Materials for ring-opening metathesis polymerization and uses thereof

Abstract

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

Description

[Technical field]

[0001] Cross-reference to related applications This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 180,403, filed April 27, 2021, the contents of which are incorporated by reference in their entirety for all purposes.

[0002] Additive manufacturing, also known as 3D printing, refers to a relatively broad range of techniques for producing objects by selectively adding material according to a computer-controlled process to conform to desired 3D specifications, usually solid models. Many different classes of materials have been used for such 3D printing, and different materials have advantages and disadvantages that correspond to different manufacturing techniques. For example, a survey of materials can be found in Ligon et al. (Chemical Reviews 117(15):10212-10290(2017)).

[0003] Activation of latent homogeneous catalysts by external stimuli is exploited in many important industrial polymerization processes such as 3D printing. In the field of manufacturing technology, inkjet printing techniques are used to jet material for deposition on partially manufactured objects. The jetted material is typically UV cured immediately after deposition to form a thin layer of hardened material. To achieve precision manufacturing, some techniques use mechanical means to maintain a precise layered structure. For example, mechanical rollers or "flatteners" are used to control the surface shape and thus the precision of the manufactured object. Thus, rapid curing is a key feature to enable planarization and obtain precisely manufactured objects. However, the material properties obtained with such inks may be insufficient.

[0004] There is a need for new materials that can be used as inks in 3D printing, and the present disclosure addresses this need. Summary of the Invention

[0005] In some embodiments, the present disclosure provides: (i) a ring-opening metathesis polymerization (ROMP) precursor; (ii) a curing catalyst.

[0006] In some embodiments, the present disclosure provides: (i) a ring-opening metathesis polymerization (ROMP) precursor; (ii) a curing catalyst; and (iii) an activator.

[0007] In some aspects, the present disclosure provides a build material comprising the formulation disclosed herein.

[0008] In some embodiments, the present disclosure provides: (i) a ROMP precursor; (ii) a curing catalyst.

[0009] In some embodiments, the present disclosure provides: (i) a ROMP precursor; (ii) a curing catalyst; and (iii) an activator.

[0010] In some embodiments, the present disclosure provides kits comprising the formulations disclosed herein.

[0011] In some embodiments, the present disclosure provides: (i) ROMP precursors and (ii) Curing catalyst a first build material comprising: (iii) ROMP precursors, and (iv) Activator and a second build material comprising the material.

[0012] In some embodiments, the present disclosure provides: (i) ROMP precursors and (ii) Curing catalyst A molding material comprising: and supporting material.

[0013] In some embodiments, the present disclosure provides: (i) ROMP precursors, (ii) a curing catalyst; and (iii) Activator A molding material comprising: and supporting material.

[0014] In some embodiments, the present disclosure provides: (i) ROMP precursors and (ii) Curing catalyst a first build material comprising: (iii) ROMP precursors, and (iv) Activator A second material comprising: and supporting material.

[0015] In some embodiments, the present disclosure provides a method of preparing a hardened material comprising subjecting a formulation, modeling material, or kit disclosed herein to hardening conditions.

[0016] In some embodiments, the present disclosure provides a formulation, modeling material, or kit as disclosed herein for use in preparing a cured material, said preparation comprising subjecting the formulation, modeling material, or kit to curing conditions.

[0017] In some embodiments, the present disclosure provides the use of a formulation, modeling material, or kit disclosed herein for use in the manufacture of a hardened material, said manufacture comprising a step of subjecting the formulation, modeling material, or kit to hardening conditions.

[0018] In some aspects, the present disclosure provides a cured material prepared by the methods described herein.

[0019] In some embodiments, the present disclosure provides methods of printing objects using the formulations, build materials, or kits disclosed herein.

[0020] In some embodiments, the present disclosure provides a formulation, build material, or kit as disclosed herein for use in printing an object.

[0021] In some embodiments, the present disclosure provides a system for 3D printing, the system comprising: (i) a printer (e.g., an inkjet printer); and (ii) an ink comprising the formulation disclosed herein.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. In this specification, the singular form includes the plural form unless otherwise specified by the context. Methods and materials similar or equivalent to those described herein can be used to practice or test this disclosure, but suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated by reference. References cited herein are not admitted to be prior art to the claimed invention. In case of conflict, the present specification, including definitions, will prevail. Furthermore, the materials, methods and examples are merely illustrative and are not intended to be limiting. In case of conflict between the chemical structure and name of a compound disclosed herein, the chemical structure will prevail.

[0023] Other features and advantages of the present disclosure will be apparent from the following detailed description, and from the claims. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 is a schematic diagram of an exemplary 3D printer. [Diagram 2] FIG. 2 is a schematic diagram of an alternative exemplary 3D printer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] To achieve the high latency and rapid polymerization desired for applications such as 3D printing, polymers such as UV-cured epoxies and UV-cured acrylates are typically used. Cyclic olefin polymers produced by ring-opening metathesis (ROMP) exhibit excellent properties for many applications. However, ROMP technology may have limited applications due to its rapid curing at ambient (e.g., room temperature). Typically, ROMP-polymerizable formulations solidify immediately upon addition of the catalyst. This limits the use of ROMP formulations in 3D inkjet processes, which require liquid components with viscosities within a predefined range to be passed through an inkjet printhead. Latent metathesis catalysts are an important class of catalysts that require the addition of an external stimulus to promote the metathesis reaction and are therefore sometimes employed to ensure suitable stability of the components under ambient conditions.

[0026] Furthermore, low viscosity (e.g., 0.5-150 cP at 90 °C), low surface tension (e.g., 20-45 mN / m) and low particle size (e.g., filterable through a 3 μm filter) are highly desirable for inkjet printing. Furthermore, the formation of small, high-surface-area droplets is important for inkjet 3D printers and similar technologies, and many common polymerizing components, such as dicyclopentadiene (DCPD), may not be suitable for inkjet printing due to their low flash point and the high temperatures that inkjet printer surfaces and electronic components experience (without wishing to be bound by theory, droplets of flammable liquids may be more flammable than bulk liquids of the same chemical composition). On the other hand, many of the polymerizable compositions developed for other 3D printing methods, such as stereolithography (SLA), may have properties that are unnecessary or harmful for inkjet printing, such as selective photoinhibitors required to prevent polymerization outside the desired print area.

[0027] There is a need for new compositions for ROMP that have most or all of the properties that are compatible with various 3D printing methods (e.g., inkjet 3D printing), such as high overall polymerization rate, high latency, low viscosity, low particulate content, high flash point, etc. The present disclosure addresses this need.

[0028] Without wishing to be bound by any particular theory, the present disclosure relates to the discovery of new materials for ring-opening metathesis polymerization (ROMP). Such materials may be suitable for use as 3D printing inks. In some embodiments, the materials are capable of 3D printing processes that do not require contact to control the surface shape of the printed object, for example, 3D printing processes that use a non-contact (e.g., optical) feedback approach.

[0029] Suitable applications and systems for the materials of the present disclosure are described, for example, in U.S. Provisional Application No. 62 / 777,422 and PCT Application No. PCT / US2019 / 065436, which are incorporated herein by reference. Formulations, Materials, and Kits of the Present Disclosure

[0030] In some embodiments, the present disclosure provides: (i) a ring-opening metathesis polymerization (ROMP) precursor; (ii) a curing catalyst.

[0031] In some embodiments, the present disclosure provides: (i) a ring-opening metathesis polymerization (ROMP) precursor; (ii) a curing catalyst; and (iii) an activator.

[0032] In some aspects, the present disclosure provides a build material comprising the formulation disclosed herein.

[0033] In some embodiments, the present disclosure provides: (i) a ROMP precursor; (ii) a curing catalyst.

[0034] In some embodiments, the present disclosure provides: (i) a ROMP precursor; (ii) a curing catalyst; and (iii) an activator.

[0035] In some embodiments, the present disclosure provides kits comprising the formulations disclosed herein.

[0036] In some embodiments, the present disclosure provides: (i) ROMP precursors and (ii) Curing catalyst a first build material comprising: (iii) ROMP precursors, and (iv) an activator and a second build material comprising the

[0037] In some embodiments, the present disclosure provides: (i) ROMP precursors a first build material comprising: (ii) an activator, (iii) a curing catalyst; and (iv) Inert Solvent a second build material comprising: and supporting material.

[0038] In some embodiments, the present disclosure provides: (i) ROMP precursors and (ii) a build material including a curing catalyst; and supporting material.

[0039] In some embodiments, the present disclosure provides: (i) ROMP precursors, (ii) a curing catalyst; and (iii) Activator A molding material comprising: and supporting material.

[0040] In some embodiments, the present disclosure provides: (i) ROMP precursors and (ii) Curing catalyst a first build material comprising: (iii) ROMP precursors, and (iv) Activator a second build material comprising: and supporting material.

[0041] For any formulation, modeling material, or kit described herein, the ROMP precursor, curing catalyst, activator, and support material may each be selected from the groups described herein, where applicable, and any group described herein for any of the ROMP precursor, curing catalyst, activator, antioxidant, catalyst inhibitor, optical enhancing component, flame retardant, and support material may be in a formulation with any group described herein for one or more of the remaining of the ROMP precursor, curing catalyst, activator, antioxidant, catalyst inhibitor, optical enhancing component, flame retardant, and support material, where applicable. ROMP precursors

[0042] In some embodiments, the ROMP precursor is a compound of formula (MI): [ka] or a salt thereof, X is CH2 or O; R 1 are each independently (a) H, halogen, cyano, -OR 1A , -SR 1A , -C(=O)-R 1A , -C(=O)-OR 1A , -OC(=O)-R 1A , -C(=O)-N(R 1A )2, -C(=O)-NHR 1A , -NH-C(=O)-R1A , -N(R 1A )2, -Si(R 1A )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A or (b) Other R 1 and form bonds with the atoms to which they are attached, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A optionally replaced by R 1A are each independently (a) H, halogen, cyano, -OR 1B , -SR 1B , -C(=O)-R 1B , -C(=O)-OR 1B , -OC(=O)-R 1B , -C(=O)-N(R 1B )2, -C(=O)-NHR 1B , -NH-C(=O)-R 1B , -N(R 1B )2, -Si(R 1B )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B optionally replaced by (b) Other R 1A and form bonds with the atoms to which they are attached, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B optionally replaced by (c) [ka] or [ka] and R 1B are each independently [ka] Hydrogen, halogen, cyano, -OR 1C , -SR 1C , -C(=O)-R 1C , -C(=O)-OR 1C , -OC(=O)-R 1C , -C(=O)-N(R 1C )2, -C(=O)-NHR 1C , -NH-C(=O)-R 1C , -N(R 1C)2, -Si(R 1C )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is one or more R 1C optionally replaced by R 1C are each independently [ka] Hydrogen, halogen, cyano, -OR 1D , -SR 1D , -C(=O)-R 1D , -C(=O)-OR 1D , -OC(=O)-R 1D , -C(=O)-N(R 1D )2, -C(=O)-NHR 1D , -NH-C(=O)-R 1D , -N(R 1D )2, -Si(R 1D )3, C1-C20 alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R1D and R 1D are each independently cyano, -OH, -NH2, C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 It is aryl, a 3- to 20-membered heterocycloalkyl, or a 5- to 20-membered heteroaryl.

[0043] In some embodiments, the ROMP precursor is a compound of formula (MI) or a salt thereof: X is CH2 or O; R 1 are each independently (a) Hydrogen, halogen, cyano, -OR 1A , -SR 1A , -C(=O)-R 1A , -C(=O)-OR 1A , -OC(=O)-R 1A , -C(=O)-N(R 1A )2, -C(=O)-NHR 1A , -NH-C(=O)-R 1A , -N(R 1A )2, -Si(R 1A )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A or (b) Other R 1and form bonds with the atoms to which they are attached, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A optionally replaced by R 1A are each independently (a) is hydrogen, halogen, cyano, -OR 1B , -SR 1B , -C(=O)-R 1B , -C(=O)-OR 1B , -OC(=O)-R 1B , -C(=O)-N(R 1B )2, -C(=O)-NHR 1B , -NH-C(=O)-R 1B , -N(R 1B )2, -Si(R 1B )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B or (b) another R 1A and together with the atoms to which they are attached, form bonds, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B optionally replaced by R 1B are each independently hydrogen, halogen, cyano, -OR 1C , -SR 1C , -C(=O)-R 1C , -C(=O)-OR 1C , -OC(=O)-R 1C , -C(=O)-N(R 1C )2, -C(=O)-NHR 1C , -NH-C(=O)-R 1C , -N(R 1C )2, -Si(R 1C )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is one or more R 1C optionally replaced by R 1C are each independently hydrogen, halogen, cyano, -OR 1D , -SR 1D , -C(=O)-R 1D , -C(=O)-OR 1D , -OC(=O)-R 1D , -C(=O)-N(R 1D )2, -C(=O)-NHR 1D , -NH-C(=O)-R 1D , -N(R 1D )2, -Si(R 1D )3, C1-C20 alkyl, C2-C 20Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1D and R 1D are each independently hydrogen, halogen, cyano, -OH, -NH2, C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 It is aryl, a 3- to 20-membered heterocycloalkyl, or a 5- to 20-membered heteroaryl. Mutant X

[0044] In some embodiments, X is CH2.

[0045] In some embodiments, X is O. Mutant R 1

[0046] In some embodiments, at least one R 1 is hydrogen, halogen, cyano, -OR 1A , -SR 1A , -C(=O)-R 1A , -C(=O)-OR 1A , -OC(=O)-R 1A , -C(=O)-N(R 1A )2, -C(=O)-NHR 1A , -NH-C(=O)-R 1A , -N(R 1A )2, -Si(R1A )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A is optionally replaced by

[0047] In some embodiments, R 1 At least one of is hydrogen.

[0048] In some embodiments, at least one R 1 is halogen, cyano, -OR 1A , -SR 1A , -C(=O)-R 1A , -C(=O)-OR 1A , -OC(=O)-R 1A , -C(=O)-N(R 1A )2, -C(=O)-NHR 1A , -NH-C(=O)-R 1A , -N(R 1A )2, -Si(R 1A )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A is optionally replaced by

[0049] In some embodiments, R 1 At least one of is a halogen.

[0050] In some embodiments, R 1 At least one of the is cyano.

[0051] In some embodiments, R 1 At least one of -OR 1A It is.

[0052] In some embodiments, R 1 At least one of -SR 1A It is.

