Macrocyclic olefins for ring-opening metathesis polymerization (ROMP) and uses thereof

Abstract

The present disclosure relates to materials for ring-opening metathesis polymerization (ROMP). The present disclosure also relates to uses of the materials, e.g., in 3D printing.

Description

[0001] MACROCYCLIC OLEFINS FOR RING-OPENING METATHESIS POLYMERIZATION (ROMP) AND USES THEREOF

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to, and the benefit of, U. S. Provisional Application No.

[0003] 63 / 713,134, filed October 29, 2024, the contents of which are incorporated by reference in their entirety.

[0004] BACKGROUND

[0005] Additive manufacturing, also known as 3D printing, refers to a relatively wide class of techniques that allows objects to be fabricated via selective addition of material according to a computer-controlled process, generally to match a desired 3D specification, for example, a solid model. A number of different classes of materials have been used for such 3D printing, with different materials providing corresponding advantages and / disadvantages for different fabrication techniques. For example, a survey of materials may be found in Ligon et al. (Chemical Reviews 117(15): 10212-10290 (2017)).

[0006] A class of fabrication techniques jets material for deposition on a partially fabricated object using inkjet printing technologies. The jetted material is typically cured (e.g., by UV radiation) shortly after it is deposited, forming thin layers of cured material. To achieve precision fabrication, some techniques use mechanical approaches to maintain accurate layer-to-layer structure, for example, using mechanical rollers or “planarizers” to control the surface geometry, and therefore control the accuracy of the fabricated object. Therefore, rapid curing is a key feature to allow the planarization and obtain an accurately fabricated object. However, the resulting material properties obtained with such inks may be insufficient.

[0007] What is needed is a printable material that exhibit high tensile strength / tensile modulus combined with high elongation at break and / or high impact strength. The present invention addresses this need.

[0008] SUMMARY

[0009] In some aspects, the present disclosure provides a combination comprising:

[0010] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0011] (ii) a bridged polycyclic ROMP precursor; and

[0012] (iii) a curing catalyst. In some aspects, the present disclosure provides a kit comprising:

[0013] a build material comprising:

[0014] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0015] (iii) a latent curing catalyst;

[0016] (iv) an activator; and

[0017] a support material.

[0018] In some aspects, the present disclosure provides a kit comprising:

[0019] a first build material comprising:

[0020] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0021] (iii) an activator

[0022] a second build material comprising:

[0023] (iv) a curing catalyst

[0024] (v) a solvent; and

[0025] a support material.

[0026] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor is a strained ROMP precursor.

[0027] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-I):

[0028]

[0029] wherein W is CH2 or C=O;

[0030] Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; and

[0031]

[0032] , together with the atoms to which it is attached and any intervening atoms, forms a 14- to 50- membered ring comprising 1-10 C=C bonds.

[0033] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-Ia):

[0034]

[0035] wherein:

[0036] W is CH2or C=O;

[0037] m and n are each independently an integer between 0 and 20;

[0038] Ri and R2are each independently absent, -CH2-, -O-, or -NH-;

[0039] *

[0040] each - is independently a single bond or a double bond having either the (E) or (Z) configuration; and

[0041] *

[0042] wherein at least one - is a double bond;

[0043] provided that:

[0044] a) when neither of Ri and R2are absent, the sum of m + n is > 7; b) when one of Ri and R2is absent, the sum of m + n is > 8; and c) when both of Ri and R2are absent, the sum of m + n is > 9.

[0045] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the macrocyclic ROMP precursor comprises Compound (R-l), Compound (R-2), Compound (R-3), or Compound (R-4):

[0046]

[0047]

[0048] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-II):

[0049]

[0050] wherein:

[0051] q is 0, 1 or 2;

[0052] R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4 aryl, -O-C6-Ci4 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-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 R1A;

[0053] R4and R6are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-C14 aryl, -O-C6-C14 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-C14 aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A; or

[0054] R4and R6, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl;

[0055] each R1Ais independently halogen, Ci-Ce alkyl, or C1-C16 alkoxy;

[0056] Z is a bond, -(CR2AR3A)a-, -O(CR2AR3A)a-, -(CR2AR3A)aO-, -(CR2AR3A)a-O-(CR2AR3A)b-, -(CR2AR3A)a-O-(SiR2AR3A)b-, -(CR2AR3A)a-(C=O)O-(CR2AR3A)b-, -(CR2AR3A)-O(C=O)-(C R2AR3A)b-, -(CR2AR3A)a-(C=O)-(CR2AR3A)b-; Each R2Aand R3Ais independently hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;

[0057] R7is phenyl optionally substituted with one or more R7A;

[0058] Each R7Ais independently selected from Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;

[0059] and

[0060] each a and b is independently an integer between 1 and 12;

[0061] is a single bond or a double bond, wherein when - - is a double bond, R3and R5are both absent.

[0062] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises Compound S-l:

[0063]

[0064] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises Compound S-2:

[0065]

[0066] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises Compound S-3:

[0067]

[0068] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIa):

[0069]

[0070] wherein: R13is C1-C16 alkyl.

[0071] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises Compound S-4:

[0072]

[0073] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-III):

[0074]

[0075] wherein:

[0076] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(C6-Ci4aryl); or

[0077] R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0078] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0079] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0080] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIa):

[0081]

[0082] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)- C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4aryl, or -O-(C6-Ci4aryl); or R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0083] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4 alkoxy, -C1-C16 alkoxy, -O-(C6-Ci4 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0084] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0085] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIb):

[0086]

[0087] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4aryl, or -O-(C6-Ci4aryl); or

[0088] R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0089] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(C6-C14 aryl)-Ci-Ci4 alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0090] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0091] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of any one of Formulae (S-IVa), (S-IVb), (S-IVc), and (S-IVd):

[0092]

[0093] each Y is independently -CH2, -CH2-CH2-, -O-, or -S-;

[0094] X1is -O-, -S-, -NRa, -SiRbRc, -SiRbRcO(SiRbRcO)miSiRbRc, -SiRbRc(C6-Cio aryl)SiRbRc, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, Ci-Cis alkyl, -CH=CH-, or -C=C-;

[0095] X2is -SiRbRc, -Si(RbRc)O(SiRbRcO)miSi(RbRc), -Si(RbRc)(C6-Cio aryl)Si(RbRc), -C(=O)-, Ci-Cis alkyl, -CH=CH-, or -C=C-;

[0096] Ra, Rband Rcare each independently hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2; and

[0097] each n1, n2, n3, and n4 is independently an integer 0, 1, or 2;

[0098] each bi, b2, and b4 is independently an integer between 1 and 10;

[0099] mi is an integer between 0 and 10.

[0100] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst is a ruthenium catalyst.

[0101] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst is a latent ruthenium catalyst.

[0102] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst is a non-latent ruthenium catalyst. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst is a Grubbs catalyst.

[0103] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst is a first-generation Grubbs catalyst, a second-generation Grubbs catalyst, a third-generation Grubbs catalyst, a first-generation Grubbs-Hovey da catalyst, or a second-generation Grubbs-Hovey da catalyst.

[0104] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst is a ruthenium-indenylidene complex.

[0105] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII):

[0106]

[0107] wherein: L1-ais L2'aor L3'a;

[0108]

[0109] Each L1-bis independently L2'b, L3'b, L4'b, L8'b, L9'b, or L10'b,

[0110] L2'bis P(R5'b)3, pyridine, or dimethylsulfoxide, wherein the pyridine is optionally subsituted with one or more C1-C16 alkyl;

[0111]

[0112] L9'bis P(R9'b)3; L10'bis P(R10'b)3;

[0113] Each Ar1-a, Ar2'a, Ar3'21, Ar4'a, Arl-band Ar2'13is independently Ce-Cio aryl or biphenyl; wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl, C1-C6 alkoxy, or -N(CI-C6alkyl)(Ci-C6alkyl);

[0114]

[0115] ---- is a single bond or a double bond;

[0116] Rxis halogen;

[0117] R1-ais Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl);

[0118] each R2 aand R3 ais independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; or

[0119] R2 aand R3 a, together with the carbon to which they are attached, form a C3-C14 cycloalkyl;

[0120] R4'ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0121] R5 ais Ci-Cie alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Ci4 aryl or biphenyl, wherein the Ce-Ci4 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0122] R8'ais Ci-Ce alkyl, C3-C14 cycloalkyl, or Ce-Cio aryl;

[0123] each R1-bis independently Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl); each R2 band R3'bis independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; or

[0124] R2 band R3'b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl;

[0125] Each R4'band R5 bis independently C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0126] R6'bis absent, Ci-Ce alkyl, Ci-Ce alkoxy, Ce-Cio aryl, -0(Ci-Cio aryl), -NHC=O(Ci-Ce alkyl), -NHC=O(Ci-Ce fluoroalkyl), -SO2N(Ci-Ce alkyl)2, or -NO2;

[0127] R7 bis Ci-Ce alkyl, cyclohexyl, Ce-Cio aryl or biphenyl; wherein the cyclohexyl, Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; each R8'band R9'bis independently methyl or benzyl; wherein the benzyl is optionally substituted with one or more C1-C16 alkyl;

[0128] each R10'bis independently C1-C16 alkyl or C3-C14 cycloalkyl; and

[0129] zi is 1 or 2.

[0130] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst comprises Compound C-l:

[0131]

[0132] or a solvate thereof.

[0133] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the curing catalyst comprises Compound C-2:

[0134]

[0135] or a solvate thereof.

[0136] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising an activator.

[0137] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the activator comprises a copper(I), copper(II) or ruthenium based complex. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the activator comprises a compound of any one of Formulae (A-I), (A-II), (A- III), (A-IV), and (A-V):

[0138] RuCl2(PPh3)p(A-I),

[0139] CuRzPPh3(A-II),

[0140] CuRz- (A-III),

[0141] (Rm)cCuCl (A-IV),

[0142]

[0143] solvate thereof,

[0144] wherein Rzis halogen;

[0145] Rmis a compound of Formula (S-II), (S-III), (S-IIIa), (S-IIIb), (S-IVa), (S-IVb), (S-IVc), or (S-IVd);

[0146] nhc is an N-heterocyclic carbene;

[0147] each Ar4is Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0148] p is 3 or 4; and

[0149] c is 0, 1, 2, 3, 4, 5, or 6.

[0150] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the activator comprises Compound A-l:

[0151]

[0152] or a solvate thereof. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising a crosslinker.

[0153] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising a synthetic rubber.

[0154] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising a polymerization retardant.

[0155] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising an impact modifier.

[0156] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising a filler.

[0157] In some aspects, the present disclosure provides a build material comprising a combination disclosed herein.

[0158] In some aspects, the present disclosure provides a kit comprising a combination disclosed herein.

[0159] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising an antioxidant.

[0160] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising a stabilizer.

[0161] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, further comprising a chain transfer agent.

[0162] In some aspects, the present disclosure provides a method of preparing a cured material, comprising a step of subjecting a combination or kit disclosed herein to a curing condition. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein for use in preparing a cured material, wherein the preparation comprises a step of subjecting the combination or kit to a curing condition.

[0163] In some aspects, the present disclosure provides a use of a combination, build material, or kit of disclosed herein in the manufacture of a cured material, wherein the manufacture comprises a step of subjecting the combination or kit to a curing condition.

[0164] In some aspects, the present disclosure provides a cured material being prepared by a method disclosed herein.

[0165] In some aspects, the present disclosure provides a method of printing an object using a method, combination kit disclosed herein.

[0166] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein for use in printing an object.

[0167] In some aspects, the present disclosure provides a method, combination, build material, or kit disclosed herein, for use in printing an object wherein the printing comprises

[0168] (i) depositing the build material; and

[0169] (ii) subjecting the deposited build material to a curing condition.

[0170] In some aspects, the present disclosure provides a method, combination, build material, or kit disclosed herein, for use in printing an object wherein the printing comprises

[0171] (i) providing the build material and

[0172] (ii) providing an energy source to activate the radical initiator.

[0173] In some aspects, the present disclosure provides a method, combination, build material, or kit disclosed herein, for use in printing an object wherein the printing comprises exposing the build material to an energy source (e.g., a light source, e.g., UV light).

[0174] In some aspects, the present disclosure provides a method, combination, build material, or kit disclosed herein, for use in printing an object wherein the printing further comprises optically sensing the deposited material, and controlling the one or more repeated deposition of the material according to the sensing.

[0175] In some aspects, the present disclosure provides a system for 3D printing, comprising:

[0176] (i) a printer; and

[0177] (ii) an ink comprising the combination of any one of the preceding claims.

[0178] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of an exemplary 3D printer.

[0179] FIG. 2 is a schematic diagram of an alternative exemplary 3D printer.

[0180] DETAILED DESCRIPTION

[0181] To achieve the high tensile strength / tensile modulus combined with high elongation at break and / or high impact strength, ROMP (Ring-Opening Metathesis Polymerization)-derived materials show several advantages over typical thermosetting materials used for additive manufacturing such as acrylates or epoxies. Those advantages being among others: higher toughness, impact strength, and better chemical resistance. Typically, the low viscosity of ROMP monomers might be another advantage in some applications. Accordingly, there is a growing interest in developing new formulations for ROMP reactions.

[0182] Surprisingly, it has been found that macrocyclic compounds can be mass co-polymerised with highly strained monomers providing well cured polymers that combine high tensile strength and tensile modulus with high elongation at brake. Advantageously, the impact strength of the polymers obtained from formulations according to the present invention is not negatively affected and in some cases is even improved.

[0183] To achieve the high latency and rapid polymerization desired for applications such as 3D printing, reactive injection molding, and others, polymers such as UV-cure epoxies, UV-cure acrylates polyurethanes, polyureas, polyisocyanurates, polyesters, and polyphenols are typically used. Cyclic olefin polymers generated by Ring-Opening Metathesis (ROMP) can possess superior properties for many applications. However, the applications of ROMP technology can be limited due to its rapid curing at ambient conditions (e.g., room temperature). Typically, a formulation polymerizable by ROMP immediately solidifies once a catalyst is added. This limits the use of ROMP formulations in 3D inkjet processes, where liquid formulations that feature viscosities within a pre-determined range are required to be passed through inkjet printing heads.

[0184] In addition, in inkjet printing, low viscosity (e.g., 0.5-150 cP at 90 °C, 0.5-120 cP at room temperature, and / or 0.5-1,000 cP at room temperature), low surface tension (e.g., 20-45 mN / m) and low particulate size (e.g., filterable through a 3 pm filter) are highly desirable. Furthermore, inkjet 3D printers and similar techniques rely on the formation of small, high surface-area droplets; many common polymerization components, such as dicyclopentadiene (DCPD), may be unsuitable for inkjet printing, due to their low flash points and the hot surfaces and electronic components in such printers (without wishing to be bound by theory, droplets of a flammable liquid can be more flammable than bulk liquid of the same chemical composition). On the other hand, many polymerizable compositions developed for other 3D printing methods, such as stereolithography (SLA), may possess properties which are unnecessary or detrimental in inkjet printing, such as selective photo inhibitors needed to prevent polymerization outside the desired print area.

[0185] There is a need for novel compositions for ROMP that possess most or all of the beneficial characteristics for various 3D printing methods (e.g., inkjet 3D printing), such as high overall polymerization speed, high latency, low viscosity, low particulate content, high flash point, and the like. The present disclosure addresses this need.

[0186] Suitable applications and systems for the materials of the present disclosure are described, e.g., in U. S. Provisional Appl’n No. 62 / 777,422 and PCT Appl’n No. PCT / US2019 / 065436 (incorporated herein by reference).

[0187] In some 3D printing techniques, the building of a three-dimensional object is performed in a step-wise or layer-wise manner. In particular, layer formation is performed by solidification of a photocurable resin under irradiation of visible light or UV light. Commonly referred to as "stereolithography", two particular techniques are known: a new layer is formed on the top surface of the grown object; the other forms a new layer on the bottom surface of the grown object. Examples of such methods include those given in U. S. Pat. Nos. 5,236,637. S. 5,391,072 5,529,473 7,438,8467,892,474 and 8,110,135 More recently, a technique known as "continuous liquid interface manufacturing" (or "CLIP") has been developed. This technique enables the rapid fabrication of three-dimensional objects in a non-layered manner by which components can have desirable structural and mechanical properties. See, e.g., U. S. patent Nos. 9,211,678, 9,205,601, and 9,216,546), J. Tumbleston et al, Continuous liquid interface production of 3D Objects, Science 347,1349-1352, and Janusziewicz, Rima et al. “Layerless fabrication with continuous liquid interface production.” Proc NatlAcadSci U SA vol. 113,42 (2016): 11703-11708.

[0188] Volumetric additive manufacturing (AM) is a recently developed concept. For example, see the work of Loterie, Damien, Paul Delrot, and Christophe Moser, “VOLUMETRIC 3D PRINTING OF ELASTOMERS BY TOMOGRAPHIC BACK-PROJECTION” https: / / www.researchgate.net / publication / 328956954 (2018). Another example of volumetric AM is Kelly, Brett E., Indrasen Bhattacharya, Hossein Heidari, Maxim Shusteff, Christopher M. Spadaccini, and Hayden K. Taylor, “Volumetric additive manufacturing via tomographic reconstruction,” Science 363, no. 6431 (2019): 1075-1079. Volumetric AM has shown significant promise in accelerating the rate of polymer-based additive manufacturing, among many other benefits. Volumetric printing is carried out over a 3D volume simultaneously rather than building up a 3D structure (i.e., part or component) via scanned point or 2D-surface curing operations.

[0189] Reactive injection molding is the formation of objects by injecting resin into a mold, and then curing within the mold. Many types of polymers and polymeric objects can be manufactured via reactive injection molding, including polyurethanes, polyamides, polyesters, and / or molded thermosets. Process variables that can be manipulated during reactive injection molding include cure speed, ease of initiation, stability of precursor resins, thermal management, and additives used to control these properties.

[0190] The reactive injection molding of cyclic olefin resins via ROMP can be used in the manufacturing of functional parts that require extreme toughness, chemical resistance, heat resistance, and light weight. Examples include hoods, wind deflectors, and fasciae for heavy truck and agricultural and industrial equipment. Examples of commercial cyclic olefin products produced via ROMP include Telene®, Pentam®, Metton®, Cyonyx®, Prom eta®, Norsorex®, Zeonex®, Zeonor®, and Arton®. The use of ROMP reactions in reaction injection molding (RIM) has been described, for example, in U. S. Patent Application Publication Nos.

[0191] 2011 / 0171147, and U. S. Pat. No. 8,487,046.

[0192] ROMP processes described herein may have several advantages to other existing technologies, such as high tensile strength / tensile modulus combined with high elongation at break and / or high impact strength, which are desirable for applications such as 3D printing, reactive injection molding, resin transfer molding, pultrusion, vacuum infusion, coatings, and others.

[0193] Coatings modify the surface characteristics of a material, for the purpose of making the surface more wear resistant, UV resistant, chemical resistant, hydrophobic, hydrophilic, colored, less oxygen permeable, and other properties. Cyclic olefin polymers prepared via ROMP are especially suitable in the fabrication of tough and wear-resistant coatings. Using a photomask, catalyst activation can be confined to regions irradiated with light.

[0194] The compositions herein may also be advantageous for the manufacture of adhesives and dental fillings, in which a fast-curing resin with high post-curing toughness can be advantageous.

[0195] In some aspects, the present disclosure provides a combination comprising:

[0196] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0197] (ii) a bridged polycyclic ROMP precursor; and

[0198] (iii) a curing catalyst.

[0199] In some aspects, the present disclosure provides a kit comprising:

[0200] a build material comprising:

[0201] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0202] (iii) a latent curing catalyst;

[0203] (iv) an activator; and

[0204] a support material.

