C1-C6 alkyl), -NHC=O(C1-C6 fluoroalkyl), -SO2N(C1-C6 alkyl)2, or - NO2; R^7-b is C₁-C₆ alkyl, cyclohexyl, or Ar^1-b; wherein the cyclohexyl, is optionally substituted with one or more C1-C16 alkyl, C1-C6 alkoxy, or -N(C1- C6 alkyl)(C1-C6 alkyl); R^11-b is absent,

each R^13-b is independently C1-C16 alkyl, C6-C10 aryl, -O(C1-C6 alkyl), - O(C6-C10 aryl), or C3-C14 cycloalkyl; R^14-b is halogen, -N(C₁-C₆ alkyl)₂, or –(C₁-C₁₆ alkyl)-(C₆-C₁₀ aryl); and z1 is 1 or 2. 43. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the ROMP pre-catalyst is present in the Type B fluid material in an amount between about 0.1% and about 5% w/w, or between about 0.5% and about 2% w/w, relative to the amount of the Type B fluid material. 44. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material further comprises an antioxidant. 45. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material further comprises an antioxidant that is not an activator protecting agent. 46. The combination, kit, method, system, or Type A fluid material of any of the preceding embodiments, wherein the antioxidant is present in the Type B fluid material in an amount between about 100 and about 10,000 ppm w/w, or between about 200 and about 1,000 ppm w/w, relative to the amount of the Type B fluid material. 47. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material further comprises a catalyst inhibitor. 48. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the molar ratio of catalyst inhibitor to ROMP pre- catalyst is between about 0.1:1 and about 10:1, between about 0.5:1 and about 1.5:1, between about 0.9:1 and about 1.1:1, between about 0.95:1 and about 1.05:1, between about 0.99:1 and about 1.01:1, or about 1:1. 49. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material further comprises one or more additives independently selected from a reinforcing agent, an impact modifier, a dye, a pigment, and a flame retardant.

50. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material further comprises a ring- opening-metathesis-polymerization (ROMP) precursor.

51. The combination, kit, method, system, or Type B fluid material of any of the preceding embodiments, wherein the Type B fluid material does not further comprise a ring-opening-metathesis-polymerization (ROMP) precursor.

5 EXAMPLES

Terms Used

Example 1. Fluid Material Compositions

[0403] Nine batches of Type A Fluid Material (containing a transition metal activator) and three batches of Type B Fluid Material (containing a ROMP precatalyst) were prepared according to Table 2 below:

Table 2: Type A Fluid Material Batches

Table 2: Type B Fluid Material Batches

Example 2. Fluid Material Compositions Cast into Teflon Mold

[0404] Batches of Type A Fluid Material and Type B Fluid Material were mixed to a total volume of 2 mL and immediately poured into an ASTM D638 Type IV tensile bar mold made of Teflon. The elapsed time between initial mixing and gelation was recorded. Samples were transferred to a vacuum oven and heated to 150 °C for 30 minutes and allowed to cool below 100 °C under vacuum. The glass transition temperature (Tg) of the fully cured samples was recorded by dynamic scanning calorimetry. The results are shown in Table 3 below.

Table 3:

Example 3. Stability Testing of Fluid Material Compositions

[0405] To evaluate the long-term stability of the Type A and Type B Fluid Materials, samples were placed in vials and stored in ovens set to 50 °C. Periodically, the resins were sampled and tested using the methods described in Example 2. No change in viscosity in any of the Type A and Type B Fluid Materials was observed.

The results are shown in Table 4 below.

Table 4:

Example 4. Fluid Material Compositions Cast into Silicone Mold

[0406] Type A and Type B Fluid Materials were mixed to the total volume required to fill the intended molds then immediately poured into an ASTM D638 Type IV tensile bar mold, and/or an ASTM D256 Izod impact bar mold made of silicone. Samples were transferred to a vacuum oven and heated to 150 °C for 30 minutes and allowed to cool below 100 °C under vacuum. The tensile properties were determined according to the ASTM D638 standard. If recorded, the impact strength was determined according to the ASTM D256 standard. The T_g was recorded by DSC. The results are shown in Table 5 below. Table 5:

Example 5. Samples Printed on an Inkbit Vista Inkjet 3D Printer

[0407] Type A and Type B Fluid Materials and a support material were loaded into three separate modules on one Inkbit Vista inkjet 3D printer configured as described herein. After being printed, the objects encased in support material were immersed in a molten bath of the support material at 80 °C to remove most of the support material. Then the objects were fully cured by heating to near their respective T_g in a vacuum oven or a thermal bath (e.g. silicone oil) for 30 minutes. The tensile properties were determined according to the ASTM D638 standard. The impact strength was determined according to the ASTM D256 standard. The T_g was recorded by DSC. The results are shown in Table 6 below.

Table 6:

EQUIVALENTS

[0408] The details of one or more embodiments of the disclosure are set forth in the accompanying description above. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. Other features, objects, and advantages of the disclosure will be apparent from the description and from the claims. In the specification and the appended claims, the singular forms include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents and publications cited in this specification are incorporated by reference.