[0053] In some embodiments, R 1 At least one of the following is -C(=O)-R 1A It is.

[0054] In some embodiments, R 1 At least one of the following is -C(=O)-OR 1A It is.

[0055] In some embodiments, R 1 At least one of the following is -OC(=O)-R 1A It is.

[0056] In some embodiments, R 1 At least one of the following is -C(=O)-N(R 1A )2.

[0057] In some embodiments, R 1 At least one of the following is -C(=O)-NHR 1A It is.

[0058] In some embodiments, R1 At least one of the following is -NH-C(=O)-R 1A It is.

[0059] In some embodiments, R 1 At least one of -N(R 1A )2.

[0060] In some embodiments, R 1 At least one of -Si(R 1A )3.

[0061] In some embodiments, at least one R 1 is C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is one or more R 1A is optionally replaced by

[0062] In some embodiments, R 1 At least one of the following has an R of 1 or more: 1A C1 to C optionally substituted with 20 It is an alkyl.

[0063] In some embodiments, R 1 At least one of the following has an R of 1 or more: 1A C2 to C optionally substituted with 20 It is alkenyl.

[0064] In some embodiments, R 1At least one of the following has an R of 1 or more: 1A C2 to C optionally substituted with 20 It is alkynyl.

[0065] In some embodiments, R 1 At least one of the following has an R of 1 or more: 1A C3 to C optionally substituted with 20 It is cycloalkyl.

[0066] In some embodiments, R 1 At least one of the following has an R of 1 or more: 1A C6 to C optionally substituted with 20 Aryl (eg, phenyl).

[0067] In some embodiments, R 1 At least one of the following has an R of 1 or more: 1A is a 3- to 20-membered heterocycloalkyl optionally substituted with

[0068] In some embodiments, R 1 At least one of the following has an R of 1 or more: 1A is a 5- to 20-membered heteroaryl optionally substituted with

[0069] In some embodiments, at least two R 1 form bonds with the atoms to which they are attached, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A is optionally replaced by

[0070] In some embodiments, at least two R 1 form bonds with the atoms to which they are attached.

[0071] In some embodiments, at least two R 1 are C3 to C6 along with the atoms to which they are attached. 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A is optionally replaced by

[0072] In some embodiments, at least two R 1 are one or more R 1A C3 to C optionally substituted with 20 Forms a cycloalkyl.

[0073] In some embodiments, at least two R 1 are one or more R 1A C6 to C optionally substituted with 20 Forms an aryl (eg, phenyl).

[0074] In some embodiments, at least two R 1 are one or more R 1A and forming a 3- to 20-membered heterocycloalkyl ring optionally substituted with

[0075] In some embodiments, at least two R 1 are one or more R 1A and forming a 5- to 20-membered heteroaryl ring optionally substituted with Mutant R 1A

[0076] In some embodiments, at least one R 1A is hydrogen.

[0077] In some embodiments, at least one R 1A is halogen, cyano, -OR 1B , -SR 1B , -C(=O)-R 1B , -C(=O)-OR 1B , -OC(=O)-R 1B , -C(=O)-N(R 1B )2, -C(=O)-NHR 1B , -NH-C(=O)-R 1B , -N(R 1B )2, -Si(R 1B )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B is optionally replaced by

[0078] In some embodiments, at least one R 1A is a halogen.

[0079] In some embodiments, at least one R 1A is a cyano group.

[0080] In some embodiments, at least one R 1A -OR 1B It is.

[0081] In some embodiments, at least one R 1A -SR 1BIt is.

[0082] In some embodiments, at least one R 1A is -C(=O)-R 1B It is.

[0083] In some embodiments, at least one R 1A is -C(=O)-OR 1B It is.

[0084] In some embodiments, at least one R 1A is -OC(=O)-R 1B It is.

[0085] In some embodiments, at least one R 1A is -C(=O)-N(R 1B )2.

[0086] In some embodiments, at least one R 1A is -C(=O)-NHR 1B It is.

[0087] In some embodiments, at least one R 1A is -NH-C(=O)-R 1B It is.

[0088] In some embodiments, at least one R 1A is -N(R 1B )2.

[0089] In some embodiments, at least one R 1A is -Si(R 1B )3.

[0090] In some embodiments, at least one R 1A is C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B is optionally replaced by

[0091] In some embodiments, at least one R 1A is an R of 1 or more. 1B C1 to C optionally substituted with 20 It is an alkyl.

[0092] In some embodiments, at least one R 1A is an R of 1 or more. 1B C2 to C optionally substituted with 20 It is alkenyl.

[0093] In some embodiments, at least one R 1A is an R of 1 or more. 1B C2 to C optionally substituted with 20 It is alkynyl.

[0094] In some embodiments, at least one R 1A is an R of 1 or more. 1B C3 to C optionally substituted with 20 It is cycloalkyl.

[0095] In some embodiments, at least one R 1A is an R of 1 or more. 1B C6 to C optionally substituted with 20 Aryl (eg, phenyl).

[0096] In some embodiments, at least one R 1A is an R of 1 or more.1B is a 3- to 20-membered heterocycloalkyl optionally substituted with

[0097] In some embodiments, at least one R 1A is an R of 1 or more. 1B is a 5- to 20-membered heteroaryl optionally substituted with

[0098] In some embodiments, at least two R 1A are C3 to C6 along with the atoms to which they are attached. 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B is optionally replaced by

[0099] In some embodiments, at least two R 1 form bonds with the atoms to which they are attached.

[0100] In some embodiments, at least two R 1 are C3 to C6 along with the atoms to which they are attached. 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B is optionally replaced by

[0101] In some embodiments, at least two R 1A are one or more R 1B C3 to C optionally substituted with 20 Forms a cycloalkyl.

[0102] In some embodiments, at least two R 1A are one or more R 1B C6 to C optionally substituted with 20 Forms an aryl (eg, phenyl).

[0103] In some embodiments, at least two R 1A are one or more R 1B and forming a 3- to 20-membered heterocycloalkyl ring optionally substituted with

[0104] In some embodiments, at least two R 1A are one or more R 1B and forming a 5- to 20-membered heteroaryl ring optionally substituted with Mutant R 1B

[0105] In some embodiments, R 1B At least one of is a halogen.

[0106] In some embodiments, R 1B At least one of the is cyano.

[0107] In some embodiments, R 1B At least one of -OR 1C It is.

[0108] In some embodiments, R 1B At least one of -SR 1C It is.

[0109] In some embodiments, R 1B At least one of the following is -C(=O)-R 1C It is.

[0110] In some embodiments, R1B At least one of the following is -C(=O)-OR 1C It is.

[0111] In some embodiments, R 1B At least one of the following is -OC(=O)-R 1C It is.

[0112] In some embodiments, R 1B At least one of the following is -C(=O)-N(R 1C )2.

[0113] In some embodiments, R 1B At least one of the following is -C(=O)-NHR 1C It is.

[0114] In some embodiments, R 1B At least one of the following is -NH-C(=O)-R 1C It is.

[0115] In some embodiments, R 1B At least one of -N(R 1C )2.

[0116] In some embodiments, R 1B At least one of -Si(R 1C )3.

[0117] In some embodiments, R 1B At least one of C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1C is optionally replaced by

[0118] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C C1 to C optionally substituted with 20 It is an alkyl.

[0119] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C C2 to C optionally substituted with 20 It is alkenyl.

[0120] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C C2 to C optionally substituted with 20 It is alkynyl.

[0121] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C C3 to C optionally substituted with 20 It is cycloalkyl.

[0122] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C C6 to C optionally substituted with 20 Aryl (eg, phenyl).

[0123] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C is a 3- to 20-membered heterocycloalkyl optionally substituted with

[0124] In some embodiments, R 1B At least one of the following has an R of 1 or more: 1C is a 5- to 20-membered heteroaryl optionally substituted with Mutant R 1C

[0125] In some embodiments, R 1C At least one of is a halogen.

[0126] In some embodiments, R 1C At least one of the is cyano.

[0127] In some embodiments, R 1C At least one of -OR 1D It is.

[0128] In some embodiments, R 1C At least one of -SR 1D It is.

[0129] In some embodiments, R 1C At least one of the following is -C(=O)-R 1D It is.

[0130] In some embodiments, R 1C At least one of the following is -C(=O)-OR 1D It is.

[0131] In some embodiments, R 1C At least one of the following is -OC(=O)-R 1D It is.

[0132] In some embodiments, R 1C At least one of the following is -C(=O)-N(R 1D )2.

[0133] In some embodiments, R 1C At least one of the following is -C(=O)-NHR 1D It is.

[0134] In some embodiments, R 1C At least one of the following is -NH-C(=O)-R 1DIt is.

[0135] In some embodiments, R 1C At least one of -N(R 1D )2.

[0136] In some embodiments, R 1C At least one of -Si(R 1D )3.

[0137] In some embodiments, R 1C At least one of C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1D is optionally replaced by

[0138] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D C1 to C optionally substituted with 20 It is an alkyl.

[0139] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D C2 to C optionally substituted with 20 It is alkenyl.

[0140] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D C2 to C optionally substituted with 20It is alkynyl.

[0141] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D C3 to C optionally substituted with 20 It is cycloalkyl.

[0142] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D C6 to C optionally substituted with 20 Aryl (eg, phenyl).

[0143] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D is a 3- to 20-membered heterocycloalkyl optionally substituted with

[0144] In some embodiments, R 1C At least one of the following has an R of 1 or more: 1D is a 5- to 20-membered heteroaryl optionally substituted with Mutant R 1D

[0145] In some embodiments, R 1D At least one of is hydrogen.

[0146] In some embodiments, R 1D At least one of is halogen, cyano, -OH, -NH2, C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 It is aryl, a 3- to 20-membered heterocycloalkyl, or a 5- to 20-membered heteroaryl.

[0147] In some embodiments, R 1D At least one of is a halogen.

[0148] In some embodiments, R 1D At least one of the is cyano.

[0149] In some embodiments, R 1D At least one of is -OH.

[0150] In some embodiments, R 1D At least one of is -NH2.

[0151] In some embodiments, R 1D At least one of C1~C 20 It is an alkyl.

[0152] In some embodiments, R 1D At least one of C2~C 20 It is alkenyl.

[0153] In some embodiments, R 1D At least one of C2~C 20 It is alkynyl.

[0154] In some embodiments, R 1D At least one of the following is C3~C 20 It is cycloalkyl.

[0155] In some embodiments, R 1D At least one of the following is C6~C 20 Aryl (eg, phenyl).

[0156] In some embodiments, R 1D At least one of is a 3- to 20-membered heterocycloalkyl.

[0157] In some embodiments, R 1D At least one of is a 5- to 20-membered heteroaryl.

[0158] For the compound of formula (MI), X, R 1 , R 1A , R 1B , R 1C and R 1D may each be selected from the groups described herein, where applicable; X, R 1 , R 1A , R 1B , R 1C and R 1D Any group described herein for any of the remaining X, R 1 , R 1A , R 1B , R 1C and R 1D It is understood that one or more of the following may be combined with any group described herein. Exemplary ROMP Precursors

[0159] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0160] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0161] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0162] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0163] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0164] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0165] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0166] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof.

[0167] In some embodiments, the ROMP precursor is the following compound: [ka] or a salt thereof, wherein R 1F is H, halogen, cyano, -OH, NH2, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 alkynyl, R 1E teeth, [ka] or [ka] It is.

[0168] In some embodiments, the ROMP precursor is the following compound: [ka] or [ka] or a salt thereof, 1E is as described herein.

[0169] In some embodiments, the ROMP precursor is the following compound: [ka] or [ka] It is.

[0170] In some embodiments, the ROMP precursor is selected from the compounds set forth in Table 1 below, and salts thereof. [Table 1] JPEG2024519463000023.jpg219170JPEG2024519463000024.jpg224170JPEG2024519463000025.jpg219170JPEG2024 519463000026.jpg219170JPEG2024519463000027.jpg219170JPEG2024519463000028.jpg219170JPEG2024519463000 029.jpg219170JPEG2024519463000030.jpg214170JPEG2024519463000031.jpg219170JPEG2024519463000032.jpg219170JPEG2024519463000033.jpg219170JPEG2024519463000034.jpg224170JPEG2024519463000035.jpg219170Hardening catalyst

[0171] In some embodiments, the present disclosure provides a means for curing the compositions described herein. In some embodiments, the present disclosure provides a means for catalyzing ROMP. In some embodiments, the present disclosure provides a curing catalyst. In a preferred embodiment, the curing catalyst is a latent catalyst.

[0172] In some embodiments, the latent catalyst is a thermal latent catalyst, a photo latent catalyst, or a chemical latent catalyst.

[0173] In some embodiments, the curing catalyst is activated by radiation.

[0174] In some embodiments, the cure catalyst is UV activated.

[0175] In some embodiments, the cure catalyst is activated by elevated temperature.

[0176] In some embodiments, the curing catalyst is activated by an activator.

[0177] In some embodiments, the curing catalyst is a ruthenium catalyst.

[0178] In some embodiments, the cure catalyst is Grubbs' catalyst.

[0179] In some embodiments, the cure catalyst is a first generation Grubbs catalyst, a second generation Grubbs catalyst, or a third generation Grubbs catalyst.

[0180] In some embodiments, the latent Ru complex is a Grubbs-type catalyst. In some embodiments, the Grubbs-type catalyst comprises at least one of an N-heterocyclic carbene (NHC) or a cyclic (alkyl)(amino)carbene (CAAC) ligand. In some embodiments, the Ru complex comprises a 16-electron species.

[0181] The activated Ru complex may include at least one of an N-heterocyclic carbene (NHC) or a cyclic (alkyl) (amino) carbene (CAAC) ligand. The activated Ru complex may include one N-heterocyclic carbene (NHC) or a cyclic (alkyl) (amino) carbene (CAAC) ligand. The activated Ru complex may include a 14-electron species.

[0182] In some embodiments, the curing catalyst is a compound described in ACS Catal. 10(3):2033-2038, which is incorporated herein by reference.

[0183] In some embodiments, the curing catalyst is [ka] Or an isomer or a salt thereof.

[0184] In some embodiments, the curing catalyst is a compound described in U.S. Patent Application Publication No. 2020 / 0183276 and / or U.S. Patent Application Publication No. 2021 / 0163676A1, which are incorporated by reference herein.