[0205] In some aspects, the present disclosure provides a kit comprising:

[0206] a first build material comprising: (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0207] (iii) an activator

[0208] a second build material comprising:

[0209] (iii) a curing catalyst

[0210] (iv) a solvent; and

[0211] a support material.

[0212] It is understood that, for a combination, build material, or kit described herein, the macrocyclic ROMP precursor, bridged polycyclic ROMP precursor, curing catalyst, activator, solvent, antioxidant, crosslinker, impact modifier, filler, chain transfer agent, and support material can each be, where applicable, selected from the groups described herein, and any group described herein for any of the macrocyclic ROMP precursor, bridged polycyclic ROMP precursor, curing catalyst, activator, solvent, antioxidant, crosslinker, impact modifier, filler, chain transfer agent, and / or support material can be combined, where applicable, with any group described herein for one or more of the remainder of the macrocyclic ROMP precursor, bridged polycyclic ROMP precursor, curing catalyst, activator, solvent, antioxidant, crosslinker, impact modifier, filler, chain transfer agent, and / or support material.

[0213] Macrocyclic ROMP Precursors

[0214] In some embodiments, the macrocyclic ROMP precursor comprises a compound of Formula (R-I):

[0215]

[0216] wherein W is CH2 or C=O;

[0217] Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; and

[0218]

[0219] , together with the atoms to which it is attached and any intervening atoms, forms a 14- to 50- membered ring comprising 1-10 C=C bonds.

[0220] In some embodiments, the macrocyclic ROMP precursor comprises a compound of Formula (R-Ia):

[0221]

[0222] wherein:

[0223] W, Ri, and R2 are as described herein;

[0224] m and n are each independently an integer between 0 and 20; and

[0225] *

[0226] each - is independently a single bond or a double bond having either the (E) or (Z) configuration;

[0227] *

[0228] wherein at least one - is a double bond;

[0229] provided that:

[0230] a) when neither of Ri and R2 are absent, the sum of m + n is > 7; b) when one of Ri and R2 is absent, the sum of m + n is > 8; and c) when both of Ri and R2 are absent, the sum of m + n is > 9.

[0231] In some embodiments, the macrocyclic ROMP precursor comprises a compound of Formula (R-Ib):

[0232]

[0233] wherein Ri, R2 m, and n are as described herein; and = is a double bond having either the (E) or (Z) configuration.

[0234] In some embodiments, the macrocyclic ROMP precursor comprises a compound of Formula (R-Ic):

[0235]

[0236] wherein Ri, R2 m, n, and = are as described herein.

[0237] In some embodiments, the macrocyclic ROMP precursor comprises a compound of Formula (R-Id):

[0238]

[0239] wherein m, n, and = are as described herein.

[0240] In some embodiments, the macrocyclic ROMP precursor comprises a compound of Formula (R-Ie):

[0241]

[0242] wherein m, n, and = are as described herein.

[0243] In some embodiments, W is C=O. In some embodiments, W is CH₂.

[0244] In some embodiments, Ri is absent. In some embodiments, Ri is -CH2-. In some embodiments, Ri is -O-.

[0245] In some embodiments, R2 is absent. In some embodiments, R2 is -CH2-. In some embodiments, R2 is -O-. In some embodiments, Ri is CH2 and R2 is CH2. In some embodiments, Ri is CH2 and R2 is -O-. In some embodiments, Ri is -O- and R2 is CH2. In some embodiments, Ri is CH2 and R2 is absent.

[0246] In some embodiments, Ri is absent and R2 is CH2. In some embodiments, Ri and R2 are absent.

[0247] In some embodiments, W is C=O, Ri is CH2, and R2 is CH2. In some embodiments, W is C=O, Ri is CH2, and R2 is -O-. In some embodiments, W is C=O, Ri is CH2, and R2 is absent. In some embodiments, W is C=O, Ri is absent, and R2 is CH2. In some embodiments, W is C=O and Ri and R2 are absent. In some embodiments, W is CH2, Ri is CH2, and R2 is CH2. In some embodiments, W is CH2, Ri is CH2, and R2 is absent. In some embodiments, W is CH2, Ri is absent, and R2 is CH2. In some embodiments, W is CH2 and Ri and R2 are absent.

[0248]

[0249] In some embodiments,

[0250]

[0251] , together with the atoms to which it is attached and any intervening atoms, forms a 14-membered ring comprising 1 C=C bond.

[0252]

[0253] In some embodiments,

[0254]

[0255] , together with the atoms to which it is attached and any intervening atoms, forms a 15-membered ring comprising 1 C=C bond.

[0256]

[0257] In some embodiments,

[0258]

[0259] , together with the atoms to which it is attached and any intervening atoms, forms a 16-membered ring comprising 1 C=C bond.

[0260]

[0261] In some embodiments,

[0262]

[0263] , together with the atoms to which it is attached and any intervening atoms, forms a 17-membered ring comprising 1 C=C bond. In some embodiments,

[0264]

[0265] , together with the atoms to which it is attached and any intervening atoms, forms a 16-membered ring comprising 2 C=C bonds.

[0266]

[0267] In some embodiments,

[0268]

[0269] , together with the atoms to which it is attached and any intervening atoms, forms a 14-16 membered ring comprising 1 C=C bond.

[0270]

[0271] In some embodiments,

[0272]

[0273] , together with the atoms to which it is attached and any intervening atoms, forms a 14-15 membered ring comprising 1 C=C bond.

[0274] In some embodiments,

[0275]

[0276] , together with the atoms to which it is attached and any intervening atoms, forms a 14-17 membered ring comprising 1 C=C bond.

[0277]

[0278] In some embodiments,

[0279]

[0280] , together with the atoms to which it is attached and any intervening atoms, forms a 14-16 membered ring comprising 1 C=C bond.

[0281]

[0282] In some embodiments,

[0283]

[0284] , together with the atoms to which it is attached and any intervening atoms, forms a 14-18 membered ring comprising 1 C=C bond.

[0285]

[0286] In some embodiments,

[0287]

[0288] , together with the atoms to which it is attached and any intervening atoms, forms a 14-19 membered ring comprising 1 C=C bond. In some embodiments,

[0289]

[0290] , together with the atoms to which it is attached and any intervening atoms, forms a 14-20 membered ring comprising 1 C=C bond.

[0291]

[0292] In some embodiments,

[0293]

[0294] , together with the atoms to which it is attached and any intervening atoms, forms a 14-21 membered ring comprising 1 C=C bond.

[0295]

[0296] In some embodiments,

[0297]

[0298] , together with the atoms to which it is attached and any intervening atoms, forms a 14-25 membered ring comprising 1 C=C bond.

[0299] In some embodiments,

[0300]

[0301] , together with the atoms to which it is attached and any intervening atoms, forms a 14-26 membered ring comprising 1 C=C bond.

[0302]

[0303] In some embodiments,

[0304]

[0305] , together with the atoms to which it is attached and any intervening atoms, forms a 14-30 membered ring comprising 1 C=C bond.

[0306]

[0307] In some embodiments,

[0308]

[0309] , together with the atoms to which it is attached and any intervening atoms, forms a 14-35 membered ring comprising 1 C=C bond.

[0310]

[0311] In some embodiments,

[0312]

[0313] , together with the atoms to which it is attached and any intervening atoms, forms a 14-50 membered ring comprising 1 C=C bond. In some embodiments,

[0314]

[0315] , together with the atoms to which it is attached and any intervening atoms, forms a 14-45 membered ring comprising 1 C=C bond.

[0316]

[0317] In some embodiments,

[0318]

[0319] , together with the atoms to which it is attached and any intervening atoms, forms a 15-18 membered ring comprising 1 C=C bond.

[0320] In some embodiments,

[0321]

[0322] , together with the atoms to which it is attached and any intervening atoms, forms a 14-15 membered ring comprising 1-3 C=C bonds.

[0323]

[0324] In some embodiments,

[0325]

[0326] , together with the atoms to which it is attached and any intervening atoms, forms a 14-16 membered ring comprising 1-3 C=C bonds.

[0327]

[0328] In some embodiments,

[0329]

[0330] , together with the atoms to which it is attached and any intervening atoms, forms a 14-17 membered ring comprising 1-3 C=C bonds.

[0331]

[0332] In some embodiments,

[0333]

[0334] , together with the atoms to which it is attached and any intervening atoms, forms a 14-18 membered ring comprising 1-3 C=C bonds.

[0335]

[0336] In some embodiments,

[0337]

[0338] , together with the atoms to which it is attached and any intervening atoms, forms a 14-20 membered ring comprising 1-3 C=C bonds. In some embodiments,

[0339]

[0340] , together with the atoms to which it is attached and any intervening atoms, forms a 14-25 membered ring comprising 1-3 C=C bonds.

[0341]

[0342] In some embodiments,

[0343]

[0344] , together with the atoms to which it is attached and any intervening atoms, forms a 14-30 membered ring comprising 1-3 C=C bonds.

[0345]

[0346] In some embodiments,

[0347]

[0348] , together with the atoms to which it is attached and any intervening atoms, forms a 14-50 membered ring comprising 1-3 C=C bonds.

[0349] In some embodiments,

[0350]

[0351] , together with the atoms to which it is attached and any intervening atoms, forms a 15-18 membered ring comprising 1-3 C=C bonds.

[0352]

[0353] In some embodiments,

[0354]

[0355] , together with the atoms to which it is attached and any intervening atoms, forms a 15-18 membered ring comprising 1-10 C=C bonds.

[0356]

[0357] In some embodiments,

[0358]

[0359] , together with the atoms to which it is attached and any intervening atoms, forms a 15-18 membered ring.

[0360]

[0361] In some embodiments,

[0362]

[0363] , together with the atoms to which it is attached and any intervening atoms, forms a 16-membered ring. In some embodiments,

[0364]

[0365] , together with the atoms to which it is attached and any intervening atoms, forms a 17-membered ring.

[0366] In some embodiments, m is an integer between 3 and 6. In some embodiments, m is an integer between 4 and 5. In some embodiments, m is an integer between 1 and 6. In some embodiments, m is an integer between 1 and 7.

[0367] In some embodiments, m is 3. In some embodiments, m is 4. In some embodiments, m is 5. In some embodiments, m is 6.

[0368] In some embodiments, n is an integer between 3 and 6. In some embodiments, n is an integer between 4 and 5. In some embodiments, n is an integer between 1 and 6. In some embodiments, n is an integer between 1 and 7.

[0369] In some embodiments, n is 3. In some embodiments, n is 4. In some embodiments, n is 5. In some embodiments, n is 6.

[0370] In some embodiments, m is 0 and n is an integer between 7 and 20. In some embodiments, m is 1 and n is an integer between 6 and 20. In some embodiments, m is 2 and n is an integer between 5 and 20. In some embodiments, m is 3 and n is an integer between 4 and 20. In some embodiments, m is 4 and n is an integer between 3 and 20. In some embodiments, m is 5 and n is an integer between 2 and 20. In some embodiments, m is 6 and n is an integer between 1 and 20. In some embodiments, m is 7 and n is an integer between 0 and 20. In some embodiments, n is 0 and m is an integer between 7 and 20. In some embodiments, n is 1 and m is an integer between 6 and 20. In some embodiments, n is 2 and m is an integer between 5 and 20. In some embodiments, n is 3 and m is an integer between 4 and 20. In some embodiments, n is 4 and m is an integer between 3 and 20. In some embodiments, n is 5 and m is an integer between 2 and 20. In some embodiments, n is 6 and m is an integer between 1 and 20. In some embodiments, n is 7 and m is an integer between 0 and 20. In some embodiments, m is an integer between 3 and 6 and n is an integer between 3 and 6, provided that:

[0371] a) when neither of Ri and R2 are absent, the sum of m + n is > 7;

[0372] b) when one of Ri and R2 is absent, the sum of m + n is > 8; and

[0373] c) when both of Ri and R2 are absent, the sum of m + n is 9.

[0374] In some embodiments, m is an integer between 2 and 7 and n is an integer between 2 and 7, provided that:

[0375] a) when neither of Ri and R2 are absent, the sum of m + n is > 7;

[0376] b) when one of Ri and R2 is absent, the sum of m + n is > 8; and

[0377] c) when both of Ri and R2 are absent, the sum of m + n is 9.

[0378] In some embodiments, m is 3 and n is 6. In some embodiments, m is 4 and n is 6. In some embodiments, m is 5 and n is 4. In some embodiments, m is 5 and n is 5. In some embodiments, m is 6 and n is 3. In some embodiments, m is 5 and n is 5. In some embodiments, m is 2 and n is 7. In some embodiments, m is 7 and n is 2. In some embodiments, m is 3 and n is 7. In some embodiments, m is 7 and n is 3.

[0379] In some embodiments, the macrocyclic ROMP precursor comprises a compound described in Table 1.

[0380] Table 1

[0381]

[0382]

[0383]

[0384] In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-l). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-la). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-lb). In some embodiments, the macrocyclic ROMP precursor comprises a mixture of Compound (R-la) and Compound (R-lb).

[0385] In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-2). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-2a). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-2b). In some embodiments, the macrocyclic ROMP precursor comprises a mixture of Compound (R-2a) and Compound (R-2b).

[0386] In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3a). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3b). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3e). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3f). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3g). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-3h). In some embodiments, the macrocyclic ROMP precursor comprises a mixture of two or more of Compound (R-3e), Compound (R-3f), Compound (R-3g), and Compound (R-3h). In some embodiments, the macrocyclic ROMP precursor comprises a mixture of Compound (R-3e), Compound (R-3f), Compound (R-3g), and Compound (R-3h).

[0387] In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-4). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-4a). In some embodiments, the macrocyclic ROMP precursor comprises Compound (R-4b).

[0388] Bridged Polycyclic ROMP Precursors

[0389] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of Formula (S-II):

[0390]

[0391] wherein: q is 0, 1 or 2;

[0392] R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4 aryl, -O-C6-Ci4 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3-to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A;

[0393] R4and R6are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A; or

[0394] R4and R6, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl;

[0395] each R1Ais independently halogen, Ci-Ce alkyl, or C1-C16 alkoxy;

[0396] Z is a bond, -(CR2AR3A)a-, -O(CR2AR3A)a-, -(CR2AR3A)aO-, -(CR2AR3A)a-O-(CR2AR3A)b-, -(CR2AR3A)a-O-(SiR2AR3A)b-, -(CR2AR3A)a-(C=O)O-(CR2AR3A)b-, -(CR2AR3A)-O(C=O)-(C R2AR3A)b-, -(CR2AR3A)a-(C=O)-(CR2AR3A)b-;

[0397] Each R2Aand R3Ais independently hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;

[0398] R7is phenyl optionally substituted with one or more R7A;

[0399] Each R7Ais independently selected from Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;

[0400] and

[0401] each a and b is independently an integer between 1 and 12;

[0402] is a single bond or a double bond, wherein when is a double bond, R3and R5are both absent.

[0403] In some embodiments, q is 0, 1 or 2. In some embodiments, q is 0 or 1. In some embodiments, q is 0. In some embodiments, q is 1.

[0404] In some embodiments, R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4 aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A. In some embodiments, R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7). In some embodiments, R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, or C2-C16 alkenyl. In some embodiments, R3and R5are each independently Cs alkyl, C10 alkyl, or C2 alkenyl.

[0405] In some embodiments, one of R3and R5is C1-C16 alkyl. In some embodiments, one of R3and R5is C2-C16 alkenyl. In some embodiments, one of R3and R5is C3-C14 cycloalkyl. In some embodiments, one of R3and R5is C1-C16 alkoxy. In some embodiments, one of R3and R5is -C(=O)-R1A. In some embodiments, one of R3and R5is -O-C(=O)-R1A. In some embodiments, one of R3and R5is Ce-Cw aryl. In some embodiments, one of R3and R5is -O-Ce-Cw aryl. In some embodiments, one of R3and R5is 3- to 14-membered heterocycloalkyl. In some embodiments, one of R3and R5is 5- to 14-membered heteroaryl. In some embodiments, one of R3and R5is -Si(R1A)3. In some embodiments, one of R3and R5is -Z-(R7). In some embodiments, one of R3and R5is Cs alkyl, C10 alkyl, or C2 alkenyl.

[0406] In some embodiments, R3is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A. In some embodiments, R3is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-Cw cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, Cs-Cw cycloalkyl, Cs-Cw cycloalkenyl, Ce-Cw aryl, 3-to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R3is Ci-16 alkyl substituted with one or more F, C2-C16 alkenyl substituted with one or more F, Cs-Cw cycloalkyl substituted with one or more F, C3-Cw cycloalkenyl substituted with one or more F, Ce-Cw 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, R3is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7). In some embodiments, R3is Cs alkyl, C10 alkyl, or C2 alkenyl.

[0407] In some embodiments, R3is absent. In some embodiments, R3is hydrogen. In some embodiments, R3is C1-C16 alkyl. In some embodiments, R3is C2-C16 alkenyl. In some embodiments, R3is C3-C14 cycloalkyl. In some embodiments, R3is C1-C16 alkoxy. In some embodiments, R3is -C(=O)-R1A. In some embodiments, R3is -O-C(=O)-R1A. In some embodiments, R3is Ce-Cw aryl. In some embodiments, R3is -O-Ce-Cw aryl. In some embodiments, R3is 3- to 14-membered heterocycloalkyl. In some embodiments, R3is 5- to 14-membered heteroaryl. In some embodiments, R3is -Si(R1A)3. In some embodiments, R3is -Z-(R7). In some embodiments, R3is Cs alkyl. In some embodiments, R3is C10 alkyl. In some embodiments, R3is C2 alkenyl.

[0408] In some embodiments, R5is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the C1-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A. In some embodiments, R5is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3-to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R5is Ci-16 alkyl substituted with one or more F, C2-C16 alkenyl substituted with one or more F, Cs-Cw cycloalkyl substituted with one or more F, C3-Cw cycloalkenyl substituted with one or more F, Ce-Cw 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, R5is absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, Cs-Cw cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14- membered heteroaryl, -Si(R1A)3, or -Z-(R7). In some embodiments, R5is Cs alkyl, Cio alkyl, or C2 alkenyl.

[0409] In some embodiments, R5is absent. In some embodiments, R5is hydrogen. In some embodiments, R5is C1-C16 alkyl. In some embodiments, R5is C2-C16 alkenyl. In some embodiments, R5is C3-C14 cycloalkyl. In some embodiments, R5is C1-C16 alkoxy. In some embodiments, R5is -C(=O)-R1A. In some embodiments, R5is -O-C(=O)-R1A. In some embodiments, R5is Ce-Cw aryl. In some embodiments, R5is -O-Ce-Cw aryl. In some embodiments, R5is 3- to 14-membered heterocycloalkyl. In some embodiments, R5is 5- to 14-membered heteroaryl. In some embodiments, R5is -Si(R1A)3. In some embodiments, R5is -Z-(R7). In some embodiments, R5is Cs alkyl. In some embodiments, R5is Cio alkyl. In some embodiments, R5is C2 alkenyl.

[0410] In some embodiments, R4and R6are each independently hydrogen, halogen, C1-C16 alkyl, C2-Ci6 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A. In some embodiments, R4and R6are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7). In some embodiments, one of R4and R6is C1-C16 alkyl. In some embodiments, one of R4and R6is C2-Ci6 alkenyl. In some embodiments, one of R4and R6is Cs alkyl, Cio alkyl, or C2 alkenyl.

[0411] In some embodiments, one of R4and R6is C1-C16 alkyl. In some embodiments, one of R4and R6is Ce-Cw alkyl. In some embodiments, one of R4and R6is Cs-Cio alkyl. In some embodiments, one of R4and R6is Cs alkyl. In some embodiments, one of R4and R6is Cio alkyl.