[0409] The foregoing description has been presented only for the purposes of illustration and is not intended to limit the disclosure to the precise form disclosed, but by the claims appended hereto.

Claims

WHAT IS CLAIMED IS:

1. A method for additive manufacturing of an object, the method comprising: depositing a plurality of layers of material, the depositing including, for at least some layers of the plurality of layers of material, depositing a first fluid material, the first fluid material including an activator and a monomer; depositing a second fluid material including a pre-catalyst for reacting with the activator of the deposited first fluid material; wherein the depositing causes the second fluid material to disperse through the first fluid material, causing the pre-catalyst in the deposited second fluid material to react with the activator in the deposited first fluid material to form a polymerization catalyst with a concentration determined from a concentration of the activator in the deposited first fluid material, initiating a polymerization reaction.

2. The method of claim 1 wherein the initiating of the polymerization reaction includes generating a polymerization catalyst by reaction of the pre-catalyst with the activator, where the polymerization catalyst reacts with the monomer to generate a polymer and a polymerization catalyst.

3. The method of claim 1 wherein the polymerization reaction causes solidification of the deposited layer sufficient for deposition of a subsequent layer on the deposited layer.

4. The method of claim 1 wherein the second material includes a solvent.

5. The method of claim 1 wherein the second material does not include a monomer.

6. The method of claim 1 wherein the dispersion of the second fluid material through the first fluid material is due at least in part to diffusion.

7. The method of claim 1 wherein depositing the plurality of layers of material further comprises depositing a support material prior to depositing the first fluid material and the second fluid material, depositing the second fluid material onto the support material, and depositing the first fluid material onto the second fluid material.

8. The method of claim 7 wherein: depositing the support material includes depositing a plurality of layers of support material to form a well, depositing the second fluid material onto the support material includes coating an inner surface of the support material in the well with the second fluid material, and depositing the first fluid material onto the second fluid material includes depositing the first fluid material into the well.

9. The method of claim 1 wherein the pre-catalyst is UltraLatMet, the activator is the Cu Co-Cat C7 copper(II) coordination complex, and the monomer is a blend of strained cyclic olefins 2-Ethylidene-l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8- dimethanonaphthalene and 5-decylbicyclo[2.2.1]hept-2-ene.

10. A combination comprising:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator;

(iii) a ROMP pre-catalyst; and

(iv) optionally, an activator protecting agent.

11. A kit comprising the combination of claim 10, the kit comprising a Type A fluid material and a Type B fluid material, wherein: the Type A fluid material comprises:

(i) the ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) the transition metal activator; and the Type B fluid material comprises:

(iii) the ROMP pre-catalyst.

12. A kit comprising the combination of claim 10, the kit comprising one or more Type A fluid materials and one or more Type B fluid materials, wherein each Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor;

(ii) a transition metal activator; and the Type B fluid material comprises:

(iii) a ROMP pre-catalyst.

13. The kit of claim 11 or claim 12, further comprising a support material.

14. A system for 3D printing, comprising

(a) a printer; and

(b) the combination or kit of any one of the preceding claims.

15. A method for additive manufacturing of an object, the method comprising: depositing a plurality of layers of material, the depositing including, for at least some layers of the plurality of layers of material, depositing a Type A fluid material, wherein the Type A fluid material comprises:

(i) a ring-opening-metathesis-polymerization (ROMP) precursor; and

(ii) a transition metal activator; and depositing a Type B fluid material, wherein the Type B fluid material comprises:

(iii) a ROMP pre-catalyst; wherein the depositing causes the Type B fluid material to disperse through the Type A fluid material, causing the ROMP pre-catalyst in the deposited Type B fluid material to react with the transition metal activator in the deposited Type A fluid material to form a ROMP catalyst.

16. A method for additive manufacturing of an object, the method comprising: depositing a Type A fluid material, wherein the Type A fluid material comprises: (i) a ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a transition metal activator; and depositing a Type B fluid material, wherein the Type B fluid material comprises: (iii) a ROMP pre-catalyst; wherein the ROMP pre-catalyst reacts with the transition metal activator to form a ROMP catalyst.

17. The method of any of claims 15-16, wherein the method is not conducted under an inert atmosphere.

18. The method of any of claims 15-17, wherein the Type B fluid is deposited in an amount such that the ROMP pre-catalyst is always in stoichiometric excess of the transition metal activator.