[0185] In some embodiments, the curing catalyst is a compound of formula (CI): [ka] Or an isomer or a salt thereof. X 1 and X 2 is an independent anionic ligand; Y is O, NR 1 or S, preferably O; Q is -CR 11 R 12 -CR 13 R 14 -OR-CR 11 =CR 13 -, preferably -CR 11 R 12 -CR 13 R 14 - is a two-atom bond having the structure R 11 , R 12 , R 13 and R 14 is independently hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl, or a functional group; R 1 and R 2 may be linked to form independently hydrogen, an optionally substituted hydrocarbyl, an optionally substituted heteroatom-containing hydrocarbyl, or an optionally substituted cycloaliphatic group; R 3 and R 4 is independently optionally substituted hydrocarbyl, preferably optionally substituted adamantyl or substituted phenyl; R5 and R6 are independently hydrogen or an electron-withdrawing or electron-donating group; C 1-24 Alkyl, C 1-24 Alkoxy, C 1-24 Fluoroalkyl (including perfluoroalkyl), C 1-24 Fluoroalkoxy (including perfluoroalkoxy), C 1-24 Alkyl hydroxy, C1-24 Alkoxyhydroxy, C 1-24 Fluoroalkylhydroxy (including perfluoroalkylhydroxy), C 1-24 including fluoroalkoxyhydroxy (including perfluoroalkoxyhydroxy), halo (e.g., F, Cl, Br), cyano, nitro, hydroxyl, silyl, or phosphonyl; and m and n are independently 1, 2, 3 or 4.

[0186] In some embodiments, the curing catalyst is a compound [ka] Or an isomer or a salt thereof.

[0187] In some embodiments, the curing catalyst is [ka] or an isomer or a salt thereof.

[0188] In some embodiments, the curing catalyst is a compound described in U.S. Patent Application Publication No. 2020 / 0002466, which is incorporated herein by reference.

[0189] In some embodiments, the curing catalyst is a compound selected from the group consisting of: [ka] Or an isomer or a salt thereof. X is a halogen or an anionic ligand; Y is selected from the group consisting of O and S; Y' is OR9, SR9 or -N=CHC(O)O(C1-C6)alkyl, where R9 is methyl, ethyl, straight or branched (C1-C6)alkyl, (C6-C 10 )aryl, methoxy, ethoxy, straight or branched (C1-C6)alkoxy, (C6-C 10)aryloxy and -OCH(CH3)C(O)N(CH3)(OCH3); L is PR3 or O=PR3, and R is independently isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C5-C 10 ) selected from the group consisting of alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy; or X and L form a bidentate anionic ligand of formula XL; R7 is selected from the group consisting of isopropyl, sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl; R8 is methyl, ethyl, linear or branched (C1-C6) alkyl, (C6-C 10 )aryl, methoxy, ethoxy, straight or branched (C1-C6)alkoxy, (C6-C 10 )aryloxy, -NHCO(C1-C6)alkyl, -NHCO-perfluoro(C1-C6)alkyl, -SON((C1-C6)alkyl)2 and -NO2; Ar1, Ar2, Ar3 and Ar4 are the same or different and each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl; The substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl.

[0190] In some embodiments, the curing catalyst is [ka] (X=halogen, -OR a or -O(CO)R a -OSO2R a and R a (C1~C 12 ) Alkyl, (C3-C12 ) cycloalkyl or (C6-C 14 )aryl), [ka] (X is Cl or I, R 10 is hydrogen, NO2 or Cl), [ka] [ka] Or an isomer or a salt thereof.

[0191] In some embodiments, the curing catalyst is CATALYST 1: [ka] (Catalyst 1) (1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-((2-ethoxy-2-oxoethylidene)amino)benzylidene)ruthenium(II)), an isomer thereof, or a salt thereof. In some embodiments, the curing catalyst is catalyst 1. In further embodiments, catalyst 1 is commercially available from Apeiron Synthesis under the name HeatMet.

[0192] In some embodiments, the curing catalyst is catalyst 2: [ka] (dichloro(1,3-diisopropylphenylimidazolidin-2-ylidene{2-[(ethoxy-2-oxoethylidene)amino]benzylidene}ruthenium(II)), an isomer thereof, or a salt thereof. In some embodiments, the curing catalyst is Catalyst 2. In further embodiments, Catalyst 2 is commercially available from Apeiron Synthesis under the name HeatMetSIPr®.

[0193] In some embodiments, the curing catalyst is a catalyst described in US Pat. No. 9,610,572, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0194] In some embodiments, the cure catalyst is a compound of formula (CI). [ka] L 1 teeth, [ka] or [ka] and X 1 is a halogen, C 1-24 is an alkoxy or a thiol; X 2 is absent or halogen, C 1-24 is an alkoxy or a thiol; R 2 are each independently hydrogen, halogen, OH, C 1-24 Alkyl, C 1-24 Alkoxy, C 1-24 Fluoroalkyl, C 1-24 Fluoroalkoxy, C 1-24 Alkyl hydroxy, C 1-24 Alkoxyhydroxy, C 1-24 Fluoroalkylhydroxy, C 1-24 Fluoroalkoxyhydroxy, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, 5- to 20-membered heteroaryl, NO2, NR 8 R 9 , O.C.(O)R 10 , C(O)OR 10 , N.R. 11 C(O)R 10 , C(O)NR 11 R 10 , cyano, nitro, silyl or phosphonyl; R 3 is hydrogen, C 1-24 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, 5- to 20-membered heteroaryl, OC(O)R 12 , C(O)OR 12 , N.R. 13 C(O)R 12 or C(O)NR 12 R 13 and X 2 If does not exist, R 3 is attached to Ru via an oxy moiety (e.g., -O-); R 4 is hydrogen, C 1-24 Alkyl, C3-C 20 Cycloalkyl or C6-C 20 is aryl; R 5 are each independently C6 to C 20 aryl, said aryl being one or more R 14 may be optionally substituted with; R 6 are each independently 1-24 Alkyl or C6-C 20 aryl, wherein the alkyl or the aryl is one or more R 14 may be optionally substituted with; R 7 are each independently hydrogen or C 1-24 alkyl, said alkyl being one or more R 14 may be optionally substituted with; Adjacent R 6 and R 7 together with the carbon atom to which they are attached form a 3- to 20-membered heterocycloalkyl ring; and R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently hydrogen, C 1-24 Alkyl, C3-C20 Cycloalkyl or C6-C 20 It is aryl.

[0195] In some embodiments, X 2 is halogen, C 1-24 It is an alkoxy or a thiol.

[0196] In some embodiments, R 6 are each independently 1-24 Alkyl or C6-C 20 aryl, wherein the alkyl or the aryl is one or more R 14 Optionally replaced by R 7 are each independently hydrogen or C 1-24 alkyl, said alkyl being one or more R 14 may be optionally substituted with

[0197] In some embodiments, the curing catalyst is a compound of formula (C-II): [ka] or a salt thereof, 1 , X 1 , X 2 and R 2 is as described herein, and R 15 is hydrogen, C 1-24 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 It is aryl, a 3- to 20-membered heterocycloalkyl, or a 5- to 20-membered heteroaryl.

[0198] In some embodiments, the curing catalyst is [ka] or a salt thereof; R 15 are each independently 1-24 Alkyl or C6-C 20 It is aryl.

[0199] In some embodiments, the curing catalyst is [ka] or a salt thereof selected from the above curing catalysts, 15 is as described herein, and L2 is [ka] is selected from.

[0200] In some embodiments, the curing catalyst is a compound described in U.S. Patent Application Publication No. 2020 / 0002466, which is incorporated herein by reference.

[0201] In some embodiments, the curing catalyst is a compound selected from the group consisting of: [ka] [ka] [ka] or [ka] And L 1 , X 1 , X 2 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 14 is as described herein, and A 1 are each independently C6 to C 20 It is aryl.

[0202] For compounds of formula (CI) or (C-II), X 1 , X 2 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 11 , R 12 , R 13 , R 14 , L 1 , and A 1 may each be selected from the groups described herein, where applicable; X 1 , X 2 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 11 , R 12 , R 13 , R 14 , L 1 , and A 1 Any group described herein for any of the remaining X 1 , X 2 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 11 , R 12 , R 13 , R 14 , L 1 , and A 1 It is understood that one or more of the following may be combined with any group described herein.

[0203] In some embodiments, the curing catalyst is catalyst 1, catalyst 2, [ka] or a salt thereof.

[0204] In some embodiments, the cure catalyst is present in a formulation, build material, or kit described herein at a concentration of from about 1 molar ppm to about 1000 molar ppm or from about 100 molar ppm to about 800 molar ppm. Activator

[0205] In some embodiments, the activating agent is an acid.

[0206] In some embodiments, the activator is a photogenerated acid.

[0207] In some embodiments, the activator is a UV-activated acid.

[0208] In some embodiments, the activator is a precursor (eg, a latent precursor) of the acid.

[0209] In some embodiments, the activator releases an acid upon activation (eg, chemical activation or photoactivation).

[0210] In some embodiments, the activator is a compound described in U.S. Patent Application Publication No. 2019 / 0127517, which is incorporated herein by reference.

[0211] In some embodiments, the activator is trichloro(phenyl)silane, chlorophenylsilane, dichloro(phenyl)silane, dichloromethyl(phenyl)silane, chlorodimethylphenylsilane, chlorotrimethylsilane, butyl(chloro)dimethylsilane, chloro-decyl-dimethylsilane, chloro(chloromethyl)dimethyl, chloro(dichloromethyl)dimethylsilane, pentafluoropropionic acid, trifluoroacetic acid, trichloroacetic acid, trichlorodecylsilane (TCSA), trichloro(octadecyl)silane, dichlorodiphenylsilane, perfluorodecylmethylchlorosilane, or perfluorodecylmethyldichlorosilane.

[0212] In some embodiments, the activator is a compound described in U.S. Patent Application Publication No. 2020 / 0002466, which is incorporated herein by reference.

[0213] In some embodiments, the activator is a xanthone derivative.

[0214] In some embodiments, the activator is a compound of formula (AI): [ka] or a salt thereof, Y is a halogen and R 30 and R 31 are the same or different and independently represent hydrogen, methyl, ethyl, straight or branched chain (C3-C 12 ) Alkyl, (C3-C 12 )Cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) Tricycloalkyl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 )Cycloalkoxy, (C6-C 12 ) Bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl and (C6-C 10 )-aryloxy.

[0215] In some embodiments, the activator is [ka] or a salt thereof.

[0216] In some embodiments, the activator is [ka] In some embodiments, the activator is [ka] In some embodiments, the activator is [ka] isn't it.

[0217] In some embodiments, the activator is a triazine derivative.

[0218] In some embodiments, the activator is a compound of formula (A-II): [ka] or a salt thereof, R 32 , R 33 and R 34 are the same or different and independently represent halogen, methyl, ethyl, straight or branched chain (C3-C 12 ) alkyl, trihalomethyl, pentahaloethyl, straight or branched perhalo (C3-C 12 ) Alkyl, (C6-C 10 )Aryl, (C6-C 10 )Aryl(C1-C3)Alkyl, Perhalo(C6-C 10 )Aryl, perhalo(C6~C 10 )arylperhalo(C1-C3)alkyl, substituted or unsubstituted 5- or 6-membered heteroaryl(C2-C4)alkenyl or substituted or unsubstituted (C6-C 10 )aryl(C2-C4)alkenyl, where R 32 , R 33 and R 34 One of the following is trihalomethyl, pentahaloethyl or straight or branched chain perhalo (C3-C 12 ) alkyl.

[0219] In some embodiments, the activator is [ka] or a salt thereof. Antioxidants

[0220] In some embodiments, the formulation or build material further comprises an antioxidant. Antioxidants are classified as primary and secondary antioxidants depending on the method of preventing oxidation. Without wishing to be bound by a particular theory, primary antioxidants function by donating reactive hydrogen to peroxy free radicals to prevent the subsequent proliferation of free radicals. Antioxidant free radicals are stabilized by electron delocalization. Secondary antioxidants decompose hydroperoxides to generate non-reactive products, thereby preventing the proliferation of alkoxy and hydroxyl radicals and slowing down oxidation. These ingredients can be used in synergistic combinations with primary antioxidants.

[0221] Suitable antioxidants include, for example, organic phosphites such as tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylation reaction products of polyphenols such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane with dienes; butylation reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene bisphenols; benzyl compounds; β-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate); esters of β-(5-di-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as distearyl thiopropionate, dilauryl thiopropionate, ditridecyl thiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; amides, such as β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, or a formulation comprising at least one of the foregoing antioxidants.

[0222] In some embodiments, the primary antioxidant is selected from hindered phenols and secondary arylamines, or a combination thereof. In some embodiments, the hindered phenol is selected from butylated hydroxytoluene (BHT), triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl]propionate], 1,6-hexanediol bis ... )propionate], 2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene 3,5-di-tert-butyl-hydroxycinnamamide)methane, and octadecyl 3,5-di-tert-butyl hydroxyhydrocinnamamide.

[0223] In some embodiments, the secondary antioxidant is selected from organic phosphites, thioethers and thioesters, or combinations thereof. In some embodiments, the secondary antioxidant comprises one or more compounds selected from tetrakis(2,4-di-tert-butylphenyl)[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)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, and distearyl pentaerythritol diphosphite. In further aspects, the secondary antioxidant comprises tris(2,4-di-tert-butylphenyl)phosphite. Catalytic inhibitors

[0224] In some embodiments, the formulation or build material further comprises a catalyst inhibitor. As used herein, a "catalyst inhibitor" is a second chemical species that slows or stops the initiation or propagation of a catalyst. Catalyst inhibitors are suitable, for example, to prevent premature polymerization during preparation, purification, shipping, and storage of the formulation or build material. Suitable catalyst inhibitors include amines (e.g., alkylamines, such as triethylamine, diisopropylmethylamine), azaheterocycles (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene, DBN (1,5-diazabicyclo[4.3.0]non-5-ene), and DABCO (1,4-diazabicyclo[2.2.2]octane), phosphites (e.g., trialkyl phosphites, triaryl phosphites, and tribenzyl phosphites), pyridines (e.g., 4-dimethylaminopyridine), and organic superbases (e.g., amidine, guanidene, and phosphazene superbases). Optical strengthening component

[0225] In some embodiments, the formulations or build materials described herein are used in a method of manufacturing an object, during which the properties of the partially manufactured object are scanned, and the information obtained from the scan is used to correct the addition of further material so that the object matches the desired characteristics, e.g., in dimensions or composition. Such emitted light can be utilized in many different types of scanning techniques, including laser profilometry (e.g., using confocal or geometric approaches), structured light scanning (e.g., projection techniques using incoherent light), and the like.