[0412] In some embodiments, one of R4and R6is C2-C6 alkenyl. In some embodiments, one of R4and R6is C2-C3 alkenyl. In some embodiments, one of R4and R6is C2 alkenyl. In some embodiments, R3is absent

[0413]

[0414] In some embodiments, R4is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A. In some embodiments, R4is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R4is 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, Ce-Cw 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, R4is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, Cs-Cw cycloalkyl, Cs-Cw cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7). In some embodiments, R4is C1-C16 alkyl. In some embodiments, R4is C2-C16 alkenyl. In some embodiments, R4is Cs alkyl, C10 alkyl, or C2 alkenyl.

[0415] In some embodiments, R4is hydrogen. In some embodiments, R4is halogen. In some embodiments, R4is C1-C16 alkyl. In some embodiments, R4is C2-C16 alkenyl. In some embodiments, R4is Cs-Cw cycloalkyl. In some embodiments, R4is Cs-Cw cycloalkenyl. In some embodiments, R4is C1-C16 alkoxy. In some embodiments, R4is -C(=O)-R1A. In some embodiments, R4is -O-C(=O)-R1A. In some embodiments, R4is Ce-Cw aryl. In some embodiments, R4is -O-Ce-Cw aryl. In some embodiments, R4is 3- to 14-membered heterocycloalkyl. In some embodiments, R4is 5- to 14-membered heteroaryl. In some embodiments, R4is -Si(R1A)3. In some embodiments, R4is -Z-(R7).

[0416] In some embodiments, R6is C1-C16 alkyl. In some embodiments, R6is Ce-Cw alkyl. In some embodiments, R6is Cs-Cio alkyl. In some embodiments, R6is C8o alkyl. In some embodiments, R6is C10 alkyl. In some embodiments, R6is C2-C6 alkenyl. In some embodiments, R6is C2-C3 alkenyl. In some embodiments, R6is C2 alkenyl. In some embodiments, R5is absent and R6is

[0417]

[0418] .

[0419] In some embodiments, R6is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A. In some embodiments, R6is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more F. In some embodiments, R6is 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, Ce-Cw 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, R6is hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, Cs-Cw cycloalkyl, Cs-Cw cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7). In some embodiments, R6is C1-C16 alkyl. In some embodiments, R6is C2-C16 alkenyl. In some embodiments, R6is Cs alkyl, C10 alkyl, or C2 alkenyl.

[0420] In some embodiments, R6is hydrogen. In some embodiments, R6is halogen. In some embodiments, R6is C1-C16 alkyl. In some embodiments, R6is C2-C16 alkenyl. In some embodiments, R6is Cs-Cw cycloalkyl. In some embodiments, R6is Cs-Cw cycloalkenyl. In some embodiments, R6is C1-C16 alkoxy. In some embodiments, R6is -C(=O)-R1A. In some embodiments, R6is -O-C(=O)-R1A. In some embodiments, R6is Ce-Cw aryl. In some embodiments, R6is -O-Ce-Cw aryl. In some embodiments, R6is 3- to 14-membered heterocycloalkyl. In some embodiments, R6is 5- to 14-membered heteroaryl. In some embodiments, R6is -Si(R1A)3. In some embodiments, R6is or -Z-(R7). In some embodiments, R6is C1-C16 alkyl. In some embodiments, R6is Ce-Ci6 alkyl. In some embodiments, R6is Cs-Cio alkyl. In some embodiments, R6is Cs alkyl. In some embodiments, R6is C10 alkyl.

[0421] In some embodiments, R6is C2-C6 alkenyl. In some embodiments, R6is C2-C3 alkenyl. In some embodiments, R6is C2 alkenyl.

[0422] In some embodiments, R4and R6, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl. In some embodiments, R4and R6, together with the carbon atoms to which they are attached, form a Cs cycloalkyl. In some embodiments, R4and R6, together with the carbon atoms to which they are attached, form a Cs cycloalkenyl.

[0423] In some embodiments, each R1Ais independently halogen, Ci-Ce alkyl or C1-C16 alkoxy. In some embodiments, each R1Ais Ci-Ce alkyl. In some embodiments, each R1Ais C1-C16 alkoxy.

[0424] In some embodiments, Z is a bond, -(CR2AR3A)a-, -O(CR2AR3A)a-, -(CR2AR3A)aO-, -(CR2AR3A)a-O-(CR2AR3A)b-, -(CR2AR3A)a-O-(SiR2AR3A)b-, -(CR2AR3A)a-(C=O)O-(CR2AR3A)b-, -(CR2AR3A)-O(C=O)-(C R2AR3A)b-, -(CR2AR3A)a-(C=O)-(CR2AR3A)b-. In some embodiments, Z is a bond. In some embodiments, Z is -(CR2AR3A)a-. In some embodiments, Z is -O(CR2AR3A)a-. In some embodiments, Z is -(CR2AR3A)aO-. In some embodiments, Z is -(CR2AR3A)a-O-(CR2AR3A)b-. In some embodiments, Z is -(CR2AR3A)a-O-(SiR2AR3A)b-. In some embodiments, Z is -(CR2AR3A)a-(C=O)O-(CR2AR3A)b-. In some embodiments, Z is -(CR2AR3A)-O(C=O)-(C R2AR3A)b-. In some embodiments, Z is -(CR2AR3A)a-(C=O)-(CR2AR3A)b-.

[0425] In some embodiments, each R2Aand R3Ais independently hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl. In some embodiments, one of R2Aand R3Ais hydrogen. In some embodiments, one of R2Aand R3Ais Ci-Ce alkyl. In some embodiments, one of R2Aand R3Ais Ci-Ce alkoxy. In some embodiments, one of R2Aand R3Ais O-C(=O)-Ci-Ce alkyl. In some embodiments, one of R2Aand R3Ais -C(=O)-(Ci-Ce alkyl). In some embodiments, one of R2Aand R3Ais phenyl. In some embodiments, one of R2Aand R3Ais -O-phenyl. In some embodiments, each R2Ais hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl. In some embodiments, R2Ais hydrogen. In some embodiments, R2Ais Ci-Ce alkyl. In some embodiments, R2Ais Ci-Ce alkoxy. In some embodiments, R2Ais O-C(=O)-Ci-Ce alkyl. In some embodiments, R2Ais -C(=O)-(Ci-Ce alkyl). In some embodiments, R2Ais phenyl. In some embodiments, R2Ais -O-phenyl.

[0426] In some embodiments, each R3Ais hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl. In some embodiments, R3Ais hydrogen. In some embodiments, R3Ais Ci-Ce alkyl. In some embodiments, R3Ais Ci-Ce alkoxy. In some embodiments, R3Ais O-C(=O)-Ci-Ce alkyl. In some embodiments, R3Ais -C(=O)-(Ci-Ce alkyl). In some embodiments, R3Ais phenyl. In some embodiments, R3Ais -O-phenyl.

[0427] In some embodiments, each R7Ais independently selected from Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl. In some embodiments, R7Ais Ci-Ce alkyl. In some embodiments, R7Ais Ci-Ce alkoxy. In some embodiments, R7Ais O-C(=O)-Ci-Ce alkyl. In some embodiments, R7Ais -C(=O)-(Ci-Ce alkyl). In some embodiments, R7Ais phenyl. In some embodiments, R7Ais -O-phenyl.

[0428] 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.

[0429] 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.

[0430] 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.

[0431] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIa):

[0432]

[0433] wherein R13is C1-C16 alkyl.

[0434] In some embodiments, R13is C1-C16 alkyl. In some embodiments, R13is Cs alkyl. In some embodiments, R13is n-octyl.

[0435] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of Formula (S-III):

[0436]

[0437] wherein:

[0438] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(C6-Ci4aryl); or

[0439] R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0440] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0441] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0442] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIa):

[0443]

[0444] wherein R9, R10, and R11are as described herein.

[0445] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIb):

[0446]

[0447] wherein R9, R10, and R11are as described herein.

[0448] In some embodiments, R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-Ci-Ci6 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(Ce-Cwaryl); or R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl. In some embodiments, one of R9and R10is hydrogen. In some embodiments, one of R9and R10is Ci-C 16 alkyl. In some embodiments, one of R9and R10is C1-C16 alkoxy. In some embodiments, one of R9and R10is -O-C(=O)-Ci-Ci6 alkyl. In some embodiments, one of R9and R10is -C(=O)-(Ci-Ci6 alkyl). In some embodiments, one of R9and R10is Ce-Cw aryl. In some embodiments, one of R9and R10is -O-(Ce-Ci4 aryl). In some embodiments, R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl.

[0449] In some embodiments, R9is hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-Ci-Ci6 alkyl, -C(=O)-(Ci-Ci6 alkyl), Ce-Cw aryl, or -O-(Ce-Ci4aryl). In some embodiments, R9is hydrogen. In some embodiments, R9is C1-C16 alkyl. In some embodiments, R9is C1-C16 alkoxy. In some embodiments, R9is -O-C(=O)-Ci-Ci6 alkyl. In some embodiments, R9is -C(=O)-(Ci-Ci6 alkyl). In some embodiments, R9is Ce-Cw aryl. In some embodiments, R9is -O-(Ce-Ci4aryl).

[0450] In some embodiments, R10is hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-Ci-Ci6 alkyl, -C(=O)-(Ci-Ci6 alkyl), Ce-Cw aryl, or -O-(Ce-Cwaryl). In some embodiments, R10is hydrogen. In some embodiments, R10is C1-C16 alkyl. In some embodiments, R10is C1-C16 alkoxy. In some embodiments, R10is -O-C(=O)-Ci-Ci6 alkyl. In some embodiments, R10is -C(=O)-(Ci-Ci6 alkyl). In some embodiments, R10is Ce-Ci4 aryl. In some embodiments, R10is -O-(Ce-Ci4aryl).

[0451] In some embodiments, R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-C1-C14 alkoxy, -C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12. In some embodiments, R11is hydrogen. In some embodiments, R11is halogen. In some embodiments, R11is OH. In some embodiments, R11is C1-C16 alkyl. In some embodiments, R11is Ce-Ci6 aryl. In some embodiments, R11is -(Ce-Cu aryl)-Ci-Ci4 alkoxy. In some embodiments, R11is -Ci-Ci6 alkoxy. In some embodiments, R11is -O-(Ce-Ci4 aryl). In some embodiments, R11is -O(C=O)R12. In some embodiments, R11is -O(C=O)OR12.

[0452] In some embodiments, R12is C1-C16 alkyl, Ce-Cu aryl, or (Ce-Cu aryl)-(Ci-Ci6 alkyl). In some embodiments, R12is C1-C16 alkyl. In some embodiments, R12is Ce-Cu aryl. In some embodiments, R12is (Ce-Cu aryl)-(Ci-Ci6 alkyl).

[0453] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of any one of Formulae (S-IVa), (S-IVb), (S-IVc), and (S-IVd):

[0454]

[0455] wherein:

[0456] each Y is independently -CH2, -CH2-CH2-, -O-, or -S-;

[0457] X1is -O-, -S-, -NRa, -SiRbRc, -SiRbRcO(SiRbRcO)miSiRbRc, -SiRbRc(C6-Cio aryl)SiRbRc, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, Ci-Cis alkyl, -CH=CH-, or -C=C-;

[0458] X2is -SiRbRc, -Si(RbRc)O(SiRbRcO)miSi(RbRc), -Si(RbRc)(C6-Cio aryl)Si(RbRc), -C(=O)-, Ci-Cis alkyl, -CH=CH-, or -C=C-;

[0459] Ra, Rband Rcare each independently hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2; and

[0460] each n1, n2, n3, and n4 is independently an integer 0, 1, or 2;

[0461] each bi, b2, and b4 is independently an integer between 1 and 10;

[0462] mi is an integer between 0 and 10.

[0463] In some embodiments, X1is -O-, -S-, -NRa, -SiRbRc, -SiRbRcO(SiRbRcO)miSiRbRc, -SiRbRc(C6-Cio aryl)SiRbRc, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, Ci-Cis alkyl, -CH=CH-, or -C=C-. In some embodiments, X1is -O-. In some embodiments, X1is -S-. In some embodiments, X1is -NRa. In some embodiments, X1is -SiRbRc. In some embodiments, X1is -SiRbRcO(SiRbRcO)miSiRbRc. In some embodiments, X1is -SiRbRc(Ce-Cio aryl)SiRbRc. In some embodiments, X1is -C(=O)-. In some embodiments, X1is -C(=O)O-. In some embodiments, X1is -OC(=O)-. In some embodiments, X1is -OC(=O)-O-. In some embodiments, X1is -SC(=O)-. In some embodiments, X1is -C(=O)-S-. In some embodiments, X1is Ci-Cis alkyl. In some embodiments, X1is -CH=CH-. In some embodiments, X1is -C=C-

[0464] In some embodiments, X2is -SiRbRc, -Si(RbRc)O(SiRbRcO)miSi(RbRc), -Si(RbRc)(C6-Cio aryl)Si(RbRc), -C(=O)-, Ci-Cis alkyl, -CH=CH-, or -C=C-. In some embodiments, X2is -SiRbRc. In some embodiments, X2is -Si(RbRc)O(SiRbRcO)miSi(RbRc). In some embodiments, X2is -Si(RbRc)(Ce-Cio aryl)Si(RbRc). In some embodiments, X2is -C(=O)-. In some embodiments, X2is Ci-Cis alkyl. In some embodiments, X2is -CH=CH-. In some embodiments, X2is -C=C-.

[0465] In some embodiments, Ra, Rband Rcare each independently hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2. In some embodiments, at least one of Ra, Rband Rcis hydrogen. In some embodiments, at least one of Ra, Rband Rcis C1-C12 alkyl. In some embodiments, at least one of Ra, Rband Rcis C3 -C12 cycloalkyl. In some embodiments, at least one of Ra, Rband Rcis C3-C12 cycloalkenyl. In some embodiments, at least one of Ra, Rband Rcis (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2.

[0466] In some embodiments, Rais hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2. In some embodiments, Rais hydrogen. In some embodiments, Rais C1-C12 alkyl. In some embodiments, Rais C3 -C12 cycloalkyl. In some embodiments, Rais C3-C12 cycloalkenyl. In some embodiments, Rais (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2.

[0467] In some embodiments, Rbis hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2. In some embodiments, Rbis hydrogen. In some embodiments, Rbis C1-C12 alkyl. In some embodiments, Rbis C3 -C12 cycloalkyl. In some embodiments, Rbis C3-C12 cycloalkenyl. In some embodiments, Rbis (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2.

[0468] In some embodiments, Rcis hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2. In some embodiments, Rcis hydrogen. In some embodiments, Rcis C1-C12 alkyl. In some embodiments, Rcis C3 -C12 cycloalkyl. In some embodiments, Rcis C3-C12 cycloalkenyl. In some embodiments, Rcis (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2.

[0469] In some embodiments, each m, n2, ns, and is independently 0, 1, or 2. In some embodiments, each m, n2, ns, and n4 is independently 0 or 1. In some embodiments, each m, n2, ns, and is independently 1 or 2.

[0470] In some embodiments, m is 0, 1, or 2. In some embodiments, is 0, 1, or 2. In some embodiments, ns is 0, 1, or 2. In some embodiments, is 0, 1, or 2.

[0471] In some embodiments, each bi, b2, and b4 is independently an integer between 1 and 10. In some embodiments, each bi, b2, and b4 is independently an integer between 1 and 5. In some embodiments, each bi, b2, and b4 is independently an integer between 1 and 3. In some embodiments, bi is an integer between 1 and 10. In some embodiments, b2 is an integer between 1 and 10. In some embodiments, bs is an integer between 1 and 10. In some embodiments, b4 is an integer between 1 and 10.

[0472] In some embodiments, mi is an integer between 0 and 10. In some embodiments, mi is an integer between 0 and 5. In some embodiments, mi is an integer between 0 and 3.

[0473] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IVa). In some embodiments, the bridged polycyclic ROMP precursor ROMP precursor comprises a compound of Formula (S-IVb). In some embodiments, the bridged polycyclic ROMP precursor ROMP precursor comprises a compound of Formula (S-IVc). In some embodiments, the bridged polycyclic ROMP precursor ROMP precursor comprises a compound of Formula (S-IVd).

[0474] In some embodiments, the bridged polycyclic ROMP precursor comprises a compound described in Table 2.

[0475] Table 2

[0476]

[0477] In some embodiments, the bridged polycyclic ROMP precursor comprises compound S-l. In some embodiments, the bridged polycyclic ROMP precursor comprises compound S-2. In some embodiments, the bridged polycyclic ROMP precursor comprises compound S-3. In some embodiments, the bridged polycyclic ROMP precursor comprises compound S-4. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-2. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-3.

[0478] In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-2, wherein the bridged polycyclic ROMP precursor comprises between about 1% (w / w) and about 9% (2 / 2) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-2, wherein the bridged polycyclic ROMP precursor comprises between about 3% (w / w) and about 6% (2 / 2) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-2, wherein the bridged polycyclic ROMP precursor comprises about 4% (w / w) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-2, wherein the bridged polycyclic ROMP precursor comprises about 5% (w / w) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor.

[0479] In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-3, wherein the bridged polycyclic ROMP precursor Comprises between about 1% (w / w) and about 9% (2 / 2) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-3, wherein the bridged polycyclic ROMP precursor Comprises between about 3% (w / w) and about 6% (2 / 2) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-3, wherein the bridged polycyclic ROMP precursor Comprises about 4% (w / w) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises a mixture of Compound S-l and Compound S-3, wherein the bridged polycyclic ROMP precursor Comprises about 5% (w / w) Compound S-l, relative to the total weight of the bridged polycyclic ROMP precursor. In some embodiments, the bridged polycyclic ROMP precursor comprises less than about 10% (w / w) Compound S-l. In some embodiments, the bridged polycyclic ROMP precursor comprises less than about 9% (w / w) Compound S-l. In some embodiments, the bridged polycyclic ROMP precursor comprises less than about 8% (w / w) Compound S-l. In some embodiments, the bridged polycyclic ROMP precursor comprises less than about 7% (w / w) Compound S-l. In some embodiments, the bridged polycyclic ROMP precursor comprises less than about 6% (w / w) Compound S-l. In some embodiments, the bridged polycyclic ROMP precursor comprises less than about 5% (w / w) Compound S-l.

[0480] In some embodiments, the bridged polycyclic ROMP precursor is a strained polycyclic ROMP precursor. As used herein, a “strained polycyclic ROMP precursor” or “strained ROMP precursor” refers to a bridged polycyclic ROMP precursor with a ring strain larger than 15 kcal / mol (e.g., greater than 15 kcal / mol, or greater than 25 kcal / mol).

[0481] Curing Catalysts

[0482] In some embodiments, the disclosure provides a means for curing a composition disclosed herein. In some embodiments, the disclosure provides a means for catalyzing ROMP. In some embodiments, the disclosure provides a curing catalyst. In some embodiments, the curing catalyst is a latent catalyst. In some embodiments, the curing catalyst is a non-latent catalyst. In some embodiments, the latent catalyst is a thermally latent catalyst, a photo-latent catalyst, or a chemically latent catalyst.

[0483] In some embodiments, the curing catalyst is activated by irradiation. In some embodiments, the curing catalyst is activated by UV. In some embodiments, the curing catalyst is activated by elevated temperature. In some embodiments, the curing catalyst is activated by an activator. In some embodiments, the curing catalyst is a Ruthenium catalyst. In some embodiments, the curing catalyst is a Grubbs catalyst. In some embodiments, the curing catalyst is first-generation Grubbs catalyst, second-generation Grubbs catalyst, or third-generation Grubbs catalyst. In some embodiments, the curing catalyst is a first-generation Grubbs-Hovey da catalyst. In some embodiments, the curing catalyst is a second-generation Grubbs-Hovey da catalyst. In some embodiments, the curing catalyst is a ruthenium-indenylidene complex. In some embodiments, the curing catalyst is a Grubbs-type catalyst. In some embodiments, the Grubbs-type catalyst comprises at least one N-heterocyclic carbene (NHC) or cyclic (alkyl)(amino)carbene (CAAC) ligand. In some embodiments, the Ru complex comprises a 16-electron species.