19. The combination, kit, method, or system of any of the preceding claims, wherein the ROMP precursor comprises a compound of Formula (M-I):

or a salt thereof, wherein: Z^M is CH2 or O; each R^M-1 independently: (a) is H, halogen, cyano, -OR^M-1A, -SR^M-1A, -C(=O)-R^M-1A, -C(=O)-OR^M-1A, - O-C(=O)-R^M-1A, -C(=O)-N(R^M-1A)2, -C(=O)-NHR^M-1A, -NH-C(=O)-R^M-1A, -N(R^M-1A)2, -Si(R^M-1A)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A; or (b) together with another R^M-1 and the atoms to which they attach, form a bond, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1A; each R^M-1A independently: (a) is H, halogen, cyano, -OR^M-1B, -SR^M-1B, -C(=O)-R^M-1B, -C(=O)-OR^M-1B, - O-C(=O)-R^M-1B, -C(=O)-N(R^M-1B)2, -C(=O)-NHR^M-1B, -NH-C(=O)-R^M-1B, -N(R^M-1B)2, -Si(R^M-1B)₃, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1B; or (b) together with another R^M-1A and the atoms to which they attach, form a bond, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20- membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R^M-1B; each R^M-1B independently is H, halogen, cyano, -OR^M-1C, -SR^M-1C, -C(=O)-R^M-1C, -C(=O)-OR^M-1C, -O-C(=O)-R^M-1C, -C(=O)-N(R^M-1C)₂, -C(=O)-NHR^M-1C, -NH- C(=O)-R^M-1C, -N(R^M-1C)2, -Si(R^M-1C)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl, wherein the C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃- C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl is optionally substituted with one or more R^M-1C; each R^M-1C independently is H, halogen, cyano, -OR^M-1D, -SR^M-1D, -C(=O)-R^M-1D, -C(=O)-OR^M-1D, -O-C(=O)-R^M-1D, -C(=O)-N(R^M-1D)2, -C(=O)-NHR^M-1D, -NH- C(=O)-R^M-1D, -N(R^M-1D)2, -Si(R^M-1D)3, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl, wherein the C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₃- C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20- membered heteroaryl is optionally substituted with one or more R^M-1D; and each R^M'^1D independently is H, halogen, cyano, -OH, -NH2, C1-C20 alkyl, C2- C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C6-C20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl.

20. The combination, kit, method, or system of any of the preceding claims, wherein the transition metal activator comprises a Cu(I) complex, and Cu(II) complex, or a mixture thereof.

21. The combination, kit, method, or system of any of the preceding claims, wherein the transition metal activator comprises a compound of Formula (A-I):

LmCu*Xn (A-I); wherein:

Cu* is Cu(I) or Cu(II); each X is independently an X-type ligand; each L is independently an L-type ligand; m is 0, 1, 2, 3, 4, or 5; and when Cu* is Cu(I), n is 1, and when Cu* is Cu(II), n is 2.

22. The combination, kit, method, or system of any of the preceding claims, wherein the Type A fluid material further comprises an activator protecting agent.

23. The combination, kit, method, or system of claim 22, wherein the activator protecting agent comprises hydroquinone, ascorbic acid, catechol, 4-tert- butyl catechol, or a mixture thereof.

24. The combination, kit, method, or system of any of the preceding claims, wherein the Type B fluid material further comprises an inert solvent.

25. The combination, kit, method, or system of any of the preceding claims, wherein the ROMP pre-catalyst comprises a compound of Formula (C-I) or (C-II):

or a salt or a solvate thereof; wherein:

each R^x is independently Cl, Br, or I; each L^1-b is independently

represents either a single or double bond; each Ar^1-b is independently C6-C10 aryl or biphenyl; wherein the C6-C10 aryl or biphenyl is optionally substituted with one or more C₁-C₁₆ alkyl, C₁-C₆ alkoxy, or -N(C₁-C₆ alkyl)(C₁-C₆ alkyl); each R^1-a is independently H or C1-C6 alkyl; each R^1-b is independently C₁-C₆ alkyl, C₆-C₁₀ aryl, C₁-C₆ alkoxy, or - O(C₆-C₁₀ aryl); each R^2-b and R^3-b is independently C1-C6 alkyl, C3-C14 cycloalkyl, C6- C₁₀ aryl or biphenyl, wherein the C₆-C₁₀ aryl or biphenyl is optionally substituted with one or more C₁-C₁₆ alkyl; or R^2-b and R^3-b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl; each R^4-b is independently C₁-C₁₆ alkyl, C₃-C₁₄ cycloalkyl, C₂-C₁₆ alkenyl, C6-C14 aryl, 5- to 14-membered heteroaryl, or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; R^6-b is absent, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₆-C₁₀ aryl, -O(C₁-C₁₀ aryl), - NHC=O(C1-C6 alkyl), -NHC=O(C1-C6 fluoroalkyl), -SO2N(C1-C6 alkyl)2, or - NO₂; R^7-b is C1-C6 alkyl, cyclohexyl, or Ar^1-b; wherein the cyclohexyl, is optionally substituted with one or more C1-C16 alkyl, C1-C6 alkoxy, or -N(C1- C₆ alkyl)(C₁-C₆ alkyl); R^11-b is absent,

each R^13-b is independently C1-C16 alkyl, C6-C10 aryl, -O(C1-C6 alkyl), - O(C6-C10 aryl), or C3-C14 cycloalkyl; R^14-b is halogen, -N(C₁-C₆ alkyl)₂, or –(C₁-C₁₆ alkyl)-(C₆-C₁₀ aryl); and z₁ is 1 or 2.

26. The combination, kit, method, system, or Type B fluid material of any of the preceding claims, wherein the Type B fluid material does not further comprise a ring- opening-metathesis-polymerization (ROMP) precursor.