[0226] In some embodiments, the formulation or build material described herein includes an optical enhancement component. In some embodiments, the build material is modified prior to use by incorporating an additive (e.g., an optical enhancement component) into the material that changes the properties of the optical emission during manufacture. For example, the additive may increase the scattering of light from the material and / or fluoresce when excited. The additive may be incorporated at the time of printing (as generally described below), but may also be incorporated at an earlier stage, for example, when preparing and storing the build material for use in later manufacture. Results of initial optical scans of 3D printed objects and optical enhancement components are described in WO2021 / 086392, the contents of which are incorporated herein by reference. Any of the scanning techniques described herein may be used to scan a partially manufactured object.

[0227] A wide variety of additives can be used, including small molecules, macromolecules, supramolecular aggregates, proteins, polymers, quantum dots, metallic nanoparticles (e.g. gold and silver nanoparticles, nanorods, nanoplates), non-metallic nanoparticles (e.g. silica, zeolites, mesoporous particles), pigments, and fine powder dispersions. Another alternative additive includes dyes that degrade at a known rate under UV light irradiation. Therefore, they are only visible in the most recently deposited layer. The intensity at each point can be used to extract a depth map of the newly deposited layer. When the successive layers are then exposed to UV light in the 3D printing process, the dyes degrade and are not visible when the product is in functional use. Another example is the use of OCT (Optical Coherence Tomography), which allows depth data to be obtained rather than just a surface map. In the case of OCT, additives are preferably coherent scatterers rather than fluorescent scatterers. Yet another method is to mix specific molecules in the manufacturing material and determine if polymerization has occurred completely. In this case, determining means evaluating whether the layer is fully cured or whether additional exposure to UV light is required. For example, the life science literature is filled with a number of fluorescent dyes that can be used to detect the presence of reactive oxygen species, e.g. unreacted monomers, or to determine the presence of other molecules. As an example, Thermo Fisher's catalog page provides a list of fluorescent dyes available for the detection of ROSs. In general, additives can be used to detect the state of polymerization of the material during printing, or whether unwanted by-products have been formed during UV light exposure. Such detection goes beyond completeness or geometric correctness, to determine whether the production process is proceeding correctly. Of course, it should be recognized that multiple additives can be formulated to provide different types of emission, for example, some related to the degree of curing, others used to determine the surface or body structure of the object being produced.

[0228] It is also possible to use pure absorption, where the amount of additive reduces the emission rather than producing a darkening reaction. Thus, a "brightener" can be broadly understood as a material that simply changes the detectable emission. Also, an emission that is not visible to the human eye (to maintain the desired color and transparency of the manufactured object) but is detectable by a detector may be desired, such as with molecules that absorb in the UV region and emit in the visible region, or gold nanorods that scatter only in the infrared region but are not visible to the human eye. Instead of adding different enhancers to the same material, a composite brightener can also be added. A composite brightener contains different molecules that act together to perform a specific function. For example, it is possible to carry fluorescent molecules within mesoporous silica nanoparticles with sizes between 10 and 500 nm. Flame retardants

[0229] In some embodiments, the compositions described herein may include a flame retardant. In some embodiments, the flame retardant may include an organophosphorus material including phosphates (triphenyl phosphate, ammonium polyphosphate), phosphonates (dimethyl methyl phosphonate), and / or phosphinates (diethyl phosphinate salts). In some embodiments, the flame retardant may include melamine (melamine, melamine cyanurate). In some embodiments, the flame retardant may include an organohalogen material such as chlorinated paraffins, chlorendic acid, organic bromine, debrominated diphenyl ether, brominated polystyrene, hexabromocyclododecane, and / or tetrabromobisphenol A. Other Ingredients

[0230] In some embodiments, the formulation or build material further comprises a stabilizer.

[0231] In some embodiments, the stabilizer is a thermal stabilizer (eg, one that stabilizes the formulation or build material at elevated temperatures).

[0232] In some embodiments, the stabilizer is 4-tert-butylcatechol (TBC), 4-methoxyphenol (MEHQ), butylated hydroxytoluene (BHT), hydroquinone (HQ), Irganox 1010, Irganox 245, Irganox 1076, Irgafos 126, Irgafos 168, or any combination thereof.

[0233] In some embodiments, the formulation or building material further comprises an impact modifier.

[0234] In some embodiments, the formulation or build material further comprises a pigment, dye, or a combination thereof.

[0235] In some embodiments, the formulation or build material further comprises a pigment.

[0236] In some embodiments, the pigment is an organic pigment, an inorganic pigment, or a combination thereof.

[0237] In some embodiments, the formulation or build material further comprises a dye.

[0238] In some embodiments, the dye is an organic dye, an inorganic dye, or a combination thereof.

[0239] It is noted that, without wishing to be bound by any particular theory, the pigment or dye can enable optical sensing (e.g., scanning) of the deposited material during printing. In some embodiments, the formulation or build material containing the pigment or dye is colored, thereby enabling optical sensing (e.g., scanning) of the deposited material by its color. In some embodiments, the formulation or build material containing the pigment or dye is colorless but fluorescent, thereby enabling optical sensing (e.g., scanning) of the deposited material by its fluorescence.

[0240] In some embodiments, the formulation or build material further comprises a surfactant, a filler, a pigment, a dispersant, or any combination thereof. Properties of the molding material

[0241] In some embodiments, the viscosity of the modeling material (e.g., at the spray temperature) is from about 1 cp to about 100 cp, from about 2 cp to about 80 cp, from about 3 cp to about 70 cp, from about 4 cp to about 60 cp, from about 5 cp to about 50 cp, from about 6 cp to about 40 cp, from about 7 cp to about 30 cp, or from about 8 cp to about 20 cp.

[0242] In some embodiments, the viscosity of the modeling material is about 1 cp to about 100 cp, about 2 cp to about 80 cp, about 3 cp to about 70 cp, about 4 cp to about 60 cp, about 5 cp to about 50 cp, about 6 cp to about 40 cp, about 7 cp to about 30 cp, or about 8 cp to about 20 cp when measured at about 20° C. to about 25° C., about 30° C. to about 35° C., about 40° C., about 45° C., about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 75° C., about 80° C., about 85° C., about 90° C., about 95° C., about 100° C., about 110° C., about 120° C., about 130° C., about 140° C., or about 150° C.

[0243] In some embodiments, the viscosity of the modeling material upon storage for 2 weeks (e.g., at the spray temperature) changes by about 10 cp or less, about 9 cp or less, about 8 cp or less, about 7 cp or less, about 6 cp or less, about 5 cp or less, about 4 cp or less, about 3 cp or less, about 2 cp or less, or about 1 cp or less.

[0244] In some embodiments, the viscosity of the build material changes by about 10 cp or less, about 9 cp or less, about 8 cp or less, about 7 cp or less, about 6 cp or less, about 5 cp or less, about 4 cp or less, about 3 cp or less, about 2 cp or less, or about 1 cp or less upon storage for 2 weeks at about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0245] In some embodiments, the hardened modeling material has a tensile strength of 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 65 MPa, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa, about 90 MPa, about 95 MPa, about 100 MPa, or any range therebetween.

[0246] In some embodiments, the elongation at break of the hardened building material is about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100%, about 105%, about 110%, about 115%, about 120%, about 125%, about 130%, or any range therebetween.

[0247] In some embodiments, the Young's modulus of the hardened build material is about 0.8 GPa, about 0.9 GPa, about 1.0 GPa, about 1.1 GPa, 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, about 2.6 GPa, about 2.7 GPa, about 2.8 GPa, about 2.9 GPa, about 3.0 GPa, or a range therebetween.

[0248] In some embodiments, the notched Izod impact strength of the cured build material is about 5 J / m, about 10 J / m, about 20 J / m, about 30 J / m, about 40 J / m, about 50 J / m, about 100 J / m, about 150 J / m, about 200 J / m, about 250 J / m, about 300 J / m, about 350 J / m, about 400 J / m, about 450 J / m, about 500 J / m, about 550 J / m, about 600 J / m, about 650 J / m, about 700 J / m, about 750 J / m, about 800 J / m, or a range therebetween. Build materials and hardening conditions

[0249] In some embodiments, the build material is deposited (eg, sprayed) under build material deposition conditions (eg, build material jetting conditions).

[0250] In some embodiments, the build material is cured under build material curing conditions.

[0251] In some embodiments, the build material is liquid under build material deposition conditions (eg, build material spray conditions).

[0252] In some embodiments, the build material is a wax.

[0253] In some embodiments, the melting point of the build material is at or below the temperature of the build material deposition conditions.

[0254] In some embodiments, upon deposition, the build material is transformed (eg, via a phase change) into a solid.

[0255] In some embodiments, upon deposition, the build material is converted to a solid upon cooling.

[0256] In some embodiments, upon deposition, the build material is converted to a solid by curing.

[0257] In some embodiments, the build material is UV curable.

[0258] In some embodiments, the build material is substantially stable (eg, chemically and / or physically) relative to the support material.

[0259] In some embodiments, the build material is substantially stable (eg, chemically and / or physically) under support material curing conditions.

[0260] In some embodiments, the build material is substantially stable (eg, chemically and / or physically) relative to the hardened support material.

[0261] In some embodiments, the curing catalyst, when activated, cures the build material and does not cure the support material.

[0262] In some embodiments, the build material curing conditions include irradiation (eg, with visible or UV light).

[0263] In some embodiments, the build material curing conditions include elevated temperature.

[0264] In some embodiments, the build material hardening conditions include chemical activation (eg, addition of water).

[0265] In some embodiments, the build material curing conditions are substantially free of air (eg, oxygen).

[0266] In some embodiments, the build material curing conditions are substantially free of water.

[0267] In some embodiments, the hardened build material is substantially stable (eg, chemically and / or physically) relative to the hardened support material.

[0268] In some embodiments, the hardened build material is substantially stable (eg, chemically and / or physically) under support material removal conditions.

[0269] In some embodiments, the build material comprises a polymer.

[0270] In some embodiments, the polymer is formed by ring-opening metathesis polymerization. Support Materials

[0271] In some embodiments, the support material is deposited (eg, sprayed) under support material deposition conditions (eg, support material spray conditions).

[0272] In some embodiments, the support material is cured under support material curing conditions.

[0273] In some embodiments, the support material or hardened support material is removed under support material removal conditions.

[0274] In some embodiments, the support material is liquid under support material deposition conditions (eg, support material spray conditions).

[0275] In some embodiments, the support material is a wax.

[0276] In some embodiments, the melting point of the support material is the same as or lower than the temperature of the support material deposition conditions.

[0277] In some embodiments, upon deposition, the support material is transformed into a solid (eg, via a phase change).

[0278] In some embodiments, upon deposition, the support material is converted to a solid upon cooling.

[0279] In some embodiments, upon deposition, the support material is converted to a solid by curing.

[0280] In some embodiments, the support material is UV curable.

[0281] In some embodiments, the support material is thermoset.

[0282] In some embodiments, the support material curing conditions include irradiation (eg, with visible light or UV).

[0283] In some embodiments, the support material curing conditions include elevated temperature.

[0284] In some embodiments, the support material curing conditions are substantially free of air (eg, oxygen).

[0285] In some embodiments, the support material curing conditions are substantially free of water.

[0286] In some embodiments, the hardened support material is substantially stable (eg, chemically and / or physically) relative to the build material.

[0287] In some embodiments, the hardened support material is substantially stable (eg, chemically and / or physically) under the build material hardening conditions.

[0288] In some embodiments, the hardened support material comprises a polymer.

[0289] In some embodiments, the support material removal conditions include the addition of a solvent, thereby dissolving the hardened support material.

[0290] In some embodiments, the support material removal conditions include mechanical removal of the hardened support material.

[0291] In some embodiments, the support material removal conditions include a transformation (eg, via a phase change) from a solid to a liquid. Use of formulations, materials, and kits

[0292] In some embodiments, the present disclosure provides a method of preparing a hardened material comprising subjecting a formulation, modeling material, or kit disclosed herein to hardening conditions.

[0293] In some embodiments, the present disclosure provides a formulation, modeling material, or kit as disclosed herein for use in preparing a cured material, said preparation comprising subjecting the formulation, modeling material, or kit to curing conditions.

[0294] In some embodiments, the present disclosure provides the use of a formulation, modeling material, or kit disclosed herein for use in the manufacture of a hardened material, said manufacture comprising a step of subjecting the formulation, modeling material, or kit to hardening conditions.

[0295] In some embodiments, the build material curing conditions include light irradiation (eg, with visible or UV light).

[0296] In some embodiments, the build material curing conditions include elevated temperature.

[0297] In some embodiments, the build material hardening conditions include chemical activation (eg, addition of water).

[0298] In some aspects, the present disclosure provides a cured material prepared by the methods described herein.

[0299] In some embodiments, the present disclosure provides methods of printing objects using the formulations, build materials, or kits disclosed herein.

[0300] In some embodiments, the present disclosure provides a formulation, build material, or kit as disclosed herein for use in printing an object.

[0301] In some embodiments, the printing comprises: (i) depositing (e.g., spraying) a build material described herein; (ii) subjecting the deposition modeling material to curing conditions.

[0302] In some embodiments, the printing comprises: (i) depositing (e.g., spraying) a first build material described herein and a second build material described herein; (ii) subjecting the deposited first and second build materials to curing conditions.

[0303] In some embodiments, the printing comprises: (i) depositing (e.g., spraying) a build material described herein onto a support material; (ii) subjecting the deposited build material to curing conditions.

[0304] In some embodiments, the printing comprises: (i) depositing (e.g., spraying) a first build material described herein and a second build material described herein onto a support material; (ii) subjecting the deposited first and second build materials to curing conditions.

[0305] In some embodiments, the printing further comprises repeating the step of depositing the material one or more times.

[0306] In some embodiments, the printing optionally further comprises optically sensing the deposited material and controlling one or more repeated depositions of the material according to the sensing.

[0307] In some embodiments, any sensing of the deposited material is performed when at least a portion of the material has hardened.

[0308] In some embodiments, each repetition of deposition of the material is performed when at least a portion of a previously deposited layer of the material has been cured.

[0309] In some embodiments, the printing further comprises depositing an agent that enhances one or more of the mechanical, thermal, and / or optical properties of the material.