[0484] The activated Ru complex may comprise at least one N-heterocyclic carbene (NHC) or cyclic (alkyl)(amino)carbene (CAAC) ligand. The activated Ru complex may comprise one N-heterocyclic carbene (NHC) or cyclic (alkyl)(amino)carbene (CAAC) ligand. The activated Ru complex may comprise a 14-electron species.

[0485] In some embodiments, the curing catalyst comprises a compound described in U. S. Patent Appl’n Pub. Nos. 2020 / 0183276 and / or US20210163676A1 (incorporated herein by reference). In some embodiments, the curing catalyst comprises a compound described in U. S. Patent Appl’n Pub. No. 2020 / 0002466 (incorporated herein by reference).

[0486] In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C- I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII):

[0487]

[0488] or a salt or a solvate thereof; wherein: L1-ais L2'aor L3'a;

[0489]

[0490] Each L1-bis independently L2'b, L3'b, L4'b, L8'b, L9'b, or L10'b,

[0491] L2'bis P(R5'b)3, pyridine, or dimethylsulfoxide, wherein the pyridine is optionally subsituted with one or more C1-C16 alkyl;

[0492]

[0493] L9'bis P(R9'b)3; L10'bis P(R10'b)3;

[0494] each Ar1-a, Ar2'a, Ar3'a, Ar4'a, Ar1-band Ar2'bis independently Ce-Cio aryl or biphenyl; wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl, C1-C6 alkoxy, or -N(CI-C6alkyl)(Ci-C6alkyl);

[0495]

[0496] ---- is a single bond or a double bond;

[0497] Rxis halogen;

[0498] R1-ais Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl);

[0499] each R2 aand R3 ais independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; or

[0500] R2 aand R3 a, together with the carbon to which they are attached, form a C3-C14 cycloalkyl;

[0501] R4'ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0502] R5 ais Ci-Cie alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Ci4 aryl or biphenyl, wherein the Ce-Ci4 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0503] R8'ais Ci-Ce alkyl, C3-C14 cycloalkyl, or Ce-Cio aryl;

[0504] each R1-bis independently Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl); each R2 band R3'bis independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; or

[0505] R2 band R3'b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl;

[0506] Each R4'band R5 bis independently C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0507] R6'bis absent, Ci-Ce alkyl, Ci-Ce alkoxy, Ce-Cio aryl, -0(Ci-Cio aryl), -NHC=O(Ci-Ce alkyl), -NHC=O(Ci-Ce fluoroalkyl), -SO2N(Ci-Ce alkyl)2, or -NO2;

[0508] R7 bis Ci-Ce alkyl, cyclohexyl, Ce-Cio aryl or biphenyl; wherein the cyclohexyl, Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; each R8'band R9'bis independently methyl or benzyl; wherein the benzyl is optionally substituted with one or more C1-C16 alkyl;

[0509] each R10'bis independently C1-C16 alkyl or C3-C14 cycloalkyl; and

[0510] zi is 0, 1, or 2.

[0511] In some embodiments, the curing catalyst comprises a compound of Formula (C-I), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-II), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-III), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-IV), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-V), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-VI), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-VII), or a salt or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-I), or a salt thereof.

[0512] In some embodiments, the curing catalyst comprises a compound of Formula (C-II), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-III), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-IV), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-V), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-VI), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-VII), or a salt thereof.

[0513] In some embodiments, the curing catalyst comprises a compound of Formula (C-I), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-II), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-III), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-IV), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-V), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-VI), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-VII), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of Formula (C-I). In some embodiments, the curing catalyst comprises a compound of Formula (C-II). In some embodiments, the curing catalyst comprises a compound of Formula (C-III). In some embodiments, the curing catalyst comprises a compound of Formula (C-IV). In some embodiments, the curing catalyst comprises a compound of Formula (C-V). In some embodiments, the curing catalyst comprises a compound of Formula (C-VI). In some embodiments, the curing catalyst comprises a compound of Formula (C-VII).

[0514] In some embodiments, L1-ais L2-aor L3-a. In some embodiments, L2-ais

[0515]

[0516] some embodiments,

[0517]

[0518] In some embodiments, L5'ais L6'aor L7'a. In some embodiments,

[0519]

[0520] some

[0521] embodiments,

[0522]

[0523] In some embodiments, each L1-bis independently L2'b, L3'b, L4'b, L8'b, L9'b, or L10'b. In some embodiments, L1-bis L3'b. In some embodiments, L1-bis L4'b. In some embodiments, L1-bis L9' b

[0524] In some embodiments, L2'bis P(R5'b)3, pyridine, or dimethylsulfoxide, wherein the pyridine is optionally subsituted with one or more Ci-Cie alkyl. In some embodiments, L3'bis

[0525]

[0526] , some embodiments, L8-b

[0527] . In some embodiments, L9'bis P(R9'b)3. In some embodiments, L10'bis P(R10'

[0528]

[0529] In some embodiments, L5'bis L6'bor L7'b. In some embodiments, L5'bis L6'b. In some

[0530] embodiments,

[0531]

[0532] some embodiments, L7'bis

[0533]

[0534] In some embodiments, each Ar1-a, Ar2'21, Ar3'21, Ar4'a, Ar1-band Ar2'bis independently Ce-Cio aryl or biphenyl; wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Cie alkyl, Ci-Ce alkoxy, or -N(Ci-Ce alkyl)(Ci-Ce alkyl). In some embodiments, each Ar1'a, Ar2'a, Ar3'21, Ar4'a, Ar1'15and Ar2'bis independently phenyl or naphthyl. In some embodiments, each Ar1-a, Ar2'a, Ar3'a, Ar4'a, Ar1-band Ar2'bis phenyl. In some embodiments, each Ar1-a, Ar2'a, Ar3'a, Ar4'a, Ar1'11and Ar2'bis naphthyl. In some embodiments, Ar1'11is Ce-Cio aryl optionally substituted with one or more C1-C16 alkyl. In some embodiments, Ar1'11is phenyl optionally subsituted with one or more C2 alkyl. In some embodiments, Ar1'11is phenyl optionally subsituted with one or more ethyl. In some embodiments, Ar1'11is phenyl optionally substituted with one or more methyl. In some embodiments, Ar1'11is phenyl optionally substituted with one or more methyl. In some embodiments, Ar2'bis phenyl optionally substituted with one or more methyl. In some embodiments, Ar2'bis phenyl optionally substituted with one or more methyl.

[0535] In some embodiments,

[0536]

[0537] some embodiments, Xbis

[0538]

[0539] ,

[0540] In some embodiments, Rxis halogen. In some embodiments, Rxis Cl.

[0541] In some embodiments, R1-ais Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl). In some embodiments, R1-ais Ci-Ce alkyl. In some embodiments, R1-ais Ce-Cio aryl. In some embodiments, R1-ais Ci-Ce alkoxy. In some embodiments, R1-ais -0(Ce-Cio aryl). In some embodiments, each R2 aand R3'ais independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-C10 aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; or R2 aand R3 a, together with the carbon to which they are attached, form a C3-C14 cycloalkyl. In some embodiments, at least one of R2'aand R3'ais C1-C16 alkyl. In some embodiments, at least one of R2'aand R3'ais C3-C14 cycloalkyl. In some embodiments, at least one of R2'aand R3'ais Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0542] In some embodiments, R2 ais C1-C16 alkyl. In some embodiments, R2 ais C3-C14 cycloalkyl. In some embodiments, R2 ais Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0543] In some embodiments, R3 ais C1-C16 alkyl. In some embodiments, R3 ais C3-C14 cycloalkyl. In some embodiments, R3 ais Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0544] In some embodiments, R4'ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl. In some embodiments, R4'ais C1-C16 alkyl. In some embodiments, R4'ais C3-C14 cycloalkyl. In some embodiments, R4'ais C2-C16 alkenyl. In some embodiments, R4'ais Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0545] In some embodiments, R5 ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl. In some embodiments, R5 ais C1-C16 alkyl. In some embodiments, R5 ais C3-C14 cycloalkyl. In some embodiments, R5 ais C2-C16 alkenyl. In some embodiments, R5 ais Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0546] In some embodiments, R8'ais Ci-Ce alkyl, C3-C14 cycloalkyl, or Ce-Cio aryl. In some embodiments, R8'ais Ci-Ce alkyl. In some embodiments, R8'ais C3-C14 cycloalkyl. In some embodiments, R8'ais Ce-Cio aryl. In some embodiments, each R1-bis independently Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl). In some embodiments, R1-bis Ci-Ce alkyl. In some embodiments, R1-bis methyl.

[0547] In some embodiments, each R2 band R3'bis independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-C10 aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl; or R2 band R3'b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl. In some embodiments, R2 band R3'bcome together to form a C5-C14 cycloalkyl. In some embodiments, R2 band R3'bcome together to form a Ce cycloalkyl. In some embodiments, R2 band R3'bcome together to form cyclohexyl.

[0548] In some embodiments, each R4'band R5 bis independently C1-C16 alkyl, C3-C14 cycloalkyl, C2-Ci6 alkenyl, C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl. In some embodiments, at least one of R4'band R5 bis C1-C16 alkyl. In some embodiments, at least one of R4'band R5 bis C3-C14 cycloalkyl. In some embodiments, at least one of R4'band R5 bis C2-C16 alkenyl. In some embodiments, at least one of R4'band R5 bis C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0549] In some embodiments, R4'bis C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl. In some embodiments, R4'bis C1-C16 alkyl. In some embodiments, R4'bis C3-C14 cycloalkyl. In some embodiments, R4'bis C2-C16 alkenyl. In some embodiments, R4'bis C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0550] In some embodiments, R5 bis C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl. In some embodiments, R5 bis C1-C16 alkyl. In some embodiments, R5 bis C3-C14 cycloalkyl. In some embodiments, R5 bis C2-C16 alkenyl. In some embodiments, R5 bis C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl. In some embodiments, R6'bis absent, Ci-Ce alkyl, Ci-Ce alkoxy, Ce-Cio aryl, -0(Ci-Cio aryl), -NHC=O(Ci-Ce alkyl), -NHC=O(Ci-Ce fluoroalkyl), -SO2N(Ci-Ce alkyl)2, or -NO2. In some embodiments, R6'bis absent. In some embodiments, R6'bis Ci-Ce alkyl. In some embodiments, R6'bis Ci-Ce alkoxy. In some embodiments, R6'bis Ce-Cio aryl. In some embodiments, R6'bis -0(Ci-Cio aryl). In some embodiments, R6'bis -NHC=O(Ci-Ce alkyl). In some embodiments, R6'bis -NHC=O(Ci-Ce fluoroalkyl). In some embodiments, R6'bis -SO2N(Ci-Ce alkyl)2. In some embodiments, R6'bis -NO2.

[0551] In some embodiments, R7 bis Ci-Ce alkyl, cyclohexyl, Ce-Cio aryl or biphenyl; wherein the cyclohexyl, Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl. In some embodiments, R7 bis C1-C4 alkyl. In some embodiments, R7 bis methyl. In some embodiments, R7 bis ethyl. In some embodiments, R7 bis propyl. In some embodiments, R7 bis n-propyl. In some embodiments, R7 bis isopropyl. In some embodiments, R7 bis butyl. In some embodiments, R7 bis n-butyl. In some embodiments, R7 bis isobutyl. In some embodiments, R7 bis sec-butyl. In some embodiments, R7 bis tert-butyl.

[0552] In some embodiments, each R8'band R9'bis independently methyl or benzyl, wherein the benzyl is optionally substituted with one or more C1-C16 alkyl. In some embodiments, R9'bis benzyl. In some embodiments, each R10'bis independently C1-C16 alkyl or C3-C14 cycloalkyl. In some embodiments, each R10'bis independently C1-C16 alkyl. In some embodiments, each R10'bis independently C3-C14 cycloalkyl.

[0553] In some embodiments, zi is 1 or 2. In some embodiments, zi is 1. In some embodiments, zi is 2. In some embodiments, z is 0.

[0554] In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII).

[0555] In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), or a salt or solvate thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), or a salt thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-VI) or (CVII) or a salt or solvate thereof.

[0556] In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-VI) or (CVII) or a salt thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-VI) or (CVII) or a solvate thereof. In some embodiments, the curing catalyst comprises a compound of any one of Formulae (C-VI) or (CVII).

[0557] In some embodiments, the curing catalyst comprises a compound described in Table 3, or a salt, or a solvate thereof.

[0558] Table 3

[0559]

[0560]

[0561] In some embodiments, Compound C-l is commercially available from Millipore Sigma under the name Grubbs Catalyst® M200. In some embodiments, Compound C-2 is commercially available from Apeiron Synthesis under the name UltraLatMet.

[0562] In some embodiments, the curing catalyst comprises l,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)-(2-oxobenzylidene)-2-(((2,6-diisopropylphenyl-imino)methyl)phenoxy)ruthenium.

[0563] In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of between about 10 ppm mol / mol and about 100 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of between about 30 ppm mol / mol and about 60 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of greater than about 10 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of greater than about 20 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of greater than about 25 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of less than about 70 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of less than about 65 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of less than about 90 ppm mol / mol. In some embodiments, the curing catalyst is present in the combination, build material or kit disclosed herein at a concentration of less than about 100 ppm mol / mol.

[0564] In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of between about 10 ppm mol / mol and about 100 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of between about 30 ppm mol / mol and about 60 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of greater than about 10 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of greater than about 20 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of greater than about 25 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of less than about 70 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of less than about 65 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of less than about 90 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of less than about 100 ppm mol / mol.

[0565] In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of between about 10 ppm mol / mol and about 100 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of between about 30 ppm mol / mol and about 60 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of greater than about 10 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of greater than about 20 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of greater than about 25 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of less than about 70 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of less than about 65 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of less than about 90 ppm mol / mol. In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration of less than about 100 ppm mol / mol.

[0566] In some embodiments, the curing catalyst comprises Compound C-l and is present in the combination, build material or kit disclosed herein at a concentration of about 40 ppm mol / mol.

[0567] In some embodiments, the curing catalyst comprises Compound C-2 and is present in the combination, build material or kit disclosed herein at a concentration between about 30 ppm mol / mol and about 60 ppm mol / mol. Activators

[0568] In some embodiments, the combination, build material or kit disclosed herein further comprises an activator. As used herein, the term “activator” refers to a compound capable of increasing the activity of a curing catalyst as described herein.

[0569] In some embodiments, the activator comprises l-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

[0570] In some embodiments, the activator comprises a copper(I), copper(II) or ruthenium based complex.

[0571] In some embodiments, the activator comprises a compound of any one of Formulae (A-I), (A- II), (A-III), (A-IV), and (A-V):

[0572] RuCl2(PPh3)p(A-I),

[0573] CuRzPPh3(A-II),

[0574] CuRz- (A-III),

[0575] (Rm)cCuCl (A-IV),

[0576]

[0577] solvate thereof,

[0578] wherein Rzis halogen;

[0579] Rmis a compound of Formula (S-II), (S-III), (S-IIIa), (S-IIIb), (S-IVa), (S-IVb), (S-IVc), or (S-IVd);

[0580] nhc is an N-heterocyclic carbene;

[0581] each Ar4is Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0582] p is 3 or 4; and

[0583] c is 0, 1, 2, 3, 4, 5, or 6. In some embodiments, each each Ar4is Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl. In some embodiments, Ar4

[0584] is phenyl substituted with more than one C3 alkyl. In some embodiments,

[0585]

[0586] In some embodiments, the activator comprises a compound of Formula (A-I).

[0587] In some embodiments, the activator comprises a compound of any one of Formulae (A-II), (A- III), (A-IV), and (A-V).

[0588] In some embodiments, the activator comprises a compound of Formula (A-V).

[0589] In some embodiments, the activator comprises Compound A-l:

[0590]

[0591] or a solvate thereof.

[0592] In some embodiments, the activator comprises Compound A-l:

[0593]

[0594] In some embodiments, the activator comprises a compound described in Application No. PCT / US2022 / 026589 (incorporated herein by reference). In some embodiments, the activator comprises a compound described in Application No. PCT / US2023 / 065738 (incorporated herein by reference).

[0595] In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of between about 10 ppm mol / mol and about 100 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of between about 30 ppm mol / mol and about 60 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of greater than about 10 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of greater than about 20 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of greater than about 25 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of less than about 70 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of less than about 65 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of less than about 80 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of less than about 90 ppm mol / mol. In some embodiments, the activator is present in the combination, build material or kit disclosed herein at a concentration of less than about 100 ppm mol / mol.

[0596] Crosslinkers

[0597] In some embodiments, the combination, build material or kit disclosed herein further comprises a crosslinker. In some embodiments, the crosslinker is a norbornene-based crosslinker. In some embodiments, the crosslinker comprises a norbornene moiety. In some embodiments, the crosslinker comprises a norbornene terminated oligomer. In some embodiments, the crosslinker comprises a norbornene terminated polymer. In some embodiments, the crosslinker comprises a norbornene terminated siloxane. In some embodiments, the crosslinker comprises a norbomene terminated polydimethylsiloxane. In some embodiments, the crosslinker comprises a polydimethylsiloxane functionalized with at least one norbomene moiety.

[0598] In some embodiments, the crosslinker is present in the combination, build material or kit disclosed herein at a concentration of between about 0.5% wt / wt and about 20% wt / wt. In some embodiments, the crosslinker is present in the combination, build material or kit disclosed herein at a concentration of between about 1% wt / wt and about 15% wt / wt. In some embodiments, the crosslinker is present in the combination, build material or kit disclosed herein at a concentration of between about 2% wt / wt and about 10% wt / wt. In some embodiments, the crosslinker is present in the combination, build material or kit disclosed herein at a concentration of about 1% wt / wt, about 2% wt / wt, about 3% wt / wt, about 4% wt / wt, about 5% wt / wt, about 6% wt / wt, about 7% wt / wt, about 8% wt / wt, about 9% wt / wt, or about 10% wt / wt.

[0599] Polymerization Retardants

[0600] In some embodiments, the combination, build material or kit disclosed herein further comprises a polymerization retardant.

[0601] As used herein, a “polymerization retardant” is a chemical species which retards or ceases catalyst initiation or propagation. Polymerization retardants may be desirable for, e.g., preventing the premature polymerization during the preparation, purification, transportation and storage of the combination or build material. Suitable polymerization retardants include, but are not limited to, phosphites (e.g., trialkyl phosphites, triarylphosphites, and tribenzylphosphites), phosphines, pyridines (e.g., 4-dimethylaminopyridine), imidazoles (e.g. N-methyl imidazole) and sulfides.

[0602] In some embodiments, the polymerization retardant comprises a phosphine, a phosphite, an aromatic amine, a sulfide, or a combination thereof. In some embodiments, the polymerization retardant comprises a phosphine. In some embodiments, the polymerization retardant comprises a phosphite. In some embodiments, the polymerization retardant comprises an aromatic amine. In some embodiments, the polymerization retardant comprises a sulfide.

[0603] Impact Modifiers

[0604] In some embodiments, the combination, build material or kit disclosed herein further comprises an impact modifier.

[0605] 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. In some embodiments, the impact modifier comprises a synthetic rubber.

[0606] In some embodiments, the synthetic rubber comprises an ethylene propylene diene monomer (EPDM) rubber.

[0607] In some embodiments, the synthetic rubber comprises a liquid ethylene propylene diene monomer (EPDM) rubber.

[0608] In some embodiments, the impact modifier is present in the combination, build material or kit disclosed herein at a concentration of between about 0.5% wt / wt and about 10% wt / wt. In some embodiments, the impact modifier is present in the combination, build material or kit disclosed herein at a concentration of between about 1% wt / wt and about 5% wt / wt. In some embodiments, the impact modifier is present in the combination, build material or kit disclosed herein at a concentration of between about 2% wt / wt and about 4% wt / wt. In some embodiments, the impact modifier is present in the combination, build material or kit disclosed herein at a concentration of about 1% wt / wt, about 2% wt / wt, about 3% wt / wt, about 4% wt / wt, or about 5% wt / wt.

[0609] Fillers

[0610] In some embodiments, the combination, build material or kit disclosed herein further comprises a filler.

[0611] In some embodiments, the filler comprises carbon black, a carbon nanotube, silica, metal oxide nanoparticle, or a combination thereof. In some embodiments, the filler comprises a carbon nanotube, silica, metal oxide nanoparticle, or a combination thereof. In some embodiments, the filler comprises a nanoparticle, silica, or a combination thereof. In some embodiments, the filler comprises an organic nanoparticle, inorganic nanoparticle, silica, or a combination thereof. In some embodiments, the filler comprises carbon black. In some embodiments, the filler comprises a carbon nanotube. In some embodiments, the filler comprises a modified carbon nanotube. In some embodiments, the filler comprises a chemically modified carbon nanotube. In some embodiments, the filler comprises a carbon nanotube reacted with a bridged polycyclic ROMP precursor as described herein. In some embodiments, the filler comprises a singlewalled carbon nanotube. In some embodiments, the filler comprises a multi-walled carbon nanotube. In some embodiments, the filler comprises silica. In some embodiments, the filler comprises nanosilica. In some embodiments, the filler comprises silicon dioxide. In some embodiments, the filler comprises fumed silica. In some embodiments, the filler comprises colloidal silica. In some embodiments, the filler comprises colloidal silica powder. In some embodiments, the filler comprises colloidal silica functionalized with an alkylsilane. In some embodiments, the filler comprises colloidal silica functionalized with triethoxyoctylsilane. In some embodiments, the filler comprises colloidal silver commercially available under the tradename “CAB-O-SIL™ TGC- 191.” In some embodiments, the filler comprises a metal oxide nanoparticle.

[0612] In some embodiments, the filler is present in the combination, build material or kit disclosed herein at a concentration of between about 1% wt / wt and about 25% wt / wt. In some embodiments, the filler is present in the combination, build material or kit disclosed herein at a concentration of between about 5% wt / wt and about 15% wt / wt. In some embodiments, the filler is present in the combination, build material or kit disclosed herein at a concentration of between about 9% wt / wt and about 14% wt / wt. In some embodiments, the filler is present in the combination, build material or kit disclosed herein at a concentration of about 5% wt / wt, about 6% wt / wt, about 7% wt / wt, about 8% wt / wt, about 9% wt / wt, about 10% wt / wt, about 11% wt / wt, about 12% wt / wt, about 13% wt / wt, about 14% wt / wt, or about 15% wt / wt.

[0613] Solvents

[0614] In some embodiments, the combination, build material or kit disclosed herein further comprises a solvent.

[0615] In some embodiments, the solvent comprises an inert solvent.

[0616] In some embodiments, the inert solvent comprises an organic solvent.

[0617] In some embodiments, the inert solvent comprises a non-polar solvent.

[0618] In some embodiments, the inert solvent comprises a non-polar, organic solvent.

[0619] In some embodiments, the inert solvent comprises an aromatic ether.

[0620] In some embodiments, the inert solvent comprises biphenyl.

[0621] In some embodiments, the inert solvent comprises at least one benzyl moiety.

[0622] In some embodiments, the inert solvent comprises a eutectic mixture of diphenyl ether and biphenyl. In some embodiments, the inert solvent comprises a mixture of about 27 % (w / w) biphenyl and about 73 % (w / w) diphenyl ether. In some embodiments, the combination, build material, or kit disclosed herein comprises less than about 15 % (w / w), less than about 14 % (w / w), less than about 13 % (w / w), less than about 12 % (w / w), less than about 11 % (w / w), less than about 10 % (w / w), less than about 9 % (w / w), less than about 8 % (w / w), less than about 7 % (w / w), less than about 6 % (w / w), less than about 5 % (w / w), less than about 4 % (w / w), less than about 3 % (w / w), less than about 2 % (w / w), or less than about 1 % (w / w) inert solvent.

[0623] Activator Protecting Agents

[0624] 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).

[0625] Without wishing to be bound by theory, it has been observed that Cu(I) complexes can activate latent ROMP 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 latent ROMP catalyst is activated, thereby reducing the cure time of polymerization reactions described herein.

[0626] 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.

[0627] 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-butylcatechol and other alkylated derivatives of catechol). 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.

[0628] In some embodiments, the activator protecting agent is an organic molecule.

[0629] Antioxidants

[0630] In some embodiments, the combination, build material or kit disclosed herein further comprises an antioxidant.

[0631] 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. 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 paracresol 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 distearylthiopropionate, 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, or combinations comprising at least one of the foregoing antioxidants.

[0632] 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.

[0633] 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.

[0634] 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.

[0635] 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). 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 non-alkylated 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)-l,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodi ethylene 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.

[0636] In some embodiments, the benzene polyol comprises a phenyl group that is directly substituted with two or more alcohol groups. In some embodiments, the benzene polyol may comprise a dihydroxybenzene or a trihydroxybenzene. In some embodiments, the dihydroxybenzene may comprise a catechol, a resorcinol, or a hydroquinone. In some embodiments, the trihydroxybenzene may comprise a pyrogallol, a hydroxyquinol, or a phloroglucinol. In some embodiments, the benzene polyol may comprise a compound of Formula (X-I):

[0637]

[0638] or a salt thereof, wherein:

[0639] each of R16A, R16B, R16C, and R16Dis independently H, a halogen, cyano, -OR17, -SR17, -C(=O)-R17, -C(=O)-OR17, -O-C(=O)-R17, -C(=O)-N(R17)2, -C(=O)-NHR17, -NH-C(=O)-R17, -N(R17)2, -Si(R17)3, Ci-C2o alkyl, C2-C2o alkenyl, C2-C2o alkynyl, C3-C20 cycloalkyl, Ce-C2o aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the Ci-C2o alkyl, C2-C2o alkenyl, C2-C2o alkynyl, C3-C20 cycloalkyl, Ce-C2o aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R17; and each R17is independently H, a 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.

[0640] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis H.

[0641] In some embodiments, at least two of R16A, R16B, R16C, and R16Dare H.

[0642] In some embodiments, at least three of R16A, R16B, R16C, and R16Dare H.

[0643] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis a halogen, cyano, -OR17, -SR17, -C(=O)-R17, -C(=O)-OR17, -O-C(=O)-R17, -C(=O)-N(R17)2, -C(=O)-NHR17, -NH-C(=O)-R17, -N(R17)2, -Si(R17)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 R17.

[0644] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis a C1-C20 alkyl.

[0645] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis a C2-C20 alkenyl.

[0646] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis a C2-C20 alkynyl.

[0647] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis a C3-C20 cycloalkyl.

[0648] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis a 3- to 20-membered heterocycloalkyl.

[0649] In some embodiments, at least one of R16A, R16B, R16C, and R16Dis -OR17. In some embodiments at least one of R16A, R16B, R16C, and R16Dis OR17and R17is H.

[0650] In some embodiments, the compound of Formula (X-I) may be a catechol. In some embodiments, the catechol is 4-tert-butylcatechol or 3, 5 -di -tert-butyl catechol. In some embodiments, the catechol is 4-tert-butylcatechol. In some embodiments, the catechol is 3,5-di -tert-butyl catechol.

[0651] In some embodiments, the compound of Formula (X-I) may be a trihydroxybenzene. In some embodiments, the trihydroxybenzene is octyl gallate.

[0652] In some embodiments the secondary antioxidant is selected from an organophosphite, thioether and thioester, or a combination thereof. In some embodiments, the secondary antioxidant comprises one or more compounds selected from tetrakis(2,4-di-tert-butylphenyl)phosphite, tributylphosphite, triisodecylphosphite, triphenylphosphite, [1,1- biphenyl]-4,4'-diylbisphosphonite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerytritoldiphosphite, tris(nonyl phenyl)phosphite, and distearyl pentaerythritol diphosphite. In yet a further aspect, the secondary antioxidant comprises tris(2,4-di-tert-butylphenyl)phosphite.

[0653] 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.

[0654] Stabilizers

[0655] In some embodiments, the combination, build material or kit disclosed herein further comprises a stabilizer. In some embodiments, the stabilizer is a thermal stabilizer (e.g., a compound that stabilizes the combination or build material at an elevated temperature).

[0656] In some embodiments, the stabilizer is 4-tert-butylcatechol (TBC), 4-methoxyphenol (MEHQ), butylated hydroxytoluene (BHT), Hydroquinone (HQ), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (e.g., as sold under the name IRGANOX® 1010), ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate) (e.g., as sold under the name IRGANOX® 245), octadecyl-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (e.g., as sold under the name IRGANOX® 1076), bis-(2,4-di-tert-butylphenol)pentaerythritol diphosphate (e.g., as sold under the name IRGAFOS® 126), tris(2,4-di-tert-butylphenyl)phosphite (e.g., as sold under the name IRGAFOS® 168), 4-dimethylamino pyridine (DMAP), Vitamin E, or any combination thereof.

[0657] Chain Transfer Agents

[0658] In some embodiments, the combination, build material or kit disclosed herein further comprises a chain transfer agent. As used herein, the term “chain transfer agent” refers to a compound which functions to ensure homogeneous growth of macromolecular chains via reversible transfer reactions between growing species. This reversible transfer process makes it possible to control the molecular masses of the copolymers thus prepared. In some embodiments, a chain transfer agent may also function as a polymerization retardant. In some embodiments, a polymerization retardant may comprise a chain transfer agent as described herein. In some embodiments, the chain transfer agent comprises an alkene. In some embodiments, the chain transfer agent comprises an internal alkene. In some embodiments, the chain transfer agent comprises a functionalized alkene. In some embodiments, the chain transfer agent comprises a diene. In some embodiments, the chain transfer agent comprises an internal diene. In some embodiments, the chain transfer agent comprises a polyene. In some embodiments, the chain transfer agent comprises an internal polyene.

[0659] Physical Properties of the Printed Product

[0660] In some embodiments, the printed product herein has an ultimate tensile strength of about 2 MPa, about 3 MPa, about 4 MPa, about 5 MPa, about 10 MPa, about 15 MPa, about 20 MPa, about 25 MPa, about 30 MPa, about 35 MPa, about 40 MPa, about 45 MPa, about 50 MPa, about 55 MPa, about 60 MPa, about 70 MPa, or any range therebetween. In some embodiments, the printed product herein has an ultimate tensile strength of between about 2 MPa and about 70 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 10 MPa and about 70 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 15 MPa and about 70 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 20 MPa and about 70 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 25 MPa and about 70 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 30 MPa and about 60 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 35 MPa and about 60 MPa. In some embodiments, the printed product herein has an ultimate tensile strength of between about 40 MPa and about 60 MPa.

[0661] In some embodiments, the printed product disclosed herein has a Young’s Modulus of about 1.2 GPa, about 1.3 GPa, about 1.4 GPa, about 1.5 GPa, about 1.6 GPa, about 1.7 GPa, about 1.8 GPa, about 1.9 GPa, about 2.0 GPa, about 2.1 GPa, about 2.2 GPa, about 2.3 GPa, about 2.4 GPa, about 2.5 GPa, or any range therebetween. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.0 GPa and about 3.0 GPa. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.5 GPa and about 2.5 GPa. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.2 GPa and about 2.5 GPa. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.3 GPa and about 2.4 GPa. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.4 GPa and about 2.3 GPa. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.5 GPa and about 2.2 GPa. In some embodiments, the printed product disclosed herein has a Young’s Modulus of between about 1.6 GPa and about 2.2 GPa.

[0662] In some embodiments, the printed product disclosed herein has an elongation at break of about 1 %, about 2 %, about 3 %, about 4 %, about 5%, about 10 %, about 15 %, about 20 %, about 25 %, about 30 %, about 35 % about 40 %, about 50 %, about 55 %, about 60 %, about 65 %, about 70 %, about 80 %, about 90 %, about 100 %, about 200%, about 300%, about 400%, about 500%, about 600%, about 700%, about 800%, about 900%, or any range therebetween. In some embodiments, the printed product disclosed herein has an elongation at break of between about 1 % and about 900 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 1 % and about 400 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 2 % and about 400 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 3 % and about 400 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 4 % and about 400 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 5 % and about 8 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 5 % and about 7 %. In some embodiments, the printed product disclosed herein has an elongation at break of greater than about 8 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 8 % and about 900 %. In some embodiments, the printed product disclosed herein has an elongation at break of between about 8 % and about 400 %.

[0663] In some embodiments, the printed product disclosed herein has a notched Izod impact strength of about 5 KJ / m2, about 10 KJ / m2, about 15 KJ / m2, about 20 KJ / m2, about 25 KJ / m2, about 30 KJ / m2, or any range therebetween. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 5 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 6 KJ / m2and about 25 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 7 KJ / m2and about 24 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 8 KJ / m2and about 23 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 8 KJ / m2and about 22 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 8 KJ / m2and about 21 KJ / m2. In some embodiments, the printed product disclosed herein has a notched Izod impact strength of between about 8 KJ / m2and about 20 KJ / m2.

[0664] In some embodiments, the printed product disclosed herein has an elongation at break of about 1 %, about 2 %, about 3 %, about 4 %, about 5%, about 10 %, about 15 %, about 20 %, about 25 %, about 30 %, about 35 % about 40 %, about 50 %, about 55 %, about 60 %, about 65 %, about 70 %, about 80 %, about 90 %, about 100 %, about 200%, about 300%, about 400 %, or any range therebetween and a notched Izod impact strength of about 5 KJ / m2, about 10 KJ / m2, about 15 KJ / m2, about 20 KJ / m2, about 25 KJ / m2, about 30 KJ / m2, about 35 KJ / m2, about 40 KJ / m2, or any range therebetween. In some embodiments, the printed product disclosed herein has an elongation at break of between about 1 % and about 400 % and a notched Izod impact strength of between about 5 KJ / m2and about 40 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of between about 2 % and about 30 % and a notched Izod impact strength of between about 6 KJ / m2and about 35 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of between about 3 % and about 30 % and a notched Izod impact strength of between about 7 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of between about 4 % and about 25 % and a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of greater than about 4 % and a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of greater than about 5 % and a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of greater than about 6 % and a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of greater than about 7 % and a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. In some embodiments, the printed product disclosed herein has an elongation at break of greater than about 8 % and a notched Izod impact strength of between about 8 KJ / m2and about 30 KJ / m2. Build Materials and Build Curing Conditions

[0665] In some embodiments, the build material is deposited (e.g., jetted) under a build depositing condition (e.g., build jetting condition).

[0666] In some embodiments, the build material is cured under a build curing condition.

[0667] In some embodiments, the build material is a liquid under the build depositing condition (e.g., the build jetting condition).

[0668] In some embodiments, upon deposition, the build material is converted to a solid by curing.

[0669] In some embodiments, the build material is UV curable.

[0670] In some embodiments, the build material is substantially stable (e.g., chemically and / or physically) toward the support material.

[0671] In some embodiments, the build material is substantially stable (e.g., chemically and / or physically) under the support curing condition.

[0672] In some embodiments, the build material is substantially stable (e.g., chemically and / or physically) toward the cured support material.

[0673] In some embodiments, upon activation, the curing catalyst cures the build material but does not cure the support material.

[0674] In some embodiments, the build curing condition comprises irradiation (e.g., visible light or UV). In some embodiments, the build curing condition comprises an elevated temperature. In some embodiments, the build curing condition comprises a chemical activation (e.g., adding water).

[0675] In some embodiments, the build curing condition comprises mechanical agitation. In some embodiments, the build curing condition comprises activation by acoustic (i.e., sonic) waves. In some embodiments, the build curing condition comprises activation by ultrasonic waves. In some embodiments, the build curing condition is substantially free of air (e.g., oxygen). In some embodiments, the build curing condition is substantially free of water.

[0676] In some embodiments, the cured build material is substantially stable (e.g., chemically and / or physically) toward the cured support material. In some embodiments, the cured build material is substantially stable (e.g., chemically and / or physically) under the support removal condition.

[0677] In some embodiments, the build material comprises a polymer. In some embodiments, the polymer is formed by ring opening metathesis polymerization.

[0678] Support Materials

[0679] In some embodiments, the support material is deposited (e.g., jetted) under a support depositing condition (e.g., support jetting condition).

[0680] In some embodiments, the support material is cured under a support curing condition.

[0681] In some embodiments, the support material or the cured support material is removed under a support removal condition.

[0682] In some embodiments, the support material is a liquid under the support depositing condition (e.g., the support jetting condition).

[0683] In some embodiments, the support material is a wax.

[0684] In some embodiments, the support material has a melting point being the same or lower than the temperature of the support depositing condition.

[0685] In some embodiments, upon deposition, the support material is converted to a solid (e.g., via a phase change).

[0686] In some embodiments, upon deposition, the support material is converted to a solid by cooling. In some embodiments, upon deposition, the support material is converted to a solid by curing.

[0687] In some embodiments, the support material is UV curable.

[0688] In some embodiments, the support material is thermally curable.

[0689] In some embodiments, the support curing condition comprises irradiation (e.g., visible light or UV).

[0690] In some embodiments, the support curing condition comprises elevated temperature.

[0691] In some embodiments, the support curing condition comprises mechanical agitation. In some embodiments, the support curing condition comprises activation by acoustic (i.e., sonic) waves. In some embodiments, the support curing condition comprises activation by ultrasonic waves.

[0692] In some embodiments, the support curing condition is substantially free of air (e.g., oxygen).

[0693] In some embodiments, the support curing condition is substantially free of water.

[0694] In some embodiments, the cured support material is substantially stable (e.g., chemically and / or physically) toward the build material.

[0695] In some embodiments, the cured support material is substantially stable (e.g., chemically and / or physically) under the build curing condition.

[0696] In some embodiments, the cured support material comprises a polymer.

[0697] In some embodiments, the support removal condition comprises adding a solvent, thereby dissolving the cured support material.

[0698] 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).

[0699] Uses of Combinations, Materials, and Kits

[0700] In some aspects, the present disclosure provides a method of preparing a cured material, comprising a step of subjecting a combination, build material, or kit disclosed herein to a curing condition.

[0701] In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein for use in preparing a cured material, wherein the preparation comprises a step of subjecting the combination, build material, or kit to a curing condition.

[0702] In some aspects, the present disclosure provides use of a combination, build material, or kit disclosed herein in the manufacture of a cured material, wherein the manufacture comprises a step of subjecting the combination, build material, or kit to a curing condition.

[0703] In some embodiments, the build curing condition comprises irradiation (e.g., visible light or UV).

[0704] In some embodiments, the build curing condition comprises an elevated temperature.

[0705] In some embodiments, the build curing condition comprises a chemical activation (e.g., adding water).

[0706] In some embodiments, the build curing condition comprises mechanical agitation. In some embodiments, the build curing condition comprises activation by acoustic (i.e., sonic) waves. In some embodiments, the build curing condition comprises activation by ultrasonic waves.

[0707] In some aspects, the present disclosure provides a cured material being prepared by a method described herein.

[0708] In some aspects, the present disclosure provides a method of printing an object using a combination, build material, or kit disclosed herein. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein for use in printing an object.

[0709] In some aspects, the present disclosure provides a method of preparing a cured material, comprising:

[0710] (i) jetting a mixture comprising a composition as disclosed herein onto a bed of powder; (ii) submitting the composition to a curing condition.

[0711] In some embodiments, the method comprises tuning the speed of the cyclic olefin resin polymerization, such that the thermoplastic fuses via heat before, concurrently and / or after initiation of the catalyst.

[0712] In some aspects, the present disclosure provides a method of preparing a cured material, comprising:

[0713] (i) injecting a comprising a composition as disclosed herein into a mold;

[0714] (ii) submitting the composition to a curing condition.