[0310] In some embodiments, sensing the deposited material includes capturing a surface of the object to be printed.

[0311] In some embodiments, sensing the deposited material includes capturing volumetric and / or tomographic data of the printed object.

[0312] In some embodiments, controlling the deposition of the one or more repetitions of material includes modifying the deposition of the one or more repetitions of material according to data generated by the sensing using an active feedback loop.

[0313] In some embodiments, control of the deposition of one or more repeats of the material is based on measurements of the surface of the object being printed.

[0314] In some embodiments, control of one or more repeated depositions of the material is based on measurements of volumetric and / or tomographic data of the object being printed.

[0315] In some embodiments, the printing further comprises heating the material, thereby facilitating hardening of the material. Use of formulations, materials, and kits

[0316] In some embodiments, the present disclosure provides a system for 3D printing, the system comprising: (i) a printer (e.g., an inkjet printer); and (ii) an ink comprising the formulation disclosed herein.

[0317] In some embodiments, a printer (e.g., an inkjet printer) includes one or more printer jets; an optical feedback scanner; and a controller that controls the ejection of ink from the one or more printer jets according to optical feedback of the jetted ink.

[0318] In some embodiments, the printer (eg, an inkjet printer) further includes a filled printhead (eg, a printhead filled with ink).

[0319] In some embodiments, the system further includes a light source (eg, a UV lamp or a visible light lamp) for curing the deposited layer of ink.

[0320] In some embodiments, the system further includes software comprising instructions stored on a non-transitory machine-readable medium, execution of the instructions controlling one or more of the printing processes described herein.

[0321] The following description relates to an example of a system for additive manufacturing, using, for example, a jet-based 3D printer 100 as shown in FIG. 1. The printer 100 uses jets 120 (inkjets) that emit material for deposition onto a partially manufactured object layer. In the printer shown in FIG. 1, the object is manufactured on a manufacturing area, which is controlled to move relative to the jets in a raster-like pattern to form successive layers, and in this example is also controlled to move relative to the ink jets to maintain a desired separation between the ink jets and the surface of the partially manufactured object. As shown, there are multiple jets 122, 124, where one jet 122 is used to emit support material to form the support structure 142 of the object, and another jet 124 is used to emit build material to form the object 144 itself. For materials where curing is initiated by an excitation light such as ultraviolet radiation, a curing signal generator 170 (e.g., a UV lamp) initiates the curing of the material immediately after it is jetted onto the object. In other embodiments, multiple different materials can be used, e.g., a separate jet can be used for each material. In still other embodiments, curing is initiated chemically, for example by mixing multiple components prior to jetting, or by jetting separate components that are mixed on the object and initiate curing. Note that in some examples, after deposition of the additive is complete, the object may be subjected to further curing (e.g., complete curing), for example, by further exposing the object to UV radiation.

[0322] The sensor 160 is used to determine physical properties of the partially fabricated object, including one or more of surface shape (e.g., a depth map characterizing the thickness / depth of the partially fabricated object), near-surface (e.g., near-surface consisting of tens or hundreds of deposited layers) properties. Properties that can be sensed can include one or more of material density, material identity, and cure state. Various types of sensing can be used, such as triangulation scanning / profilometry, time-of-flight imaging (pulse-based and phase-shift based techniques), active stereo / multi-baseline stereo / structured light, active depth from focus / defocus, optical interferometry, optical coherence tomography, shape from polarization, shape from heating, optical coherence tomography (OCT), laser profilometry, and / or multispectral light sensing that can be used to distinguish different materials. In the illustrated printer, the sensor outputs light that can cause emission (e.g., fluorescence) and / or reflection, scattering, absorption from or in the object. The light output from the sensor may be provided from the top of the object (i.e., the most recently deposited portion), although in some embodiments the sensor output signal may be provided from the bottom of the object or from other directions.

[0323] In precision additive manufacturing using inkjet technology, optical scanning feedback has been introduced to employ deposition of material to achieve precise object structures without the need for the mechanical approaches used previously. For example, such optical feedback techniques are described in U.S. Pat. Nos. 10,252,466 and 10,456,984 (incorporated by reference). However, optical feedback printers have not become a widespread commercial approach to 3D printing, likely due to the relative simplicity of the mechanical approach of using equipment with fast-setting inks, rather than the accuracy achievable with optical feedback. Furthermore, many manufacturing materials suitable for jet additive manufacturing are not directly suitable for optical scanning, as the propagation of optical signal strength from the material during scanning may be insufficient. For example, the material may be inherently substantially transparent and may not reflect the incident light adequately to obtain precise properties of the object being manufactured. However, the ability to scan the deposited material can be enhanced by the appropriate incorporation of optical enhancing components into the manufacturing material. Suitable optical enhancing components are described in detail in PCT Application No. PCT / US2019 / 59300 (incorporated by reference herein).

[0324] By not requiring contact to control the surface shape of the manufactured object, this approach is tolerant of the relatively slow curing of the composition (e.g., when compared to acrylate compositions typically used in inkjet 3D printing), thus allowing the advantage of controlling the deposition process according to feedback during the manufacturing process. This technique provides a method for manufacturing precision objects, and offers advantages over the material properties of the manufactured object, such as isotropic properties due to at least partial slow curing of the material, and flexible structures that cannot be achieved using conventional jetted acrylates. Furthermore, in cases where continued curing after scanning may change the shape of the part, for example, due to shrinkage, predictive techniques (e.g., machine learning approaches, as described in PCT Application No. PCT / US2019 / 59567, incorporated herein by reference) can be used in the control process to predict such changes, and the cationic composition can be further used in the precision jetting manufacturing approach.

[0325] The controller 110 uses a model 190 of the object to be fabricated to control the movement of the fabrication region 130 using movable actuators 150 (e.g., providing degrees of freedom) and to control the emission of material from jets 120 according to non-contact feedback of characteristics of the object determined via sensors 160. The feedback arrangement can be used to fabricate precise objects, for example, by compensating for inherently unpredictable aspects of jetting (e.g., clogging of the jet orifice) and unpredictable material changes after deposition, including flow, mixing, absorption, and hardening of the jetted material.

[0326] It should be understood that the printer shown in Figure 1 is merely exemplary and not limiting. Other printer arrangements that can be used are described, for example, in U.S. Pat. No. 10,252,466, U.S. Pat. No. 10,456,984, U.S. Patent Application Publication No. 2018 / 0056582, and Sitthi-Amorn et al. (ACM Transactions on Graphics 34(4): 129 (2015)).

[0327] In an alternative manufacturing process known as "delayed cure" 3D printing, the build material of an object part undergoes two distinct mechanisms during an additive manufacturing stage and a subsequent or overlapping part curing stage: a phase change mechanism and a polymerization mechanism. Aspects, systems, and methods of delayed cure 3D printing are described in U.S. Patent Publication No. 2022-0088850, the contents of which are incorporated herein in their entirety for all purposes.

[0328] Phase change mechanisms occur during the additive manufacturing stage and cause the build material to change phase from liquid to non-liquid (e.g., at least partially solid, semi-solid, and / or quasi-solid), but the phase change is not typically due to polymerization, and the non-liquid build material has solidified sufficiently to allow for subsequent incremental deposition of material (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, e.g., preventing intermixing of the build material with the support material).

[0329] The polymerization mechanism occurs after additive manufacturing of the object in a curing stage, or after at least a portion of said additive manufacturing has taken place. This mechanism hardens the build material by a polymerization process. In some examples, the polymerization mechanism is initiated after additive manufacturing of the object is complete. In other examples, the polymerization mechanism is initiated before addition of the ingredients of the production is complete, for example, during the phase change mechanism (e.g., both mechanisms are initiated simultaneously, or the polymerization mechanism is initiated during the phase change mechanism).

[0330] After the build material has cured (e.g., polymerized) sufficiently during the curing stage to allow removal of the mold, the manufacturing process enters a part removal stage in which the mold is removed. Once the mold is removed, the manufactured part is obtained.

[0331] With reference to Figure 2, this alternative manufacturing process uses a jet-based 3D printer 200 as shown in Figure 2. Very generally, the manufacturing process includes three time phases: an additive manufacturing phase, a part curing phase, and a part removal phase. As will be described in more detail below, in some examples, the part curing phase occurs entirely after the additive manufacturing phase. In other examples, the additive manufacturing phase and the part curing phase overlap.

[0332] In the additive manufacturing stage, additive manufacturing is used to produce an object 204 that includes a solid (e.g., hardened) mold structure 211 that forms a cavity (e.g., a closed structure or an open container) that defines the shape of part 212, and the cavity is filled with a semi-solid, uncured or partially cured material in the shape of part 212. The solid mold structure 211 and / or the semi-solid material are added layer by layer to form object 204.

[0333] During a part curing stage, which occurs at least in part at a time after completion of the additive manufacturing stage, the object 204 including the filled mold structure 211 is subjected to a curing process to polymerize the material within the cavities.

[0334] During the additive manufacturing and part curing stages, the material used to form part 212 (sometimes referred to as the "build material") undergoes two different mechanisms: a phase change mechanism and a polymerization mechanism.

[0335] Phase change mechanisms occur during the additive manufacturing stage and cause the build material to change phase from liquid to non-liquid (e.g., at least partially solid, semi-solid, and / or quasi-solid, the three terms may be used interchangeably herein) that has solidified sufficiently to subsequently deposit material incrementally (e.g., the non-liquid build material can support the weight or force of incrementally added material).

[0336] The polymerization mechanism occurs after additive manufacturing of the object 204 in a hardening stage, or after at least a portion of said additive manufacturing has taken place. This mechanism hardens the build material by a polymerization process. In some examples, the polymerization mechanism is initiated after additive manufacturing of the object is complete. In other examples, the polymerization mechanism is initiated before addition of the ingredients of the fabrication is complete, for example, during the phase change mechanism (e.g., both mechanisms are initiated simultaneously, or the polymerization mechanism is initiated during the phase change mechanism).

[0337] In the part removal step, the solid mold structure 211 is removed, resulting in a part 212. In some examples, the part removal step occurs after the part curing step, but in other examples, the part removal step may be simultaneous with the part curing step (e.g., the part 212 is still curing, but has cured sufficiently to be removed from the solid mold structure 211). Printer

[0338] In the additive manufacturing stage, a printer 200 uses jets 202 (inkjets) to emit material for deposition of layers that form an object 204 (shown partially fabricated in FIG. 2). In the printer shown in FIG. 2, the object 204 is fabricated on a build platform 206 that is controlled to move relative to the jets in a raster-like pattern (i.e., along the xy plane) to form successive layers, and in this example moves relative to the jets (i.e., along the z-axis) to maintain a desired separation between the jets and the surface of the partially fabricated object 204.

[0339] As shown, there are multiple jets 208, 210, for example, a first jet 208 is used to emit 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 is used to emit build material 214 to form an uncured or partially cured semi-solid (e.g., gel or wax) part 212 of the object 204. The properties of the mold material 213 and build material 214 are described in more detail below.

[0340] A sensor 216 (sometimes called a scanner) is positioned relative to (e.g., above) the object under fabrication 204 and is used to determine physical properties of the partially fabricated object. For example, the sensor 216 measures one or more of the surface profile (e.g., a depth map characterizing the thickness / depth of the partially fabricated object) and near-surface properties (e.g., near-surface properties of tens or hundreds of deposited layers). Properties that can be sensed can include one or more of material density, material identity, and cure state. Most commonly, the measurements by 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 the height axis (i.e., as the object grows as it is built).

[0341] In some examples, in the context of a digital feedback loop for additive manufacturing, an additive manufacturing system builds an object by printing layers. The sensor 216 captures 3D scan information after the printer 200 prints one or more layers. For example, the sensor 216 scans the partial object (or an empty build platform), and then the printer prints a layer of material. The sensor 216 then scans the (partially built) object again. The new depth sensed by the sensor 216 should be approximately the initial depth minus the layer thickness (this implies that the sensor 216 is placed on top of the object being built, the object is built from the bottom layer to the top layer, and the distance between the sensor 216 and the build platform does not change). Various types of sensing, such as optical coherence tomography (OCT) and laser profilometry, can be used to determine depth and volume information related to the object being manufactured.

[0342] The controller 218 uses a model 220 of the object to be manufactured to control the movement of the build platform 206 using movable actuators 222 (e.g., providing degrees of freedom) and controls the ejection of material by the jets 202 according to non-contact feedback of characteristics of the object determined via the sensors 216. definition

[0343] Unless otherwise stated, the following terms used in the specification and claims have the meanings given below.

[0344] The articles "a" and "an" are used in this disclosure to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, "an element" means one element, at least one element, or two or more elements.

[0345] As used herein, the term "ring-opening metathesis polymerization" or "ROMP" refers to a form of chain-growth polymerization in which the ends of polymer chains react repeatedly with cyclic alkene monomers by olefin metathesis to form longer polymers.

[0346] As used herein, the term "curing" refers to a process of transforming a material by polymer formation and / or linking of pre-existing polymers in the material, thereby producing a cured material. In some embodiments, the transformation is initiated by irradiation (e.g., UV or visible light), elevated temperature, or an activator. In some embodiments, the transformation is initiated by irradiation (e.g., UV or visible light).

[0347] As used herein, the term "about" refers to a range that includes normal variations that would be understood by a person skilled in the relevant art. In some embodiments, the term "about" refers to a range of values ​​that falls 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 any direction (greater or less) of the stated reference value, unless otherwise stated or clear from the context (except where such numerical value exceeds 100% of the possible values).

[0348] As used herein, the term "derivative" refers to a compound that has a common core structure and / or shares one or more properties with a reference compound. In some embodiments, a derivative is substituted with various groups as described herein as compared to the reference compound.

[0349] Without wishing to be limited by this description, it is understood that although various options for the variables are described herein, the present disclosure is intended to encompass workable embodiments having combinations of the options, and the present disclosure may be interpreted as excluding inoperable embodiments caused by certain combinations of the options.

[0350] As used herein, "alkyl", "C1, C2, C3, C4, C5 or C6 alkyl" or "C1-C6 alkyl" is intended to include C1, C2, C3, C4, C5 or C6 straight chain saturated aliphatic hydrocarbon groups and C3, C4, C5 or C6 branched chain saturated aliphatic hydrocarbon groups. For example, C1-C6 alkyl is intended to include C1, C2, C3, C4, C5 and C6 alkyl groups. Alkyl includes, but is not limited to, groups having 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, and the like. In some embodiments, a straight or branched chain alkyl has 6 or fewer carbon atoms (e.g., C1-C6 for straight chain, C3-C6 for branched chain), and in other embodiments, a straight or branched chain alkyl has 4 or fewer carbon atoms.