[0715] In some aspects, the present disclosure provides a method of preparing a cured material, comprising:

[0716] (i) applying comprising a composition as disclosed herein to a surface;

[0717] (ii) submitting the composition to a curing condition.

[0718] In some aspects, the printing comprises:

[0719] (i) depositing (e.g., jetting) a build material described herein;

[0720] (ii) submitting the deposited build material to a curing condition.

[0721] In some embodiments, the printing comprises:

[0722] (i) depositing (e.g., jetting) a build material described herein and

[0723] (ii) selectively subjecting a portion of the composition to a curing condition.

[0724] In some embodiments, the printing comprises:

[0725] (i) depositing (e.g., jetting) a first build material described herein, and a second build material described herein; and (ii) subjecting the deposited first build material and deposited second build material to a curing condition.

[0726] In some embodiments, the printing comprises:

[0727] (i) depositing (e.g., jetting) a build material described herein onto a supporting material; and

[0728] (ii) subjecting the deposited build material to a curing condition.

[0729] In some embodiments, the printing comprises:

[0730] (i) depositing (e.g., jetting) a first build material described herein, and a second build material described herein, onto a supporting material; and

[0731] (ii) subjecting the deposited first build material and deposited second build material to a curing condition.

[0732] In some embodiments, the printing further comprises repeating the step of depositing the material for one or more time.

[0733] In some embodiments, the printing further comprises optically sensing the deposited material, and controlling the one or more repeated deposition of the material according to the sensing.

[0734] In some embodiments, the optionally sensing of the deposited material is performed when the material is at least partially cured.

[0735] In some embodiments, each repeated deposition of the material is performed when the previously deposited layer of the material is at least partially cured.

[0736] In some embodiments, the printing further comprises depositing an agent which enhances one or more of the mechanical, thermal, and / or optical properties of the material.

[0737] In some embodiments, sensing the deposited material comprises capturing a surface of the object being printed.

[0738] In some embodiments, the controlling one or more repeated deposition of the material is based on measurements of the volumetric / tomographic data of an object being printed. In some embodiments, the printing further comprises heating the material, thereby facilitating the curing of the material.

[0739] Systems for Using Combinations, Materials, and Kits

[0740] In some aspects, the present disclosure provides a system for 3D printing, comprising:

[0741] (i) a printer (e.g., an inkjet printer); and

[0742] (ii) an ink comprising a combination disclosed herein.

[0743] In some embodiments, the printer (e.g., the inkjet printer) comprises one or more printer jet; an optical feedback scanner; and a controller which controls the emission of the ink from the one or more printer jet according to the optical feedback of the jetted ink.

[0744] In some embodiments, the printer (e.g., the inkjet printer) further comprises a printing head loaded (e.g., a printing head loaded with the ink).

[0745] In some embodiments, the system further comprises a light source (e.g., a UV lamp or a visible-light lamp) configured to cure the deposited layers of the ink.

[0746] In some embodiments, the system further comprises a software comprising instructions stored on a non-transitory machine-readable medium, wherein execution of said instructions causes control of one or more of the printing steps described herein.

[0747] The description below relates an exemplary system for additive fabrication, e.g., using a jetting-based 3D printer 100 shown in FIG. 1. The printer 100 uses jets 120 (inkjets) to emit material for deposition on a partially fabricated objected layers. In the printer illustrated in FIG. 1, the object is fabricated on a build platform, which is controlled to move related to the jets in a raster-like pattern to form successive layers, and in this example also to move relative to the jets to maintain a desired separation of the jets and the surface of the partially-fabricated object. As illustrated, there are multiple jets 122, 124, with one jet 122 being used to emit a support material to form a support structure 142 of the object, and another jet 124 being used to emit built material to form the object 144 itself. For materials for which curing is triggered by an excitation signal, such as an ultraviolet illumination, a curing signal generator 170 (e.g., a UV lamp) triggers curing of the material shortly after it is jetted onto the object. In other embodiments, multiple different materials may be used, for example, with a separate jet being used for each material. Yet other implementations do not necessarily use an excitation signal (e.g., optical, RF, etc.) and rather the curing is triggered chemically, for example, by mixing multiple components before jetting, or jetting separate components that mix and trigger curing on the object. Note that in some examples, after the additive deposition is complete, the object may be subject to further curing (e.g., to complete the curing), for example, by further exposing the object to UV radiation.

[0748] A sensor 160 is used to determine physical characteristics of the partially fabricated object, including one or more of the surface geometry (e.g., a depth map characterizing the thickness / depth of the partially fabricated object), subsurface (e.g., in the near surface comprising, for example, 10s or 100s of deposited layers) characteristics. The characteristic that may be sensed can include one or more of a material density, material identification, and a curing state. Various types of sensing can be used, including triangulation scanning / profilometry; time-of-flight imaging (pulse based and phase-shift); active stereo methods / multi-baseline stereo / structured light; active depth from focus / defocus; interferometry; optical coherence tomography; shape from polarization; shape from heating; optical coherence tomography (OCT), laser profilometry, and / or as well as multi-spectral optical sensing, which may be used to distinguish different materials. In the illustrated printer, the sensor outputs a signal that may cause emission (e.g., fluorescence) and / or reflection, scattering, or absorption from or in the object. The sensor output signal may be provided from the top (i.e., the most recently deposited portion) of the object, while in some embodiments, the sensor output signal may come from below or other direction of the object.

[0749] Precision additive fabrication using inkjet technology has introduced use of optical-scanningbased feedback in order to adapt the deposition of material to achieve accurate object structure without requiring mechanical approaches that have been previously used. For example, such optical feedback techniques are described in U. S. Patent Nos. 10,252,466 and 10,456,984 (incorporated by reference). However, optical feedback-based printers are not a prevalent commercial approach to 3D printing, perhaps due to the relative simplicity of approaches that do not achieve the precision attainable with optical feedback or that use mechanical approaches in conjunction with rapidly curing inks. Furthermore, many fabrication materials suitable for jetted additive fabrication are not directly suitable for optical scanning as inadequate optical signal strength may propagate from the material during scanning. For example, the material may be naturally substantially transparent and not reflect incident light suitably to be captured to yield an accurate characterization of the object being fabricated. However, with suitable incorporation of an optical enhancement component in the fabrication material, the ability to scan the material that has been deposited can be enhanced. Further details regarding suitable optical enhancement components may be found in PCT Appl’n No. PCT / US2019 / 59300 (incorporated herein by reference).

[0750] By not requiring contact to control the surface geometry of the object being manufactured, the approach can be tolerant of the relative slow curing of the composition (e.g., as compared to acrylate compositions usually used in inkjet 3D printing), while maintaining the benefit of control of the deposition processes according to feedback during the fabrication processes. This approach provides a way to manufacture precision objects and benefit from material properties of the fabricated objects, for example, with isotropic properties, which may be at least partially a result of the slow curing, and flexible structures, which may not be attainable using conventional jetted acrylates. Furthermore, in cases when ongoing curing after scanning may change the geometry of the part, for example, due to shrinkage, predictive techniques (e.g., using machine-learning approaches, e.g., as described in PCT Appl’n No. PCT / US2019 / 59567 (incorporated herein by reference)) may be used in the control process to predict such changes, further accommodating the cationic compositions into a precision jetted fabrication approach.

[0751] A controller 110 uses a model 190 of the object to be fabricated to control motion of the build platform 130 using a motion actuator 150 (e.g., providing three degree of motion) and control the emission of material from the jets 120 according to the non-contact feedback of the object characteristics determined via the sensor 160. Use of the feedback arrangement can produce a precision object by compensating for inherent unpredictable aspects of jetting (e.g., clogging of jet orifices) and unpredictable material changes after deposition, including for example, flowing, mixing, absorption, and curing of the jetted materials.

[0752] It is understood that the printer shown in FIG. 1 is merely illustrative but not limiting. Other printer arrangements that may be used are described, e.g., in U. S. Patent Nos. 10,252,466 and 10,456,984, U. S. Appl’n Pub. No. 2018 / 0056582, and Sitthi-Amorn et al. (ACM Transactions on Graphics 34(4): 129 (2015)). In an alternative manufacturing process, an additive fabrication stage and a subsequent or overlapping part curing stage imparts two distinct mechanisms to the build material for the part of the object: a phase change mechanism and a polymerization mechanism.

[0753] The phase change mechanism occurs during the additive fabrication stage and causes a phase change of the build material from a liquid to a non-liquid (e.g., at least partially solid, semisolid, and / or quasi-solid), where the phase change is generally not due to polymerization. In this non-liquid form the build material is sufficiently solidified for subsequent incremental deposit of material on to it (e.g., the non-liquid build material can support the weight of incrementally added material and / or the force of the material as it is jetted to, for example, prevent mixing between the build material and the support material).

[0754] The polymerization mechanism occurs after, or at least partly after, the additive fabrication of the object during the curing stage. This mechanism cures the build material by a polymerization process. In some examples, the polymerization mechanism is initiated after additive fabrication of the object is complete. In other examples, the polymerization mechanism is initiated before additive manufacturing is complete, for example, being initiated during the phase change mechanism (e.g., with both mechanisms being initiated at the same time, or the polymerization mechanism being initiated during the phase change mechanism).

[0755] After the build material is sufficiently cured (e.g., sufficiently polymerized) in the curing stage to allow removal of the mold, the manufacturing process enters a part removal stage for removal of the mold. Removal of the mold yields the fabricated part.

[0756] Referring to FIG. 2, this alternative manufacturing process uses a jetting-based 3D printer 200 as shown in FIG. 2. Very generally, the manufacturing process includes three temporal phases: an additive fabrication stage, a part curing stage, and a part removal stage. As is described in greater detail below, in some examples, the part curing stage occurs entirely after the additive fabrication stage. In other examples the additive fabrication stage and the part curing stage partially overlap.

[0757] In the additive fabrication stage, additive fabrication is used to fabricate an object 204 including a solid (e.g., cured) mold structure 211 that forms a cavity (e.g., closed structure or open vessel) defining a shape of the part 212, where the cavity is filled with a semi-solid, uncured or partially cured material in the shape of the part 212. The solid mold structure 211 and / or the semi-solid material are added, layer by layer, to form the object 204.

[0758] In the part curing stage, at least some of which occurs at a time after completion of the additive fabrication stage, the object 204 including the filled mold structure 211 undergoes a curing process for polymerizing the material in the cavity.

[0759] In the additive manufacturing stage and the part curing stage, the material used to form the part 212 (sometimes referred to as “build material) undergoes two distinct mechanisms: a phase change mechanism and a polymerization mechanism.

[0760] The phase change mechanism occurs during the additive fabrication stage and causes a phase change of the build material from a liquid to a non-liquid (e.g., at least partially solid, semisolid, and / or quasi-solid, where these three terms may be used interchangeably herein). In this non-liquid form the build material is sufficiently solidified for subsequent incremental deposit of material on to it (e.g., the non-liquid build material can support the weight or force of incrementally added material).

[0761] The polymerization mechanism occurs after, or at least partly after, the additive fabrication of the object 204 during the curing stage. This mechanism cures the build material by a polymerization process. In some examples, the polymerization mechanism is initiated after additive fabrication of the object is complete. In other examples, the polymerization mechanism is initiated before additive manufacturing is complete, for example, being initiated during the phase change mechanism (e.g., with both mechanisms being initiated at the same time, or the polymerization mechanism being initiated after initiation and during the phase change mechanism).

[0762] In the part removal stage, the solid mold structure 211 is removed, yielding the part 212. In some examples, the part removal stage occurs after the part curing stage. But in other examples, the part removal stage may overlap with the part curing stage (e.g., the part 212 is still curing but is sufficiently cured for removal from the solid mold structure 211).

[0763] Printer In the additive fabrication stage, the printer 200 uses jets 202 (inkjets) to emit material for deposition of layers to form the object 204 (shown partially fabricated in FIG. 2). For the printer illustrated in FIG. 2, the object 204 is fabricated on a build platform 206, which is controlled to move relative to the jets (i.e., along an x-y plane) in a raster-like pattern to form successive layers, and in this example also to move relative to the jets (i.e., along a z-axis) to maintain a desired separation of the jets and the surface of the partially-fabricated object 204.

[0764] As illustrated, there are multiple jets 208, 210, for example with a first jet 208 being used to emit a mold material 213 to form a solid (e.g., cured or semi-cured) mold structure 211 of the object 204, and a second jet 210 being used to emit build material 214 to form an uncured or partially cured, semi-solid (e.g., a gel or a wax) part 212 in the object 204. Additional details of the properties of the mold material 213 and the build material 214 are described below.

[0765] A sensor 216 (sometimes referred to as a scanner) is positioned relative to (e.g., above) the object under fabrication 204 and is used to determine physical characteristics of the partially fabricated object. For example, the sensor 216 measures one or more of the surface geometry (e.g., a depth map characterizing the thickness / depth of the partially fabricated object) and subsurface characteristics (e.g., in the near surface comprising, for example, 10s or 100s of deposited layers). The characteristics that may be sensed can include one or more of a material density, material identification, and a curing state. Very generally, the measurements from the sensor 216 are associated with a three-dimensional (i.e., x, y, z) coordinate system where the x and y axes are treated as spatial axes in the plane of the build surface and the z axis is a height axis (i.e., growing as the object is fabricated).

[0766] In some examples, in the context of a digital feedback loop for additive fabrication, the additive manufacturing system builds the object by printing layers. The sensor 216 captures the 3D scan information after the printer 200 prints one or more layers. For example, the sensor 216 scans the partial object (or empty build platform), then the printer prints a layer (or layers) of material(s). Then, the sensor 216 scans the (partially built) object again. The new depth sensed by the sensor 216 should be at a distance that is approximately the old depth minus the thickness of layer (this assumes that the sensor 216 is positioned on the top of the of the object being built and the object is being built from the bottom layer to the top layer and the distance between the sensor 216 and the build platform is unchanged). Various types of sensing such as optical coherence tomography (OCT) or laser profilometry can be used to determine depth and volumetric information related to the object being fabricated.

[0767] A controller 218 uses a model 220 of the object to be fabricated to control motion of the build platform 206 using a motion actuator 222 (e.g., providing three degrees of motion) and control the emission of material from the jets 202 according to non-contact feedback of the object characteristics determined via the sensor 216.

[0768] Definitions

[0769] Unless otherwise stated, the following terms used in the specification and claims have the following meanings set out below.

[0770] The articles "a" and "an" are used in this disclosure to refer to one or more than one ( / .<., 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.

[0771] 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.

[0772] 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 radiation (e.g., UV or visible light), an elevated temperature, or an activator. In some embodiments, the conversion is initiated by radiation (e.g., UV or visible light).

[0773] 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). 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.

[0774] 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.

[0775] As used herein, “macrocycle” refers to a molecule having a chemical structure including a cycloalkyl or heterocycle formed by at least 14 covalently bonded atoms.

[0776] As used herein, “bridged polycyclic ROMP precursor” refers to a molecule comprising a) a bridged polycyclic cycloalkyl or heterocyclyl and b) at least one carbon-carbon double bond.

[0777] 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, hexadecopropyl, 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.

[0778] 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-Ce” includes alkenyl groups containing three to six carbon atoms.

[0779] As used herein, the term “internal alkene” refers to alkenyl compounds containing at least one carbon-carbon double bond, wherein neither of the carbons in the double bond is a =CH2 group.

[0780] As used herein, the term “terminal alkene” refers to alkenyl compounds containing at least one carbon-carbon double bond wherein one of the carbons in the double-bond is a =CH2 group.

[0781] 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. As used herein, “C2-C6 alkenylene linker” or “C2-C6 alkynylene linker” is intended to include C2, C3, C4, Cs or Ce chain (linear or branched) divalent unsaturated aliphatic hydrocarbon groups. For example, C2-C6alkenylene linker is intended to include C2, C3, C4, Cs and Ce alkenylene linker groups.

[0782] 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 Cs-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.

[0783] 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., 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, 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, 1-oxaspiro[4.5]decanyl, l-azaspiro[4.5]decanyl, 3'H-spiro[cyclohexane-l,l'-isobenzofuran]-yl, 7'H-spiro[cyclohexane-l,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 non-aromatic (e.g., 4, 5,6,7-tetrahydrobenzo[c]isoxazolyl).

[0784] 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.

[0785] 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., 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 (i.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, isothiazole, 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.

[0786] Furthermore, the terms “aryl” and “heteroaryl” include multicyclic aryl and heteroaryl groups, e.g., tricyclic, bicyclic, e.g., naphthalene, benzoxazole, benzodi oxazole, benzothiazole, benzoimidazole, benzothiophene, quinoline, isoquinoline, naphthrydine, indole, benzofuran, purine, benzofuran, deazapurine, indolizine.

[0787] 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.

[0788] 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 ( / .<., =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.

[0789] 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.

[0790] 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.

[0791] 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. Exemplary inert solvents can be non-polar solvent such as hexane, toluene, diphenyl ether, chloroform, ethyl acetate, THF, dichloromethane; polar aprotic solvents such as acetonitrile, acetone, di chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and polar protic solvents such as lower alcohol and water. 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.

[0792] 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. 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.

[0793] As used herein, the term “hydroxy” or “hydroxyl” includes groups with an -OH or -O'.

[0794] As used herein, the term “halo” or “halogen” refers to fluoro, chloro, bromo and iodo.

[0795] 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 moieties. Examples of halogen substituted alkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy and trichloromethoxy.

[0796] As used herein, “latent catalyst” refers to a compound that shows little or no catalytic activity under certain conditions (e.g., those conditions present prior to printing) and initiate such activity when activated (e.g., under curing conditions). Latent catalysts may be activated by a variety of conditions, including without any limitation acid and radical activation. As used herein, the term “latent ruthenium complex” refers to organo-ruthenium compounds which are latent catalysts. As used herein, “non-latent catalyst” refers to a catalyst that is not a latent catalyst.

[0797] 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.

[0798] 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.

[0799] 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.

[0800] 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.

[0801] 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 ASTMD638.

[0802] 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.

[0803] 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.

[0804] As used herein, the term “Vitamin E” refers generally to a group of compounds that include both tocopherols and tocotrienols including, but not limited to, a-tocopherol, P-tocopherol, y-tocopherol, 6-tocopherol, a-tocotrienol, P-tocotrienol, y-tocotrienol, 6-tocotrienol, salts thereof, and combinations thereof.

[0805] It is to be understood that the present disclosure provides methods for the synthesis of the compounds described herein. The present disclosure also provides detailed methods for the synthesis of various disclosed compounds of the present disclosure according to the following schemes as well as those shown in the Examples.

[0806] 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 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. 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, 5thedition, John Wiley & Sons: New York, 2001; Greene, T. W., Wuts, P. G. M., Protective Groups in Organic Synthesis, 3rdedition, John Wiley & Sons: New York, 1999; R. Larock, Comprehensive Organic Transformations, VCH Publishers (1989); L. Fieser and M. Fieser, Fieser and Fieser’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.

[0807] 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, 3rdedition, John Wiley & Sons: New York, 1999.

[0808] All percentages and ratios used herein, unless otherwise indicated, are by weight.

[0809] 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. 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.

[0810] ENUMERATED EMBODIMENTS

[0811] The aspects of the present disclosure are further described with reference to the following numbered embodiments:

[0812] 1. A combination comprising:

[0813] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0814] (ii) a bridged polycyclic ROMP precursor; and

[0815] (iii) a curing catalyst.

[0816] 2. A kit comprising:

[0817] a build material comprising:

[0818] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0819] (iii) a latent curing catalyst;

[0820] (iv) an activator; and

[0821] a support material.

[0822] 3. A kit compri sing:

[0823] a first build material comprising:

[0824] (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;

[0825] (iii) an activator

[0826] a second build material comprising: (iv) a curing catalyst

[0827] (v) a solvent; and

[0828] a support material.

[0829] 4. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor is a strained ROMP precursor.

[0830] 5. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-I):

[0831]

[0832] wherein W is CH2 or C=O;

[0833] Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; and

[0834]

[0835] , together with the atoms to which it is attached and any intervening atoms, forms a 14- to 50- membered ring comprising 1-10 C=C bonds.

[0836] 6. The combination, build material, or kit of any one of the preceding embodiments,

[0837] wherein

[0838]

[0839] forms a 16-membered ring.

[0840] 7. The combination, build material, or kit of any one of the preceding embodiments,

[0841] wherein

[0842]

[0843] forms a 17-membered ring. 8. The combination, build material, or kit of any one of the preceding embodiments,

[0844] wherein

[0845]

[0846] forms a ring comprising 1 C=C bond.

[0847] 9. The combination, build material, or kit of any one of the preceding embodiments,

[0848] wherein

[0849]

[0850] forms a ring comprising 2 C=C bonds.

[0851] 10. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-Ia):

[0852]

[0853] wherein:

[0854] W is CH2or C=O;

[0855] m and n are each independently an integer between 0 and 20;

[0856] Ri and R2 are each independently absent, -CH2-, -O-, or -NH-;

[0857] each - is independently a single bond or a double bond having either the (E) or (Z) configuration; and

[0858] wherein at least one - is a double bond;

[0859] provided that:

[0860] a) when neither of Ri and R2 are absent, the sum of m + n is > 7; b) when one of Ri and R2 is absent, the sum of m + n is > 8; and c) when both of Ri and R2 are absent, the sum of m + n is > 9.

[0861] 11. The combination, build material, or kit of any one of the preceding embodiments, wherein Ri is -CH2-. 12. The combination, build material, or kit of any one of the preceding embodiments, wherein Ri is absent.

[0862] The combination, build material, or kit of any one of the preceding embodiments, wherein R2 is absent.

[0863] 14. The combination, build material, or kit of any one of the preceding embodiments, wherein Ri is -O-.

[0864] 15. The combination, build material, or kit of any one of the preceding embodiments, wherein R2 is -CH2-.

[0865] 16. The combination, build material, or kit of any one of the preceding embodiments, wherein W is C=O.

[0866] The combination, build material, or kit of any one of the preceding embodiments, wherein W is CH2.

[0867] 18. The combination, build material, or kit of any one of the preceding embodiments, wherein m is 4 and n is 6.

[0868] 19. The combination, build material, or kit of any one of the preceding embodiments, wherein m is 3 and n is 6.

[0869] 20. The combination, build material, or kit of any one of the preceding embodiments, wherein m is 6 and n is 3.

[0870] 21. The combination, build material, or kit of any one of the preceding embodiments, wherein m is 4 and n is 6.

[0871] 22. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor comprises Compound (R-l), Compound (R-2), Compound (R-3), or Compound (R-4):

[0872]

[0873] 23. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor comprises Compound R-l.

[0874] 24. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor comprises Compound R-2.

[0875] 25. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor comprises Compound R-3.

[0876] 26. The combination, build material, or kit of any one of the preceding embodiments, wherein the macrocyclic ROMP precursor is Compound R-4.

[0877] 27. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-II):

[0878]

[0879] wherein:

[0880] q is 0, 1 or 2; R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4 aryl, -O-C6-Ci4 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3-to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A;

[0881] R4and R6are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A; or

[0882] R4and R6, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl;

[0883] each R1Ais independently halogen, Ci-Ce alkyl, or C1-C16 alkoxy;

[0884] Z is a bond, -(CR2AR3A)a-, -O(CR2AR3A)a-, -(CR2AR3A)aO-, -(CR2AR3A)a-O-(CR2AR3A)b-, -(CR2AR3A)a-O-(SiR2AR3A)b-, -(CR2AR3A)a-(C=O)O-(CR2AR3A)b-, -(CR2AR3A)-O(C=O)-(C R2AR3A)b-, -(CR2AR3A)a-(C=O)-(CR2AR3A)b-;

[0885] Each R2Aand R3Ais independently hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;

[0886] R7is phenyl optionally substituted with one or more R7A;

[0887] Each R7Ais independently selected from Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;

[0888] and

[0889] each a and b is independently an integer between 1 and 12;

[0890] is a single bond or a double bond, wherein when is a double bond, R3and R5are both absent.

[0891] 28. The combination, build material, or kit of any one of the preceding embodiments, wherein q is 0 or 1.

[0892] 29. The combination, build material, or kit of any one of the preceding embodiments, wherein q is 0. 30. The combination, build material, or kit of any one of the preceding embodiments, wherein q is 1.

[0893] 31. The combination, build material, or kit of any one of the preceding embodiments, wherein — is a single bond.

[0894] 32. The combination, build material, or kit of any one of the preceding embodiments, wherein is a double bond and R3and R5are absent.

[0895] 33. The combination, build material, or kit of any one of the preceding embodiments, wherein R4taken together with R6and the carbon atoms to which they are attached form a C5-C7 cycloalkyl.

[0896] 34. The combination, build material, or kit of any one of the preceding embodiments, wherein R4and R6, together with the carbon atoms to which they are attached, form a Cs cycloalkyl.

[0897] 35. The combination, build material, or kit of any one of the preceding embodiments, wherein one of R3, R4, R5, and R6is C1-C16 alkyl.

[0898] 36. The combination, build material, or kit of any one of the preceding embodiments, wherein R6is C10 alkyl.

[0899] 37. The combination, build material, or kit of any one of the preceding embodiments, wherein one of R3, R4, R5and R6is C2-C16 alkenyl.

[0900] 38. The combination, build material, or kit of any one of the preceding embodiments, wherein any one of R3, R4is C2 alkenyl.

[0901] 39 A. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises Compound S-l, Compound S-2, or Compound S-3:

[0902]

[0903] 39. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises Compound S-l:

[0904]

[0905] 40. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises Compound S-2:

[0906]

[0907] 41. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises Compound S-3:

[0908]

[0909] 42. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIa):

[0910]

[0911] wherein:

[0912] R13is Ci-Cie alkyl.

[0913] 43. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises Compound S-4:

[0914]

[0915] 44. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-III):

[0916]

[0917] wherein:

[0918] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(C6-Ci4aryl); or

[0919] R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0920] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0921] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0922] 45. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIa):

[0923]

[0924] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4aryl, or -O-(C6-Ci4aryl); or

[0925] R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0926] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(C6-C14 aryl)-Ci-Ci4alkoxy, -C1-C16 alkoxy, -O-(C6-Ci4 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0927] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0928] 46. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIb):

[0929]

[0930] R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)- C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(C6-Ci4aryl); or

[0931] R9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;

[0932] R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; and

[0933] R12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

[0934] 47. The combination, build material, or kit of any one of the preceding embodiments, wherein the bridged polycyclic ROMP precursor comprises a compound of any one of Formulae (S-IVa), (S-IVb), (S-IVc), and (S-IVd):

[0935]

[0936] each Y is independently -CH2, -CH2-CH2-, -O-, or -S-;

[0937] X1is -O-, -S-, -NRa, -SiRbRc, -SiRbRcO(SiRbRcO)miSiRbRc, -SiRbRc(C6-Cio aryl)SiRbRc, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, Ci-Cis alkyl, -CH=CH-, or -C=C-; X2is -SiRbRc, -Si(RbRc)O(SiRbRcO)miSi(RbRc), -Si(RbRc)(C6-Cio aryl)Si(RbRc), -C(=0)-, C1-C18 alkyl, -CH=CH-, or -C=C-;

[0938] Ra, Rband Rcare each independently hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3-C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2; and

[0939] each n1, n2, n3, and n4 is independently an integer 0, 1, or 2;

[0940] each bi, b2, and b4 is independently an integer between 1 and 10;

[0941] mi is an integer between 0 and 10.

[0942] 48. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a ruthenium catalyst.

[0943] 49. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a latent ruthenium catalyst.

[0944] 50. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a non-latent ruthenium catalyst.

[0945] 51. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a Grubbs catalyst.

[0946] 52. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a first-generation Grubbs catalyst, a second-generation Grubbs catalyst, a third-generation Grubbs catalyst, a first-generation Grubbs-Hovey da catalyst, or a second-generation Grubbs-Hovey da catalyst.

[0947] 53. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a ruthenium-indenylidene complex.

[0948] 54. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII):

[0949]

[0950]

[0951] Each L1-bis independently L2-b, L3-b, L4-b, L8-b, L9-b, or L10‘b, L2'bis P(R5'b)3, pyridine, or dimethylsulfoxide, wherein the pyridine is optionally subsituted with one or more C1-C16 alkyl;

[0952]

[0953] independently Ce-Cio aryl or biphenyl; wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl, C1-C6 alkoxy, or -N(CI-C6alkyl)(Ci-C6alkyl);

[0954]

[0955] is a single bond or a double bond;

[0956] Rxis halogen;

[0957] R1-ais Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl);

[0958] each R2 aand R3 ais independently C1-C16 alkyl, C3-Ci4 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; or

[0959] R2 aand R3-a, together with the carbon to which they are attached, form a C3-Ci4 cycloalkyl; R4'ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0960] R5 ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0961] R8'ais Ci-Ce alkyl, C3-C14 cycloalkyl, or Ce-Cio aryl;

[0962] each R1-bis independently Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl); each R2 band R3'bis independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; or

[0963] R2 band R3'b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl;

[0964] Each R4'band R5 bis independently C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.

[0965] R6'bis absent, Ci-Ce alkyl, Ci-Ce alkoxy, Ce-Cio aryl, -0(Ci-Cio aryl), -NHC=O(Ci-Ce alkyl), -NHC=O(Ci-Ce fluoroalkyl), -SO2N(Ci-Ce alkyl)2, or -NO2;

[0966] R7 bis Ci-Ce alkyl, cyclohexyl, Ce-Cio aryl or biphenyl; wherein the cyclohexyl, Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[0967] each R8'band R9'bis independently methyl or benzyl; wherein the benzyl is optionally substituted with one or more C1-C16 alkyl;

[0968] each R10'bis independently C1-C16 alkyl or C3-C14 cycloalkyl; and

[0969] zi is 1 or 2.

[0970] 55. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), or a salt or solvate thereof.

[0971] 56. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst comprises a compound of any one of Formulae (C-VI) or (CVII) or a salt or solvate thereof.

[0972] 57. The combination, build material, or kit of any one of the preceding embodiments, wherein Ll-bis L4'b. 58. The combination, build material, or kit of any one of the preceding embodiments, wherein R2 band R3'bcome together to form a C5-C14 cycloalkyl.

[0973] 59. The combination, build material, or kit of any one of the preceding embodiments, wherein R2 band R3'bcome together to form a Ce cycloalkyl.

[0974] 60. The combination, build material, or kit of any one of the preceding embodiments, wherein each R1-bis Ci-Ce alkyl.

[0975] 61. The combination, build material, or kit of any one of the preceding embodiments, wherein each R1-bis methyl.

[0976] 62. The combination, build material, or kit of any one of the preceding embodiments, wherein Arl-bis Ce-Cio aryl optionally substituted with one or more C1-C16 alkyl.

[0977] 63. The combination, build material, or kit of any one of the preceding embodiments, wherein Arl-bis phenyl optionally subsituted with one or more C2 alkyl.

[0978] 64. The combination, build material, or kit of any one of the preceding embodiments, wherein Rxis Cl.

[0979] 65. The combination, build material, or kit of any one of the preceding embodiments, wherein L1-bis L3'b.

[0980] 66. The combination, build material, or kit of any one of the preceding embodiments, wherein L1-bis L9'b.

[0981] 67. The combination, build material, or kit of any one of the preceding embodiments, wherein R9'bis benzyl.

[0982] 68. The combination, build material, or kit of any one of the preceding embodiments, wherein Arl-bis Ce-Cio aryl optionally substituted with one or more C1-C16 alkyl. 69. The combination, build material, or kit of any one of the preceding embodiments, wherein Ar2'13is Ce-Cio aryl optionally substituted with one or more C1-C16 alkyl.

[0983] 70. The combination, build material, or kit of any one of the preceding embodiments, wherein Arl-bis phenyl optionally substituted with one or more methyl.

[0984] 71. The combination, build material, or kit of any one of the preceding embodiments, wherein Ar2'13is phenyl optionally substituted with one or more methyl.

[0985] 72. The combination, build material, or kit of any one of the preceding embodiments, wherein L1'13is L5'b.

[0986] 73. The combination, build material, or kit of any one of the preceding embodiments, wherein L5'bis L6'b.

[0987] 74. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst comprises Compound C-l:

[0988]

[0989] or a solvate thereof.

[0990] 75. The combination, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst comprises Compound C-2:

[0991]

[0992] or a solvate thereof.

[0993] 76. The combination, build material, or kit of any one of the preceding embodiments, further comprising an activator.

[0994] 77. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises l-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

[0995] 78. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises a copper(I), copper(II) or ruthenium based complex.

[0996] 79. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises a compound of any one of Formulae (A-I), (A-II), (A-III), (A- IV), and (A-V):

[0997] RuCl2(PPh3)p(A-I),

[0998] CuRzPPh3(A-II),

[0999] CuRz- (A-III),

[1000] (Rm)cCuCl (A-IV),

[1001]

[1002] solvate thereof, wherein Rzis halogen;

[1003] Rmis a compound of Formula (S-II), (S-III), (S-IIIa), (S-IIIb), (S-IVa), (S-IVb), (S-IVc), or (S-IVd);

[1004] nhc is an N-heterocyclic carbene;

[1005] each Ar4is Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;

[1006] p is 3 or 4; and

[1007] c is 0, 1, 2, 3, 4, 5, or 6.

[1008] 80. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises a compound of Formula (A-I).

[1009] 81. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises a compound of any one of Formulae (A-II), (A-III), (A-IV), and (A-V).

[1010] 82. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises a compound of Formula (A-V).

[1011] 83. The combination, build material, or kit of any one of the preceding embodiments, wherein Ar4is phenyl substituted with more than one C3 alkyl.

[1012] 84. The combination, build material, or kit of any one of the preceding embodiments,

[1013] wherein

[1014]

[1015] 85. The combination, build material, or kit of any one of the preceding embodiments, wherein the activator comprises Compound A-l:

[1016]

[1017] or a solvate thereof.

[1018] 86. The combination, build material, of any of the proceeding embodiments, further comprising a crosslinker.

[1019] 87. The combination, build material, of any of the proceeding embodiments, further comprising a synthetic rubber.

[1020] 88. The combination, build material, of any of the proceeding embodiments, further comprising a polymerization retardant.

[1021] 89. The combination, build material, of any of the proceeding embodiments, further comprising an impact modifier.

[1022] 90. The combination, build material, of any of the proceeding embodiments, further comprising a filler.

[1023] 91. A build material comprising the combination of any one of the preceding embodiments.

[1024] 92. A kit comprising the combination of any one of the preceding embodiments.

[1025] 93. The combination, build material, or kit of any one of the preceding embodiments, wherein the crosslinker is a norbornene-based crosslinker.

[1026] 94. The combination, build material, or kit of any one of the preceding embodiments, wherein the crosslinker comprises a norbomene terminated polydimethylsiloxane. 95. The combination, build material, or kit of any one of the preceding embodiments, wherein 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.

[1027] 96. The combination, build material, or kit of any one of the preceding embodiments, wherein the impact modifier comprises EPDM rubber.

[1028] 97. The combination, build material, or kit of any one of the preceding embodiments, wherein the impact modifier comprises a hydrogenated styrene-ethylene-ethylene-propylene-styrene (SEEPS) copolymer.

[1029] 98. The combination, build material, or kit of any one of the preceding embodiments, wherein the impact modifier comprises hydrogenated styrene-ethylene-propylene-styrene (SEPS) copolymer.

[1030] 99. The combination, build material, or kit of any one of the preceding embodiments, wherein the filler comprises a carbon nanotube, silica, metal oxide nanoparticle, or a combination thereof.

[1031] 100. The combination, build material, or kit of any one of the preceding embodiments, wherein the filler comprises a modified carbon nanotube.

[1032] 101. The combination, build material, or kit of any one of the preceding embodiments, wherein the filler comprises colloidal silica.

[1033] 102. The combination, build material, or kit of any one of the preceding embodiments, wherein the filler comprises fumed silica.

[1034] 103. The combination, build material, or kit of any one of the preceding embodiments, wherein the polymerization retardant comprises a phosphine, a phosphite, an aromatic amine, a sulfide, or a combination thereof. 104. The combination, build material, or kit of any one of the preceding embodiments, wherein the solvent comprises a reactive solvent.

[1035] 105. The combination, build material, or kit of any one of the preceding embodiments, wherein the solvent comprises a non-reactive solvent.

[1036] 106. The combination, build material, or kit of any one of the preceding embodiments, wherein the solvent comprises a eutectic mixture of diphenyl ether and biphenyl.

[1037] 107. The combination, build material, or kit of any one of the preceding embodiments, wherein the solvent comprises a mixture of about 27 % (w / w) biphenyl and about 73 % (w / w) diphenyl ether.

[1038] 108. The combination, build material, or kit of any one of the preceding embodiments, further comprising an antioxidant.

[1039] 109. The combination, build material, or kit of any one of the preceding embodiments, wherein the antioxidant comprises a catechol.

[1040] 110. The combination, build material, or kit of any one of the preceding embodiments, wherein the antioxidant comprises 4-tert-butylcatechol.

[1041] 111. The combination, build material, or kit of any one of the preceding embodiments, further comprising a stabilizer.

[1042] 112. The combination, build material, or kit of any one of the preceding embodiments, wherein the stabilizer comprises a phosphine, a phosphite, an aromatic amine, a catechol, a pyrocatechol, a sulfide, a bidentate ligand comprising a styrene moiety, or a combination thereof.

[1043] 113. The combination, build material, or kit of any one of the preceding embodiments, wherein the stabilizer comprises 4-dimethylaminopyridine (DMAP). 114. The combination, build material, or kit of any one of the preceding embodiments, further comprising a chain transfer agent.

[1044] 115. The combination, build material, or kit of any one of the preceding embodiments, wherein the chain transfer agent comprises an alkene.

[1045] 116. The combination, build material, or kit of any one of the preceding embodiments, wherein the chain transfer agent comprises a diene.

[1046] 117. The combination, build material, or kit of any one of the preceding embodiments, wherein the chain transfer agent comprises a polyene.

[1047] 118. A method of preparing a cured material, comprising a step of subjecting the combination or kit of any one of the preceding embodiments to a curing condition.

[1048] 119. The combination, build material, or kit of any one of the preceding embodiments for use in preparing a cured material, wherein the preparation comprises a step of subjecting the combination or kit to a curing condition.

[1049] 120. Use of the combination, build material, or kit of any one of the preceding embodiments in the manufacture of a cured material, wherein the manufacture comprises a step of subjecting the combination or kit to a curing condition.

[1050] 121. A cured material being prepared by the method of any one of the preceding embodiments.

[1051] 122. A method of printing an object using the method, combination, build material, kit, or use of any one of the preceding embodiments.

[1052] 123. The combination, build material, or kit of any one of the preceding embodiments for use in printing an object.

[1053] 124. The method, combination, build material, or kit of any one of the preceding embodiments, for use in printing an object wherein the printing comprises (i) depositing the build material; and

[1054] (ii) subjecting the deposited build material to a curing condition.

[1055] 125. The method, combination, build material, or kit of any one of the preceding embodiments, for use in printing an object wherein the printing comprises

[1056] (i) providing the build material and

[1057] (ii) providing an energy source to activate the radical initiator.

[1058] 126. The method, combination, build material, or kit of any one of the preceding embodiments, for use in printing an object wherein the printing comprises exposing the build material to an energy source (e.g., a light source, e.g., UV light).