[0351] As used herein, the term "optionally substituted alkyl" refers to an unsubstituted alkyl or an alkyl having specified substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents include, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinate, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or aromatic or heteroaromatic groups.

[0352] As used herein, the term "alkenyl" includes unsaturated aliphatic groups similar in length and possible substitution to the alkyls described above, but containing 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 chain alkenyl groups. In certain embodiments, a straight or branched chain 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 2-6 carbon atoms. The term "C3-C6" includes alkenyl groups containing 3-6 carbon atoms.

[0353] As used herein, the term "optionally substituted alkenyl" refers to an unsubstituted alkenyl or an alkenyl having specified substituents replacing one or more hydrogen atoms on one or more carbon atoms of the hydrocarbon backbone. Such substituents include, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinate, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, heterocyclyl, alkylaryl, or aromatic or heteroaromatic groups.

[0354] 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 chain alkynyl groups. In certain embodiments, a straight or branched chain 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 2-6 carbon atoms. The term "C3-C6" includes alkynyl groups containing 3-6 carbon atoms. As used herein, a "C2-C6 alkenylene linker" or "C2-C6 alkynylene linker" is intended to include a C2, C3, C4, C5 or C6 chain (straight or branched) divalent unsaturated aliphatic hydrocarbon group. For example, a C2-C6 alkenylene linker is intended to include C2, C3, C4, C5 and C6 alkenylene linker groups.

[0355] As used herein, the term "optionally substituted alkynyl" refers to an unsubstituted alkynyl or an alkynyl having specified substituents replacing one or more hydrogen atoms on one or more carbon atoms of the hydrocarbon backbone. Such substituents include, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinate, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or aromatic or heteroaromatic groups.

[0356] As used herein, the term "cycloalkyl" refers to an alkyl group having 3 to 30 carbon atoms (e.g., C 12 , C3~C 10 , or C3-C8) saturated or partially unsaturated hydrocarbon monocyclic or polycyclic (e.g., fused, bridged, or spirocyclic) systems. Cycloalkyls 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 a polycyclic cycloalkyl, only one of the rings of the cycloalkyl need be non-aromatic.

[0357] As used herein, the term "heterocycloalkyl," unless otherwise specified, refers to a saturated or partially unsaturated 3-8 membered monocyclic, 7-12 membered bicyclic (fused, bridged, or spiro) or 11-14 membered tricyclic ring system (fused, bridged, or spiro) having one or more heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur (e.g., O, N, S, P, or Se), e.g., 1, 1-2, 1-3, 1-4, 1-5, or 1-6 heteroatoms, or e.g., 1, 2, 3, 4, 5, or 6 heteroatoms.Heterocycloalkyl groups include 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-oxazepamyl, 1,4-oxazepamyl, 1,2,3,6-tetrahydropyridinyl, tetrahydropyranyl, dihydropyranyl, pyranyl, morpholinyl, tetrahydrothiopyranyl, 1,4-diazepam ... 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, 1,4-dioxa-8-azaspiro[4.5]decanyl, 1,4-dioxaspiro[4.5]decanyl, 1-oxaspiro[4.5]decanyl, 1-azaspiro[4.5]decanyl, 3'H-spiro[cyclohexane-1,1'-isobenzofuran]-yl, 7'H-spiro[cyclohexa 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-1H-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 polycyclic heterocycloalkyls, only one of the rings of the heterocycloalkyl need be non-aromatic (e.g., 4,5,6,7-tetrahydrobenzo[c]isoxazolyl).

[0358] As used herein, the term "aryl" includes groups having aromaticity, including "conjugated" or polycyclic systems, that have one or more aromatic rings and do not contain any heteroatoms in the ring structure. The term aryl includes both monovalent and divalent species. Aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, and the like. Preferably, the aryl is phenyl.

[0359] As used herein, the term "heteroaryl" is intended to include stable 5-, 6-, or 7-membered monocyclic or 7-, 8-, 9-, 10-, 11-, or 12-membered bicyclic aromatic heterocycles consisting of carbon atoms and one or more heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, e.g., 1, 1-2, 1-3, 1-4, 1-5, or 1-6 heteroatoms, or, e.g., 1, 2, 3, 4, 5, or 6 heteroatoms. The nitrogen atom may be substituted or unsubstituted (i.e., N or NR, where R is hydrogen or other substituents as defined). The nitrogen and sulfur heteroatoms may be optionally oxidized (i.e., N→O and S(O)p, where p=1 or 2). It should be noted that the total number of S and O atoms in the aromatic heterocycle does not exceed 1. 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 that are not aromatic to form polycyclic systems (e.g., 4,5,6,7-tetrahydrobenzo[c]isoxazolyl). In some embodiments, heteroaryl is thiophenyl or benzothiophenyl. In some embodiments, heteroaryl is thiophenyl. In some embodiments, heteroaryl is benzothiophenyl.

[0360] Furthermore, the terms "aryl" and "heteroaryl" include polycyclic aryl and heteroaryl groups, e.g., tricyclic, bicyclic, such as naphthalene, benzoxazole, benzodioxazole, benzothiazole, benzimidazole, benzothiophene, quinoline, isoquinoline, naphthyridine, indole, benzofuran, purine, benzofuran, deazapurine, indolizine.

[0361] A cycloalkyl, heterocycloalkyl, aryl, or heteroaryl ring may have at one or more ring positions (e.g., a ring-forming carbon or a heteroatom such as N) a substituent 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, amine, aryloxycarbonyl ... The aryl and heteroaryl groups may be substituted with aryl, alkyl, aryl, aryl, alkyl, aryl, alkyl, aryl, alkyl, alkylamino, alkylcarbonyl, alkylthio ...

[0362] As used herein, the term "substituted" means that any one or more hydrogen atoms on the specified atom are replaced with one selected from among the indicated groups, provided that the normal valence of the specified atom is not exceeded and that the replacement results in a stable compound. If the substituent is oxo or keto (i.e., =O), two hydrogen atoms on the atom are replaced. Keto substituents do not occur on aromatic groups. Ring double bonds, as used herein, are double bonds formed between two adjacent ring atoms (e.g., C=C, C=N, or N=N). "Stable compound" and "stable structure" are intended to indicate a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mix and formulation into an effective polymeric material.

[0363] As used herein, the term "inert" refers to a functional group that is chemically unreactive, i.e., does not react with other moieties or reagents. Those skilled in the art will appreciate that the term "inert" does not exclude the presence of functional groups per se, but that functional groups potentially present in the inert group will not be reactive, e.g., in a subsequent reaction, with functional groups of moieties / reagents that come into contact with the inert group.

[0364] As used herein, the term "inert atmosphere" refers to an environment that is substantially free of oxygen and is composed primarily of non-reactive gases. Exemplary inert atmospheres include a nitrogen atmosphere or an argon atmosphere.

[0365] As used herein, the term "inert solvent" refers to a solvent that cannot participate in or inhibit the polymerization reaction disclosed herein. Those skilled in the art will recognize that in the context of the materials and methods disclosed herein, an inert solvent can be a solvent that does not contain any of the functional groups identified herein as catalyst inhibitors. Exemplary inert solvents include non-polar solvents such as hexane, toluene, diphenyl ether, chloroform, ethyl acetate, THF, dichloromethane, etc.; polar aprotic solvents such as acetonitrile, acetone, dichlorobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, etc.; polar protic solvents such as lower alcohols, water, etc. Those skilled in the art will recognize that the state of "inert" as applied to a solvent depends on the particular compound dissolved therein, and can readily ascertain by conventional means whether a given solvent is appropriately inert under the circumstances.

[0366] When a bond to a substituent is shown to cross a bond connecting two atoms in a ring, such substituent may be bonded to any atom in the ring. When such substituents are listed without indicating the atom through which they are bonded to the remainder of the compound shown in a given formula, such substituents may be bonded through any atom in such formula. Compounds of substituents and / or variables are permissible only if such compounds result in stable compounds.

[0367] 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 functional groups R, the moiety may be substituted with up to 2 functional groups R, with R at each occurrence being independently selected from the definitions of R. Additionally, combinations of substituents and / or variables are permissible, but only if such compounds result in stable compounds.

[0368] As used herein, the term "hydroxy" or "hydroxyl" includes groups with an --OH or --O--.

[0369] As used herein, the term "halo" or "halogen" refers to fluoro, chloro, bromo and iodo.

[0370] As used herein, the term "alkoxy" or "alkoxyl" includes substituted and unsubstituted alkyl, alkenyl, and alkynyl groups covalently bonded to an oxygen atom. Alkoxy groups or radicals include, but are not limited to, methoxy, ethoxy, isopropyloxy, propoxy, butoxy, and pentoxy groups. Substituted alkoxy groups include halogenated alkoxy groups. The alkoxy group may be substituted with groups such as alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinate, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or aromatic or heteroaromatic groups. Halogen substituted alkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, and trichloromethoxy.

[0371] As used herein, a "latent catalyst" refers to a compound that exhibits little catalytic activity under certain conditions (e.g., conditions present before printing) and begins to exhibit its activity upon activation (e.g., under curing conditions). Latent catalysts can be activated by a variety of conditions, including but not limited to, acid and radical activation. As used herein, the term "latent ruthenium complex" refers to an organoruthenium compound that is a latent catalyst.

[0372] As used herein, phrases such as "one or more of A, B or C", "one or more of A, B or C", "one or more of A, B and C", "of one or more of A, B and C", "selected from the group consisting of A, B and C", "selected from A, B and C" are used interchangeably and all of these phrases, unless otherwise indicated, refer to a selection from the group consisting of A, B and / or C, i.e., one or more A, one or more B, one or more C or any combination thereof.

[0373] As used herein, the term "pigment" refers to a colored, black, white, or fluorescent particulate organic or inorganic solid. In some embodiments, the pigment is insoluble in the vehicle or substrate in which it is incorporated and is essentially physically and chemically unaffected. In some embodiments, the pigment changes appearance by selective absorption and / or scattering of light. In some embodiments, the pigment is dispersed in a vehicle or substrate for application, such as in the manufacture of an ink or other polymeric material. In some embodiments, the pigment retains its crystalline or particle structure throughout the coloring process.

[0374] As used herein, the term "dye" refers to a substance that is highly colored by selective absorption of light, or that is organic and fluoresces, thereby imparting color to a substrate. In some embodiments, the dye is soluble and / or undergoes a process according to the present disclosure that disrupts, at least temporarily, any crystalline structure by absorption, solution, mechanical retention, or ionic or covalent chemical bonding.

[0375] As used herein, the term "viscosity" refers to the ability of a composition (e.g., a formulation of the present disclosure) to resist deformation at a given rate. In some embodiments, viscosity refers to the viscosity measured at the indicated temperature (25°C unless otherwise indicated) at a shear rate of 100.0hz on a TA Instrument Discovery HR-2 configured with 25mm parallel plate UHP steel.

[0376] As used herein, the term "elongation at break" refers to the ratio of the elongated length to the initial length after a test specimen is broken at a controlled temperature. In some embodiments, the elongation at break is measured by ASTM D412, ASTM D624, or ASTM D638.

[0377] As used herein, the term "Young's modulus" refers to a mechanical property that measures the stiffness of a solid material. Young's modulus relates to the relationship between stress (force per unit area) and strain (proportional deformation) of a material in the linear elastic region of uniaxial deformation. In some embodiments, Young's modulus is measured by ASTM D412, ASTM D624, or ASTM D638.

[0378] 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, notched Izod impact strength is measured by a method in which a pivoting arm is raised to a certain height (a certain potential energy) and then released. The arm is swung down to strike a notched sample, which breaks the sample. The energy absorbed by the sample is calculated from the height of the swing of the arm after striking the sample. Notched samples are commonly used to measure impact energy and notch sensitivity. Notched Izod impact strength is related to the energy lost per unit thickness (e.g., J / cm) at the notch. In some embodiments, notched Izod impact strength is measured by ASTM D256.

[0379] As used herein, the term "gelling agent" refers to a composition that, when dissolved, suspended or dispersed in a fluid (e.g., a support material or a modeling material described herein), forms a gelled semi-solid under certain conditions, e.g., at a certain temperature. In some embodiments, the gelling agent, when dissolved, suspended or dispersed in a fluid, forms a gelled semi-solid at room temperature. In some embodiments, the gelling agent, when dissolved, suspended or dispersed in a fluid, does not form a gelled semi-solid at elevated temperatures (e.g., above room temperature, e.g., between about 35°C and about 100°C). Gelling agents include, but are not limited to, waxes, silicas (e.g., fumed silica), and other rheology modifiers (e.g., polymers, e.g., Rheobyk D410®). As used herein, any gelling agent described herein may be used to convert (e.g., reversibly convert) the formulations and / or modeling materials described herein to solids and / or semi-solids.

[0380] As used herein, the term "wax" includes natural waxes, chemically modified waxes, and synthetic waxes. Natural waxes include vegetable waxes such as montan wax, animal waxes such as beeswax, mineral waxes, petrochemical waxes such as petrolatum, paraffin wax, and microwax. Chemically modified waxes include hard waxes such as montan ester wax. Synthetic waxes include, inter alia, alkane waxes, such as wax alcohols, particularly preferably water-insoluble fatty alcohols of high molecular weight having 12 or more carbon atoms, such as lignoceryl alcohol, ceryl alcohol, myricyl alcohol, melissyl alcohol, polyalkylene oxides such as polyethylene oxide, poly-THF, polyvinyl ether waxes, polyolefin waxes, oxidized polyolefin waxes, and the like.

[0381] The term wax also includes high molecular weight fatty acids, preferably those having at least 9 carbon atoms, such as behenic acid, tetracosanoic acid and cerotic acid, which can be optionally esterified with alcohols, and high molecular weight polyesters with a molecular weight of more than 1000 g / mol, preferably more than 1500 g / mol, obtained by reacting di- or polycarboxylic acids having 2 to 20 carbon atoms with di- or polyalcohols having 2 to 30 carbon atoms, the corresponding acids or alcohols being capable of containing aliphatic and / or aromatic structural units. Mixtures of the above waxes can also be used.

[0382] In a preferred embodiment, paraffin wax having a melting point of about 50° C. to about 100° C., preferably about 60° C. to about 100° C., is used. In another preferred embodiment, polyethylene wax having a melting point of about 50° C. to about 100° C., preferably about 60° C. to about 100° C., is used.

[0383] Waxes as described herein can be used to convert and / or reversibly convert formulations and / or build materials into solids or semi-solids.

[0384] It should be understood that the present disclosure provides methods for synthesizing the compounds described herein. The present disclosure also provides detailed methods for synthesizing various disclosed compounds of the present disclosure according to the following schemes, as well as the compounds shown in the Examples.

[0385] Throughout this description, when a composition is described as having, including, or comprising certain components, it should be understood that the composition is also envisioned to consist essentially of, or consist of, the recited components. Similarly, when a method or process is described as having, including, or comprising certain process steps, the process also consists essentially of, or consists of, the recited process 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 performed simultaneously.

[0386] It should be understood that the 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 that are known or will be apparent to those skilled in the art 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. Without being limited to any one or several sources, older texts such as Smith, MB, March, J., March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th edition, John Wiley & Sons: New York, 2001; Greene, TW, Wuts, PGM, Protective Groups in Organic Synthesis, 3rd edition, 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), which are incorporated herein by reference, are known to those of skill in the art and are useful and recognized reference texts in organic synthesis.

[0387] Those skilled in the art will note that the order of certain steps, such as the introduction and removal of protective groups, may be changed during the reactions and syntheses described herein. Those skilled in the art will recognize that certain groups may need to be protected from reaction conditions using protective groups. Protective groups may also be used to distinguish similar functional groups in a molecule. A list of protective groups and methods for the introduction and removal of these groups can be found in Greene, TW, Wuts, PGM, Protective Groups in Organic Synthesis, 3rd edition, John Wiley & Sons: New York, 1999.

[0388] All percentages and ratios used herein are by weight unless otherwise specified.Other features and advantages of the present disclosure are apparent from different examples.The examples provided illustrate different components and methodologies useful in carrying out the present disclosure.The examples do not limit the claims of the present disclosure.Based on the present disclosure, a person skilled in the art can identify and utilize other components and methodologies useful for carrying out the present disclosure.

[0389] All publications and patent documents cited in this specification 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 such document is relevant prior art, nor does it constitute any admission as to its contents or date. Although the invention has been described herein by written description, those skilled in the art will recognize that the invention can be implemented in various embodiments, and that the foregoing description and the following examples are for illustrative purposes only and are not intended to limit the scope of the following claims. Embodiment

[0390] Aspects of the present disclosure are further described with reference to the following numbered embodiments. 1. (i) a ring-opening metathesis polymerization (ROMP) precursor; (ii) a curing catalyst. 2. (i) a ring-opening metathesis polymerization (ROMP) precursor; (ii) a curing catalyst; and (iii) an activator. 3. (i) Formulations containing ring-opening metathesis polymerization (ROMP) precursors. 4. (ii) Formulations containing a curing catalyst. 5. (ii) a curing catalyst; and (iii) an activator. 6. The formulation of any one of the preceding embodiments, further comprising a gelling agent. 7. 7. The formulation of any one of the preceding embodiments 1-6, further comprising a wax. 8. The formulation of any one of the preceding embodiments, further comprising a means for converting the formulation into a solid or semi-solid. 9. The formulation of any one of the preceding embodiments, further comprising a means for reversibly converting the formulation into a solid or semi-solid. 10. The formulation of any one of the preceding embodiments, further comprising a means for converting the formulation into a solid. 11. The formulation of any one of the preceding embodiments, further comprising a means for converting the formulation into a semi-solid. 12. (i) a ring-opening metathesis polymerization (ROMP) precursor; (v) a means for converting said formulation into a solid or semi-solid. 13. (ii) a curing catalyst; and (v) a means for converting said formulation into a solid or semi-solid. 14. (ii) a curing catalyst; and (iii) an activator; (v) a means for converting said formulation into a solid or semi-solid. 15. (i) a ring-opening metathesis polymerization (ROMP) precursor; (v) a gelling agent or wax. 16. (ii) a curing catalyst; and (v) a gelling agent or wax. 17. (ii) a curing catalyst; and (iii) an activator; (v) a gelling agent or wax. 18. Any one of the preceding embodiments, wherein the formulation is liquid at a temperature between about 35°C and about 100°C. 19. 20. Any one of the preceding embodiments, wherein the formulation is liquid at a temperature of about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C or about 100°C. twenty one. Any one of the preceding embodiments, wherein the formulation is a solid or semi-solid at about room temperature (e.g., about 25° C.). twenty two. Any one of the preceding embodiments, wherein the formulation is solid at about room temperature (e.g., about 25° C.). twenty three. Any one of the preceding embodiments, wherein the formulation is semi-solid at about room temperature (e.g., about 25° C.). twenty four. The formulation of any one of the preceding embodiments, wherein the melting point is from about 60°C to about 100°C. twenty five. Any one of the preceding embodiments, wherein the formulation has a melting point of about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C or about 100°C. 26. The formulation of any one of the preceding embodiments, wherein the gelling agent, the wax and / or the means for converting the formulation into a solid and / or semi-solid is present in an amount of about 0.5% (w / w) to about 50% (w / w). 27. The formulation of any one of the preceding embodiments, which is free of both a ROMP precursor and a cure catalyst. 28. The blend of any one of the preceding embodiments, which is a homogenous blend. 29. A build material comprising the formulation according to any one of the preceding embodiments. 30. (i) a ROMP precursor; (ii) a curing catalyst; and a building material comprising the curing catalyst. 31. (i) a ROMP precursor; (ii) a curing catalyst; and (iii) an activator. 32. (i) a ring-opening metathesis polymerization (ROMP) precursor; (v) a means for converting the build material into a solid or semi-solid material. 33. (ii) a curing catalyst; and (v) a means for converting the build material into a solid or semi-solid material. 34. (ii) a curing catalyst; and (iii) an activator; (v) a means for converting the build material into a solid or semi-solid material. 35. (i) a ring-opening metathesis polymerization (ROMP) precursor; (v) a gelling agent or wax. 36. (ii) a curing catalyst; and (v) a gelling agent or wax. 37. (ii) a curing catalyst; and (iii) an activator; (v) a gelling agent or wax. 38. A molding material in any one of the above embodiments, having a melting point of about 60°C to about 100°C. 39. The build material, in any one of the above prevalent forms, has a melting point of about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C or about 100°C. 40. The build material, in any one of the preceding embodiments, is free of both a ROMP precursor and a curing catalyst. 41. A kit comprising the formulation or modeling material of any one of the preceding embodiments. 42. A kit comprising a formulation or modeling material of any one of the preceding embodiments and means for 3D printing. 43. A kit comprising the formulation of any one of the preceding embodiments and a means for inkjet 3D printing. 44. A kit comprising the formulation of any one of the preceding embodiments and a means for delayed cure inkjet 3D printing. 45. A kit comprising the formulation of any one of the preceding embodiments and a means for delayed cure inkjet 3D printing. 46. (i) ROMP precursors and (ii) Curing catalyst a first build material comprising: (iii) ROMP precursors, and (iv) Activator and a second build material comprising: 47. (i) ROMP precursors, (ii) a curing catalyst; and (v) Gelling agents or waxes a first build material comprising: (iii) ROMP precursors, (iv) an activator, and (v) Gelling agents or waxes and a second build material comprising: 48. (i) ROMP precursors, (ii) a curing catalyst, and (v) A means for converting the build material into a solid or semi-solid material. a first build material comprising: (iii) ROMP precursors, (iv) an activator, and (v) A means for converting the build material into a solid or semi-solid material. and a second build material comprising: 49. (i) ROMP precursors, (ii) a curing catalyst, and A molding material comprising: A kit including a support material. 50. (i) ROMP precursors, (ii) a curing catalyst, and (iii) Activator A molding material comprising: A kit including a support material. 51. (i) ROMP precursors and (ii) Curing catalyst a first build material comprising: (iii) ROMP precursors, and (iv) Activator a second build material comprising: A kit including a support material. 52. (i) ROMP precursors, (ii) a curing catalyst; and (v) Gelling agents or waxes a first build material comprising: (iii) ROMP precursors, (iv) an activator, and (v) Gelling agents or waxes a second build material comprising: A kit including a support material. 53. (i) ROMP precursors, (ii) a curing catalyst; and (v) A means for converting the build material into a solid or semi-solid material. a first build material comprising: (iii) ROMP precursors, (iv) an activator, and (v) A means for converting the build material into a solid or semi-solid material. a second build material comprising: A kit including a support material. 54. (i) a ROMP precursor; (ii) a curing catalyst; and (v) Gelling agents or waxes a first build material comprising: (iii) ROMP precursors, and (v) Gelling agents or waxes a second build material comprising: A kit including a support material. 55. (i) ROMP precursors, (ii) a curing catalyst; and (v) A means for converting the build material into a solid or semi-solid material. a first build material comprising: (iii) ROMP precursors, and (v) A means for converting the build material into a solid or semi-solid material. a second build material comprising: A kit including a support material. 56. The kit according to any one of the preceding embodiments, wherein the melting point of the first modeling material is between about 60°C and about 100°C. 57. Any one of the preceding embodiments, wherein the melting point of the first modeling material is about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C or about 100°C. 58. The kit according to any one of the preceding embodiments, wherein the melting point of the second modeling material is between about 60°C and about 100°C. 59. Any one of the preceding embodiments, wherein the melting point of the second modeling material is about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C or about 100°C. 60. Any one of the preceding embodiments, wherein the first build material does not include both a ROMP precursor and a curing catalyst. 61. Any one of the preceding embodiments, wherein the second build material does not include both a ROMP precursor and a curing catalyst. 62. A kit according to any one of the preceding embodiments, wherein the concentration of the gelling agent, the wax and / or the means for converting the formulation into a solid and / or semi-solid is higher in the first modeling material than in the second modeling material. 63. The formulation of any one of the preceding embodiments, wherein the gelling agent, the wax and / or the means for converting the formulation to a solid and / or semi-solid is present in the first modeling material in an amount greater than about 30% (w / w). 64. The formulation of any one of the preceding embodiments, wherein the gelling agent, the wax and / or the means for converting the formulation to a solid and / or semi-solid is present in the first modeling material in an amount of about 30% (w / w) to about 50% (w / w). 65. The formulation of any one of the preceding embodiments, wherein the gelling agent, the wax and / or the means for converting the formulation to a solid and / or semi-solid is present in the second modeling material in an amount of about 0.5% (w / w) to about 10% (w / w). 66. The formulation of any one of the preceding embodiments, wherein the gelling agent, the wax and / or the means for converting the formulation to a solid and / or semi-solid is present in the second modeling material in an amount of about 1% (w / w) to about 5% (w / w). 67. The ROMP precursor is a compound of formula (MI): [ka] or a salt thereof, X is CH2 or O; R 1are each independently (a) is hydrogen, halogen, cyano, -OR 1A , -SR 1A , -C(=O)-R 1A , -C(=O)-OR 1A , -OC(=O)-R 1A , -C(=O)-N(R 1A )2, -C(=O)-NHR 1A , -NH-C(=O)-R 1A , -N(R 1A )2, -Si(R 1A )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A or (b) Other R 1 and the atoms to which they are attached, bonds, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A optionally replaced by R 1A are each independently (a) is hydrogen, halogen, cyano, -OR 1B , -SR 1B , -C(=O)-R 1B , -C(=O)-OR 1B, -OC(=O)-R 1B , -C(=O)-N(R 1B )2, -C(=O)-NHR 1B , -NH-C(=O)-R 1B , -N(R 1B )2, -Si(R 1B )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B optionally replaced by (b) Other R 1A and they form bonds with adjacent atoms, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B optionally substituted with, or (c) [ka] or [ka] and R 1B are each independently [ka] Hydrogen, halogen, cyano, -OR 1C , -SR 1C , -C(=O)-R 1C , -C(=O)-OR 1C , -OC(=O)-R 1C , -C(=O)-N(R 1C )2, -C(=O)-NHR 1C , -NH-C(=O)-R 1C , -N(R 1C )2, -Si(R 1C )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is one or more R 1C optionally replaced by R 1C are each independently [ka] Hydrogen, halogen, cyano, -OR 1D , -SR 1D , -C(=O)-R 1D , -C(=O)-OR 1D , -OC(=O)-R 1D , -C(=O)-N(R 1D )2, -C(=O)-NHR 1D , -NH-C(=O)-R 1D , -N(R 1D )2, -Si(R 1D )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1D and R 1D are each independently hydrogen, halogen, cyano, -OH, -NH2, C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 The formulation, shaping material or kit of any one of embodiments 1-66, wherein the heterocycloalkyl is aryl, 3-20 membered heterocycloalkyl, or 5-20 membered heteroaryl. 68. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein X is CH2. 69. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein X is O. 70. At least one R 1 The formulation, modeling material, or kit of any one of the preceding embodiments, wherein is hydrogen. 71. R 1 At least one of the following is halogen, cyano, -OR 1A , -SR 1A , -C(=O)-R 1A , -C(=O)-OR 1A , -OC(=O)-R 1A , -C(=O)-N(R 1A )2, -C(=O)-NHR 1A , -NH-C(=O)-R1A , -N(R 1A )2, -Si(R 1A )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A Optionally, the formulation, modeling material, or kit of any one of the preceding embodiments is substituted with 72. At least two R 1 They form bonds with adjacent atoms, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1A Optionally, the formulation, modeling material, or kit of any one of the preceding embodiments is substituted with 73. At least one R 1A The formulation, modeling material, or kit of any one of the preceding embodiments, wherein is hydrogen. 74. R 1A At least one R 1A But halogen, cyano, -OR 1B , -SR 1B , -C(=O)-R 1B, -C(=O)-OR 1B , -OC(=O)-R 1B , -C(=O)-N(R 1B )2, -C(=O)-NHR 1B , -NH-C(=O)-R 1B , -N(R 1B )2, -Si(R 1B )3, C1~C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C1-C 20 Alkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B Optionally, the formulation, modeling material, or kit of any one of the preceding embodiments is substituted with 75. At least two R 1A However, they form bonds with adjacent atoms, C3 to C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; C3-C 20 Cycloalkyl, C6-C 20 Aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl may be one or more R 1B Optionally, the formulation, modeling material, or kit of any one of the preceding embodiments is substituted with 76. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 77. The ROMP precursor is a compound comprising: [ka] [ka] or a salt thereof. 78. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 79. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 80. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 81. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 82. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 83. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 85. The ROMP precursor is a compound comprising: [ka] or a salt thereof, 1F is hydrogen, halogen, cyano, -OH, NH2, C1~C 20 Alkyl, C2-C 20 Alkenyl or C2-C 20 alkynyl, R 1E teeth, [ka] or [ka] 3. The formulation, modeling material or kit of any one of the preceding embodiments, 86. The ROMP precursor is a compound comprising: [ka] or a salt thereof, 1F is hydrogen, halogen, cyano, -OH, NH2, C1~C 20 Alkyl, C2-C 20 Alkenyl or C2-C 20alkynyl, R 1E teeth, [ka] or [ka] 3. The formulation, modeling material or kit of any one of the preceding embodiments, 87. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the ROMP precursor is the following compound: 88. The ROMP precursor is a compound comprising: [ka] or a salt thereof. 89. The ROMP precursor is a compound comprising: [ka] or [ka] 3. The formulation, modeling material or kit of any one of the preceding embodiments, 90. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the ROMP precursor is the following compound: 91. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the ROMP precursor is selected from the compounds set forth in Table 1 and salts thereof. 92. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the curing catalyst is a latent catalyst. 93. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the latent catalyst is a thermal latent catalyst, a photo latent catalyst, or a chemical latent catalyst. 94. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the curing catalyst is activated by light irradiation. 95. The formulation, build material, or kit of any one of the preceding embodiments, wherein the curing catalyst is UV activated. 96. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the curing catalyst is activated by elevated temperature. 97. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the curing catalyst is activated by an activator. 98. The formulation, modeling material or kit of any one of the preceding embodiments, wherein the curing catalyst is a ruthenium catalyst. 99. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the curing catalyst is Grubbs' catalyst. 100. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the activating agent is an acid. 101. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the activator is a photogenerated acid. 102. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the activating agent is a precursor of an acid. 103. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the activator releases an acid upon activation. 104. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the gelling agent is a wax. 105. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the wax is a polyethylene wax. 106. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the wax is paraffin wax. 107. 2. The composition, modeling material or kit of any one of the preceding embodiments, wherein the wax has a melting point of about 60°C to about 100°C. 108. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the wax has a melting point of about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C. 109. The formulation, modeling material or kit of any one of the preceding embodiments, further comprising a stabilizer. 110. The formulation, modeling material, or kit of any one of the preceding embodiments, wherein the stabilizer is a thermal stabilizer. 111. The formulation, shaping material or kit of any one of the preceding embodiments, further comprising an impact modifier. 112. The formulation, modeling material or kit of any one of the preceding embodiments, further comprising an optical enhancing component. 113. The formulation, modeling material, or kit of any one of the preceding embodiments, further comprising a pigment, dye, or a combination thereof. 114. The formulation, modeling material, or kit of any one of the preceding embodiments, further comprising a surfactant, an antioxidant, a catalyst inhibitor, a filler, a pigment, a dispersant, a flame retardant, or any combination thereof. 115. The modeling material or kit according to any one of the preceding embodiments, wherein the viscosity of the modeling material is about 1 cp to about 100 cp, about 2 cp to about 80 cp, about 3 cp to about 70 cp, about 4 cp to about 60 cp, about 5 cp to about 50 cp, about 6 cp to about 40 cp, about 7 cp to about 30 cp, or about 8 cp to about 20 cp, when measured at about 20°C to about 25°C, about 30°C to about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C. 116. The modeling material or kit of any one of the preceding embodiments, wherein the viscosity of the modeling material changes by about 10 cp or less, about 9 cp or less, about 8 cp or less, about 7 cp or less, about 6 cp or less, about 5 cp or less, about 4 cp or less, about 3 cp or less, about 2 cp or less, or about 1 cp or less upon storage for 2 weeks at about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C. 117. The molding material or kit of any one of the preceding embodiments, wherein the hardened molding material has a tensile strength of 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 65 MPa, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa, about 90 MPa, about 95 MPa, about 100 MPa, or any range therebetween. 118. The molding material or kit of any one of the preceding embodiments, wherein the elongation at break of the hardened molding material is about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100%, about 105%, about 110%, about 115%, about 120%, about 125%, about 130%, or any range therebetween. 119. The modeling material or kit of any one of the preceding embodiments, wherein the Young's modulus of the hardened modeling material is about 0.8 GPa, about 0.9 GPa, about 1.0 GPa, about 1.1 GPa, 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, about 2.6 GPa, about 2.7 GPa, about 2.8 GPa, about 2.9 GPa, about 3.0 GPa, or a range therebetween. 120. The notched Izod impact strength of the cured building material is about 5 J / m, about 10 J / m, about 20 J / m, about 30 J / m, about 40 J / m, about 50 J / m, about 100 J / m, about 150 J / m, about 200 J / m, about 250 J / m, about 300 J / m, about 350 J / m, about 400 J / m, about 450 J / m, about 500 J / m, about 550 J / m, about 600 J / m, about 650 J / m, about 700 J / m, about 750 J / m, about 800 J / m, or a range therebetween. 121. A method of preparing a hardened material comprising subjecting a formulation, modeling material, or kit according to any one of the preceding embodiments to hardening conditions. 122. Preparing the hardened material comprises subjecting the formulation, modeling material or kit of any one of the preceding embodiments to hardening conditions. one two three. Use of a formulation, modeling material or kit according to any one of the previous embodiments in the manufacture of a hardened material, said manufacture comprising the step of subjecting the formulation, modeling material or kit to hardening conditions. 124. The method, formulation, build material, kit or use of any one of the preceding embodiments, wherein the curing conditions of the build material include light irradiation. 125. The method, formulation, build material, kit or use of any one of the preceding embodiments, wherein the build material curing conditions include elevated temperature. 126. The method, formulation, build material, kit or use of any one of the preceding embodiments, wherein the build material hardening conditions include chemical activation. 127. A hardened material prepared by the method of any one of the preceding embodiments. 128. A method of printing an object using the method, formulation, build material, kit or use according to any one of the preceding embodiments. 129. 2. The formulation, build material or kit of any one of the preceding embodiments for use in printing an object. 130. The printing, (i) depositing a build material onto a support material; (ii) subjecting the deposited build material to curing conditions. 131. The printing, (i) depositing a first build material and a second build material onto a support material; (ii) subjecting the deposited first and second build materials to curing conditions. 132. The method, formulation, build material or kit of any one of the preceding embodiments, wherein the printing further comprises repeating the step of depositing material one or more times. 133. The method, formulation, build material, or kit of any one of the preceding embodiments, wherein the printing further comprises optically detecting the deposited material and controlling one or more repeated depositions of the material according to the detection. 134. The method, formulation, build material, or kit of any one of the preceding embodiments, wherein the printing does not include contacting the build material and / or the support material with a means for mechanically maintaining a precise interlayer structure. 135. The method, formulation, build material, or kit of any one of the preceding embodiments, wherein the printing does not include contacting the build material and / or the support material with a roller. 136. The method, formulation, build material, or kit of any one of the preceding embodiments, wherein the printing does not include contacting the build material and / or the support material with a planarizing agent. 137. 1. A system for 3D printing, comprising: (i) a printer; (ii) an ink comprising the formulation according to any one of the preceding embodiments. 138. A 3D printing system, (i) a printer; (ii) a first ink comprising the formulation according to any one of the previous embodiments; and (iii) a second ink comprising the formulation according to any one of the preceding embodiments, The first ink comprises a ROMP precursor and no curing catalyst, and the second ink comprises a curing catalyst and no ROMP precursor. 139. 13. The system of any one of the preceding embodiments, further comprising means for scanning the partially manufactured object. 140. The system of any one of the preceding embodiments, wherein the system does not include a means for mechanically maintaining a precise interlayer structure. 141. The system of any one of the preceding embodiments, wherein the system does not include a roller. 142. The system of any one of the preceding embodiments, wherein the system does not include a planarizing agent. Working Example Example 1: Preparation of an exemplary kit containing an acid-activated catalyst for ROMP polymerization