[1059] 127. The method, combination, build material, or kit of any one of the preceding embodiments, for use in printing an object wherein the printing further comprises optically sensing the deposited material, and controlling the one or more repeated deposition of the material according to the sensing.

[1060] 128. A system for 3D printing, comprising:

[1061] (i) a printer; and

[1062] (ii) an ink comprising the combination of any one of the preceding embodiments.

[1063] EXAMPLES

[1064] Definitions

[1065]

[1066]

[1067]

[1068] Example 1. Mass Polymerization with Non-Latent Ruthenium Catalyst M200 - Batches 1A & IB

[1069] Formulations Batch 1 A and Batch IB were prepared by adding a solution of M200 and TPP in Dowtherm A to a resin according to the amounts indicated in Table 4:

[1070] Table 4:

[1071]

[1072] *contains approximately 5% (w / w) TCPD

[1073] The resulting formulations were poured into stainless steel molds and heated to 40 °C. After the peak exotherm occured, the resulting testing bars were post cured at ambient pressure in air at 140 °C for 30 min and then slowly cooled down to room temperature. The top surface of the testing bars was flattened / polished with the use of sandpaper (gradation from 180 to 300). The tensile properties were measured according to PN-EN ISO527 standard (10 mm / min, bar type B) and impact strength was measured with the Izod method (RESIL 5.5, CEAS; hammer Energy - 2J) according to the ISO 180 / B standard. The results are shown in Table 5 below.

[1074] Table 5: Tensile Properties and Impact Strength Measurements - Batches 1A & IB

[1075]

[1076] UTS = ultimate tensile strength; YM = Young’s modulus; EAB = elongation at break; IS = impact strength

[1077] Example 2. Mass Polymerization with Latent Ruthenium Catalyst ULM, Activator C7, and DMAP - Batches 2A - 2E

[1078] Formulations Batches 2 A - 2E were prepared by adding a solution of ULM and DMAP in Dowtherm A to a resin according to Table 6 and mixing thoroughly. Then a solution of activator C7 in Dowtherm A (lwt%, 30 mol ppm ) was added and mixed thoroughly. Table 6:

[1079]

[1080] *contains approximately 5% (w / w) TCPD

[1081] The resulting formulations were poured into stainless steel molds and heated to 75 °C. After the peak exotherm occurred, the resulted testing bars were post cured at ambient pressure in air at 140 °C for 30 min and then slowly cooled down to room temperature. The top surface of the testing bars was flattened / polished with the use of sandpaper (gradation from 180 to 300). The tensile properties were measured according to PN-EN ISO527 standard (10 mm / min, bar type B) and impact strength was measured with Izod method (RESIL 5.5, CEAS; hammer Energy - 2J) according to the ISO 180 / B standard. The results are shown in Table 7 below.

[1082] Table 7: Tensile Properties and Impact Strength Measurements - Batches 2A - 2E

[1083]

[1084] UTS = ultimate tensile strength; YM = Young’s modulus; EAB = elongation at break; IS = impact strength Example 3. Mass Polymerization with Latent Ruthenium Catalyst ULM, Activator C7, and ‘BuCat - Batches 3A - 3G

[1085] Formulations Batches 3 A - 3G were prepared by adding a solution of activator C7 andlBuCat in Dowtherm A to a resin according to Table 8 and mixing thoroughly followed by adding a solution of ULM in Dowtherm A also according to Table 8 and mixing thoroughly.

[1086] Table 8:

[1087]

[1088] *contains approximately 5% (w / w) TCPD

[1089] The resulting formulations were poured into silicon molds. After the peak exotherm occurred, the resulting testing bars were post cured in a vacuum oven at 145 °C for 30 min and then slowly cooled down to room temperature. The tensile properties were measured according to the ASTM D638 (5 mm / min) standard. Tgwas measured with DSC. The results are shown in Table 9 below.

[1090] Table 9: Tensile Properties and TgMeasurements - Batches A - G

[1091]

[1092] UTS = ultimate tensile strength; YM = Young’s modulus; EAB = elongation at break; IS = impact strength; Tg= glass transition temperature; NT = not tested

[1093] Example 4. Mass Polymerization with Latent Ruthenium Catalyst ULM, Activator C7, and pyrocatechol - Batches 4A & B

[1094] Formulations Batches 4 A & 4B were prepared by adding a solution of activator C7 and pyrocatechol in Dowtherm A to a resin according to Table 10 and mixing thoroughly followed by adding a solution of ULM in Dowtherm A also according to Table 10 and mixing thoroughly.

[1095] Table 10:

[1096]

[1097] *contains approximately 5% (w / w) TCPD

[1098] The resulting formulations were poured into silicon molds for tensile testing bars and to stainless steel molds (heated up to 70 °C) for impact strength testing the bars. After the peak exotherm occurred, the resulting testing bars were post cured in air at 140 °C for 30 min and then slowly cooled down to room temperature. The tensile properties were measured according to ASTM D638 (5 mm / min) standard and impact strength was measured with the Izod method (RESIL 5.5, CEAS; hammer Energy - 2J) according to the ISO 180 / B standard. The results are shown in Table 11 below.

[1099] Table 11: Tensile Properties and Impact Strength Measurements - Batches 4A & 4B

[1100]

[1101] UTS = ultimate tensile strength; YM = Young’s modulus; EAB = elongation at break; IS = impact strength

[1102] Example 5. Mass Polymerization with Latent Ruthenium Catalyst ULM, Activator C7, and ‘BuCat - Batches 5A & 5B

[1103] Formulations Batches 5 A & 5B were prepared by adding a solution of activator C7 andlBuCat in Dowtherm A to a resin according to Table 12 and mixing thoroughly followed by adding a solution of ULM in Dowtherm A also according to Table 12 and mixing thoroughly.

[1104] Table 12:

[1105]

[1106] *contains approximately 5% (w / w) TCPD

[1107] The resulting formulation was poured into silicon molds for tensile testing bars. After the peak exotherm occurred, the resulted testing bars were post cured in air at 140 °C for 30 min and then slowly cooled down to room temperature. The tensile properties were measured according to the ASTM D638 (5 mm / min) standard. The results are shown in Table 13.

[1108] Table 13: Tensile Properties Measurements - Batches 5A & 5B

[1109]

[1110] UTS = ultimate tensile strength; YM = Young’s modulus; EAB = elongation at break

[1111] Example 6. Mass Polymerization with Non-Latent Ruthenium Catalyst M200 - Batches 6A- 6C Formulations Batches 6 A - 6C were prepared by adding a solution of M200 and TPP in Dowtherm A to a resin according to the amounts indicated in Table 14.

[1112] Table 14:

[1113]

[1114] The resulting formulations were poured into silicon molds (preheated to 40 °C) to make testing boards for tensile strength and tear strength measurment. After the peak exotherm occured, the resulted testing bars were post cured in air at 110 °C for 15 min and then slowly cooled down to room temperature. The tensile properties were measured according to the ASTM D412C (100 mm / min) standard and the tear strength was measured according to the ASTM D624-C 500 mm / min) standard. Tgwas measured with DSC. The results are shown in Table 15 below.

[1115] Table 15: Tensile Properties, Tear Strength, and TgMeasurements - Batches 6A - 6C

[1116]

[1117] NF - not found

[1118] EQUIVALENTS

[1119] 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. In the case of conflict between the chemical structures and names of the compounds disclosed herein, the chemical structures will control.

[1120] 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

Claims1. A combination comprising:(i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor;(ii) a bridged polycyclic ROMP precursor; and(iii) a curing catalyst.

2. A kit comprising:a build material comprising:(i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;(iii) a latent curing catalyst;(iv) an activator; anda support material.

3. A kit comprising:a first build material comprising:(i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;(iii) an activatora second build material comprising:(iv) a curing catalyst(v) a solvent; anda support material.

4. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor is a strained ROMP precursor.

5. The combination, build material, or kit of any one of the preceding claims, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-I):wherein W is CH2 or C=O;Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; and, together with the atoms to which it is attached and any intervening atoms, forms a 14- to 50- membered ring comprising 1-10 C=C bonds.

6. The combination, build material, or kit of any one of the preceding claims, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-I):wherein W is CH2 or C=O;Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; and, together with the atoms to which it is attached and any intervening atoms, forms a 16- to 17- membered ring comprising 1-2 C=C bonds.

7. The combination, build material, or kit of any one of the preceding claims, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-Ia):wherein:W is CH2or C=O;m and n are each independently an integer between 0 and 20;Ri and R2 are each independently absent, -CH2-, -O-, or -NH-;*each - is independently a single bond or a double bond having either the (E) or (Z) configuration; and*wherein at least one - is a double bond;provided that:a) when neither of Ri and R2 are absent, the sum of m + n is > 7; b) when one of Ri and R2 is absent, the sum of m + n is > 8; and c) when both of Ri and R2 are absent, the sum of m + n is > 9.

8. The combination, build material, or kit of any one of the preceding claims, wherein the macrocyclic ROMP precursor comprises Compound (R-l), Compound (R-2), Compound (R-3), or Compound (R-4):

9. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-II):wherein:q is 0, 1 or 2;R3and R5are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4 aryl, -O-C6-Ci4 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3-to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A;R4and R6are each independently hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, Ce-Cw aryl, -O-Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, Ce-Cw aryl, 3- to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more R1A; orR4and R6, together with the carbon atoms to which they are attached, form a C5-C7 cycloalkyl;each R1Ais independently halogen, Ci-Ce alkyl, or C1-C16 alkoxy;Z is a bond, -(CR2AR3A)a-, -O(CR2AR3A)a-, -(CR2AR3A)aO-, -(CR2AR3A)a-O-(CR2AR3A)b-, -(CR2AR3A)a-O-(SiR2AR3A)b-, -(CR2AR3A)a-(C=O)O-(CR2AR3A)b-, -(CR2AR3A)-O(C=O)-(C R2AR3A)b-, -(CR2AR3A)a-(C=O)-(CR2AR3A)b-;Each R2Aand R3Ais independently hydrogen, Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;R7is phenyl optionally substituted with one or more R7A;Each R7Ais independently selected from Ci-Ce alkyl, Ci-Ce alkoxy, -O-C(=O)-Ci-Ce alkyl, -C(=O)-(Ci-Ce alkyl), phenyl, or -O-phenyl;andeach 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, R3and R5are both absent.

10. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises Compound S-l, Compound S-2, or Compound S-3:

11. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIa):wherein:R13is C1-C16 alkyl.

12. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises Compound S-4:

13. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-III):wherein:R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(C6-Ci4aryl); orR9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; andR12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

14. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIa):R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4aryl, or -O-(C6-Ci4aryl); orR9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(C6-C14 aryl)-Ci-Ci4alkoxy, -C1-C16 alkoxy, -O-(C6-Ci4 aryl), -O(C=O)R12, or -O(C=O)OR12; andR12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

15. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-IIIb):R9and R10are each independently hydrogen, C1-C16 alkyl, C1-C16 alkoxy, -O-C(=O)-C1-C16 alkyl, -C(=O)-(Ci-Ci6 alkyl), C6-Ci4 aryl, or -O-(C6-Ci4aryl); orR9taken together with R10and the carbon atoms to which they are attached to form a C5-C7 cycloalkyl;R11is hydrogen, halogen, OH, C1-C16 alkyl, Ce-Ci6 aryl, -(Ce-Cu aryl)-Ci-Ci4alkoxy, - C1-C16 alkoxy, -O-(C6-C14 aryl), -O(C=O)R12, or -O(C=O)OR12; andR12is C1-C16 alkyl, C6-Ci4aryl, or (C6-Ci4 aryl)-(Ci-Ci6alkyl).

16. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor comprises a compound of any one of Formulae (S-IVa), (S-IVb), (S-IVc), and (S-IVd):(S-IVd);wherein:each Y is independently -CH2, -CH2-CH2-, -O-, or -S-;X1is -O-, -S-, -NRa, -SiRbRc, -SiRbRcO(SiRbRcO)miSiRbRc, -SiRbRc(C6-Cio aryl)SiRbRc, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-, -C(=O)-S-, Ci-Cis alkyl, -CH=CH-, or -C=C-;X2is -SiRbRc, -Si(RbRc)O(SiRbRcO)miSi(RbRc), -Si(RbRc)(C6-Cio aryl)Si(RbRc), - C(=O)-, Ci-Cis alkyl, -CH=CH-, or -C=C-;Ra, Rband Rcare each independently hydrogen, C1-C12 alkyl, C3 -C12 cycloalkyl, C3- C12 cycloalkenyl, or (C5-C12 cycloalkyl)-(Ci-C3alkyl)Si(CH3)2; andeach n1, n2, n3, and n4 is independently an integer 0, 1, or 2;each bi, b2, and b4 is independently an integer between 1 and 10;mi is an integer between 0 and 10.

17. The combination, build material, or kit of any one of the preceding claims, wherein the curing catalyst is a ruthenium catalyst.

18. The combination, build material, or kit of any one of the preceding claims, wherein the curing catalyst comprises a compound of any one of Formulae (C-I), (C-II), (C-III), (C-IV), (C-V), (C-VI), or (C-VII):Each L1-bis independently L2-b, L3-b, L4-b, L8-b, L9-b, or L10‘b,L2'bis P(R5'b)3, pyridine, or dimethylsulfoxide, wherein the pyridine is optionally subsituted with one or more C1-C16 alkyl;independently Ce-Cio aryl or biphenyl; wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl, C1-C6 alkoxy, or -N(CI-C6alkyl)(Ci-C6alkyl);is a single bond or a double bond;Rxis halogen;R1-ais Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl);each R2 aand R3 ais independently C1-C16 alkyl, C3-Ci4 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; orR2 aand R3-a, together with the carbon to which they are attached, form a C3-Ci4 cycloalkyl;R4'ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;R5 ais C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, C6-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;R8'ais Ci-Ce alkyl, C3-C14 cycloalkyl, or Ce-Cio aryl;each R1-bis independently Ci-Ce alkyl, Ce-Cio aryl, Ci-Ce alkoxy, or -0(Ce-Cio aryl); each R2 band R3'bis independently C1-C16 alkyl, C3-C14 cycloalkyl, Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more Ci-Ci6 alkyl; orR2 band R3'b, together with the carbon to which they are attached, form a C3-C14 cycloalkyl;Each R4'band R5 bis independently C1-C16 alkyl, C3-C14 cycloalkyl, C2-C16 alkenyl, Ce-C14 aryl or biphenyl, wherein the C6-C14 aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl.R6'bis absent, Ci-Ce alkyl, Ci-Ce alkoxy, Ce-Cio aryl, -0(Ci-Cio aryl), -NHC=O(Ci-Ce alkyl), -NHC=O(Ci-Ce fluoroalkyl), -SO2N(Ci-Ce alkyl)2, or -NO2;R7 bis Ci-Ce alkyl, cyclohexyl, Ce-Cio aryl or biphenyl; wherein the cyclohexyl, Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;each R8'band R9'bis independently methyl or benzyl; wherein the benzyl is optionally substituted with one or more C1-C16 alkyl;each R10'bis independently C1-C16 alkyl or C3-C14 cycloalkyl; andzi is 1 or 2.

19. The combination, build material, or kit of any one of the preceding claims, wherein the curing catalyst comprises Compound C-l:or a solvate thereof.

20. The combination, build material, or kit of any one of the preceding claims, wherein the curing catalyst comprises Compound C-2:or a solvate thereof.

21. The combination, build material, or kit of any one of the preceding claims, further comprising an activator.

22. The combination, build material, or kit of any one of the preceding claims, wherein the activator comprises l-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX).

23. The combination, build material, or kit of any one of the preceding claims, wherein the activator comprises a compound of any one of Formulae (A-I), (A-II), (A-III), (A-IV), and (A-V):RuCl2(PPh3)p(A-I),CuRzPPh3(A-II),CuRz- (A-III),(Rm)cCuCl (A-IV),solvate thereof,wherein Rzis halogen;Rmis a compound of Formula (S-II), (S-III), (S-IIIa), (S-IIIb), (S-IVa), (S-IVb), (S-IVc), or (S-IVd);nhc is an N-heterocyclic carbene;each Ar4is Ce-Cio aryl or biphenyl, wherein the Ce-Cio aryl or biphenyl is optionally substituted with one or more C1-C16 alkyl;p is 3 or 4; andc is 0, 1, 2, 3, 4, 5, or 6.

24. The combination, build material, or kit of any one of the preceding claims, wherein the activator comprises Compound A-l:or a solvate thereof.

25. The combination, build material, or kit of any of the proceeding claims, further comprising a crosslinker, a synthetic rubber, a polymerization retardant, an impact modifier, and / or a filler.

26. A build material comprising the combination of any one of the preceding claims.

27. A kit comprising the combination of any one of the preceding claims.

28. The combination, build material, or kit of any one of the preceding claims, wherein the crosslinker is a norbornene-based crosslinker.

29. The combination, build material, or kit of any one of the preceding claims, wherein the crosslinker comprises a norbomene terminated polydimethylsiloxane.

30. The combination, build material, or kit of any one of the preceding claims, wherein 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.

31. The combination, build material, or kit of any one of the preceding claims, wherein the filler comprises a carbon nanotube, silica, metal oxide nanoparticle, or a combination thereof.

32. The combination, build material, or kit of any one of the preceding claims, wherein the polymerization retardant comprises a phosphine, a phosphite, an aromatic amine, a sulfide, or a combination thereof.

33. The combination, build material, or kit of any one of the preceding claims, wherein the solvent comprises a reactive solvent.

34. The combination, build material, or kit of any one of the preceding claims, wherein the solvent comprises a non-reactive solvent.

35. The combination, build material, or kit of any one of the preceding claims, wherein the solvent comprises a eutectic mixture of diphenyl ether and biphenyl.

36. The combination, build material, or kit of any one of the preceding claims, wherein the solvent comprises a mixture of about 27 % (w / w) biphenyl and about 73 % (w / w) diphenyl ether.

37. The combination, build material, or kit of any one of the preceding claims, further comprising an antioxidant.

38. The combination, build material, or kit of any one of the preceding claims, further comprising a stabilizer.

39. The combination, build material, or kit of any one of the preceding claims, wherein the stabilizer comprises 4-dimethylaminopyridine (DMAP).

40. The combination, build material, or kit of any one of the preceding claims, further comprising a chain transfer agent.

41. A method of preparing a cured material, comprising a step of subjecting the combination or kit of any one of the preceding claims to a curing condition.

42. The combination, build material, or kit of any one of the preceding claims for use in preparing a cured material, wherein the preparation comprises a step of subjecting the combination or kit to a curing condition.

43. Use of the combination, build material, or kit of any one of the preceding claims in the manufacture of a cured material, wherein the manufacture comprises a step of subjecting the combination or kit to a curing condition.

44. A cured material being prepared by the method of any one of the preceding claims.

45. A method of printing an object using the method, combination, build material, kit, or use of any one of the preceding claims.

46. The combination, build material, or kit of any one of the preceding claims for use in printing an object.

47. The method, combination, build material, or kit of any one of the preceding claims, for use in printing an object wherein the printing comprises(i) depositing the build material; and(ii) subjecting the deposited build material to a curing condition.

48. The method, combination, build material, or kit of any one of the preceding claims, for use in printing an object wherein the printing comprises(i) providing the build material and(ii) providing an energy source to activate the radical initiator.

49. The method, combination, build material, or kit of any one of the preceding claims, for use in printing an object wherein the printing comprises exposing the build material to anenergy source (e.g., a light source, e.g., UV light).

50. The method, combination, build material, or kit of any one of the preceding claims, for use in printing an object wherein the printing further comprises optically sensing the deposited material, and controlling the one or more repeated deposition of the material according to the sensing.

51. A system for 3D printing, comprising:(i) a printer; and(ii) an ink comprising the combination of any one of the preceding claims.

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