[0391] An exemplary kit for ROMP polymerization is prepared using an acid-activated catalyst. The components and amounts of the kit are detailed in Table A. [Table A] Example 2: Preparation of an exemplary build material containing a light-activated catalyst for ROMP polymerization

[0392] Exemplary build materials for ROMP polymerization are prepared using a light-activated catalyst. See Table B for detailed material components and their amounts. [Table B] Example 3: Preparation of an exemplary build material containing a photoactivatable agent for ROMP polymerization

[0393] Exemplary build materials for ROMP polymerization are prepared using a photoactivatable agent. See Table B for detailed material components and their amounts. [Table C] equivalent

[0394] The details of one or more embodiments of the present disclosure are set forth in the attached description above. Although similar or equivalent methods and materials described herein can be used to carry out or test the present disclosure, preferred methods and materials are now described. Other features, objects and advantages of the present disclosure will be apparent from the description and claims. In this specification and the appended claims, the singular form "a," "an," or "the" includes plural referents unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs. All patents and publications cited herein are incorporated by reference.

[0395] The preceding description has been presented for purposes of illustration only and is not intended to limit the disclosure to the precise form disclosed.

Claims

(i) a ring-opening metathesis polymerization (ROMP) precursor; A formulation comprising:

2. (ii) a curing catalyst and / or (iii) an activator, 2. The formulation of claim 1 further comprising:

3. A gelling agent, wax, means for converting said formulation into a solid or semi-solid; means for reversibly converting said formulation into a solid or semi-solid; a means for converting said formulation into a solid; and / or means for converting said formulation into a semi-solid; 20. The formulation of claim 1, further comprising:

4. A formulation that is liquid at a temperature of about 35°C to about 100°C, as described in any one of the preceding claims.

5. A formulation that is solid or semi-solid at about room temperature (e.g., about 25°C), as described in any one of the preceding claims.

6. A formulation described in any one of the preceding claims, having a melting point of about 60°C to about 100°C.

7. The ROMP precursor of claim 1, wherein the ROMP precursor is a compound of formula (MI): 【Chemistry 1】 or a salt thereof, X is CH2 or O; Each R 1 is independently (a) is hydrogen, halogen, cyano, -OR 1A , -SR 1A , -C(═O)-R 1A , -C(═O)-OR 1A , -O-C(═O)-R 1A , -C(═O)-N(R 1A ) 2 , -C(═O)-NHR 1A , -NH-C(═O)-R 1A , -N(R 1A ) 2 , -Si(R 1A ) 3 , C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl; 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl are optionally substituted with one or more R 1A , or (b) together with the other R 1 and the atoms to which they are attached form a bond, a C 3 -C 20 cycloalkyl, a C 6 -C 20 aryl, a 3- to 20-membered heterocycloalkyl, or a 5- to 20-membered heteroaryl, wherein the C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, a 3- to 20-membered heterocycloalkyl, or a 5- to 20-membered heteroaryl is optionally substituted with one or more R 1A ; Each R 1A is independently (a) is hydrogen, halogen, cyano, —OR 1B , —SR 1B , —C(═O)-R 1B , —C(═O)-OR 1B , —O-C(═O)-R 1B , —C(═O)-N(R 1B ) 2 , —C(═O)-NHR 1B , —NH-C(═O)-R 1B , —N(R 1B ) 2 , —Si(R 1B ) 3 , C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl; C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl are optionally substituted with one or more R 1B ; (b) other R 1A and adjacent atoms together form a bond to form a C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl, wherein the C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl, or 5- to 20-membered heteroaryl is optionally substituted with one or more R 1B ; or （C） 【Chemistry 2】 or 【Chemistry 3】 and Each R 1B is independently 【Chemistry 4】 hydrogen, halogen, cyano, -OR 1C , -SR 1C , -C(=O)-R 1C , -C(=O)-OR 1C , -O-C(=O)-R 1C , -C(=O)-N(R 1C ) 2 , -C(=O)-NHR 1C , -NH-C(=O)-R 1C , -N(R 1C ) 2 , -Si(R 1C ) 3 , C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl; C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl are optionally substituted with one or more R 1C ; Each R 1C is independently 【Chemistry 5】 hydrogen, halogen, cyano, -OR 1D , -SR 1D , -C(═O)-R 1D , -C(═O)-OR 1D , -O-C(═O)-R 1D , -C(═O)-N(R 1D ) 2 , -C(═O)-NHR 1D , -NH-C(═O)-R 1D , -N(R 1D ) 2 , -Si(R 1D ) 3 , C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl; C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl is optionally substituted with one or more R 1D ; and 20. The formulation, shaping material or kit of any one of the preceding claims, wherein each R 1D is independently hydrogen, halogen, cyano, -OH, -NH 2 , C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, 3- to 20-membered heterocycloalkyl or 5- to 20-membered heteroaryl.

8. The ring-opening metathesis polymerization (ROMP) precursor is 【Chemistry 6】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 or a salt of a compound selected from the group consisting of A formulation as claimed in any one of the preceding claims.

9. The curing catalyst is a latent catalyst, The curing catalyst is activated by light irradiation. The curing catalyst is UV activated. The curing catalyst is activated by increasing the temperature. The curing catalyst is activated by an activator. the curing catalyst is a ruthenium catalyst; or The curing catalyst is a Grubbs catalyst; A formulation as claimed in any one of the preceding claims.

10. The method of claim 1, wherein the activator is an acid. the activator is a photogenerated acid; the activator is a precursor of an acid, or the activator releases an acid upon activation; A formulation as claimed in any one of the preceding claims.

11. The gelling agent is a wax, The melting point of the wax is about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C or about 100°C; A formulation as claimed in any one of the preceding claims.

12. The composition further comprising a stabilizer, an optical enhancing component, a pigment, a dye, a surfactant, an antioxidant, a catalyst inhibitor, a filler, a dispersant, a flame retardant, or a combination thereof. A formulation as claimed in any one of the preceding claims.

13. The method of claim 1, further comprising the step of subjecting a formulation according to any one of the preceding claims to curing conditions. A method for preparing a hardening material.

14. A hardened material prepared by the method described in claim 13.

15. A system for 3D printing. (i) a printer; and (ii) a first ink comprising a formulation as defined in any one of the preceding claims; and Including, (iii) a second ink comprising a formulation as claimed in any one of the preceding claims; and and optionally further including the first ink comprises a ROMP precursor and no curing catalyst; the second ink comprises a curing catalyst and does not comprise a ROMP precursor; 3D printing system.

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