WO-2026096482-A2 - MACROCYCLIC OLEFINS FOR RING-OPENING METATHESIS POLYMERIZATION (ROMP) AND USES THEREOF

Abstract

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

Inventors

• SKOWERSKI, KRZYSZTOF
• TWIDDY, Scott T.
• Nelson, Zachary P.

Assignees

• Inkbit, LLC

Dates

Publication Date

20260507

Application Date

20251028

Priority Date

20241029

Claims (20)

1. Claims
2. 1. A combination comprising:
3. (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor;
4. (ii) a bridged polycyclic ROMP precursor; and
5. (iii) a curing catalyst.
6. 2. A kit comprising:
7. a build material comprising:
8. (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;
9. (iii) a latent curing catalyst;
10. (iv) an activator; and
11. a support material.
12. 3. A kit comprising:
13. a first build material comprising:
14. (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor;
15. (iii) an activator
16. a second build material comprising:
17. (iv) a curing catalyst
18. (v) a solvent; and
19. a support material.
20. 4. The combination, build material, or kit of any one of the preceding claims, wherein the bridged polycyclic ROMP precursor is a strained ROMP precursor.

Description

MACROCYCLIC OLEFINS FOR RING-OPENING METATHESIS POLYMERIZATION (ROMP) AND USES THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to, and the benefit of, U. S. Provisional Application No. 63/713,134, filed October 29, 2024, the contents of which are incorporated by reference in their entirety. BACKGROUND Additive manufacturing, also known as 3D printing, refers to a relatively wide class of techniques that allows objects to be fabricated via selective addition of material according to a computer-controlled process, generally to match a desired 3D specification, for example, a solid model. A number of different classes of materials have been used for such 3D printing, with different materials providing corresponding advantages and/disadvantages for different fabrication techniques. For example, a survey of materials may be found in Ligon et al. (Chemical Reviews 117(15): 10212-10290 (2017)). A class of fabrication techniques jets material for deposition on a partially fabricated object using inkjet printing technologies. The jetted material is typically cured (e.g., by UV radiation) shortly after it is deposited, forming thin layers of cured material. To achieve precision fabrication, some techniques use mechanical approaches to maintain accurate layer-to-layer structure, for example, using mechanical rollers or “planarizers” to control the surface geometry, and therefore control the accuracy of the fabricated object. Therefore, rapid curing is a key feature to allow the planarization and obtain an accurately fabricated object. However, the resulting material properties obtained with such inks may be insufficient. What is needed is a printable material that exhibit high tensile strength/tensile modulus combined with high elongation at break and/or high impact strength. The present invention addresses this need. SUMMARY In some aspects, the present disclosure provides a combination comprising: (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ROMP precursor; and (iii) a curing catalyst. In some aspects, the present disclosure provides a kit comprising: a build material comprising: (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor; (iii) a latent curing catalyst; (iv) an activator; and a support material. In some aspects, the present disclosure provides a kit comprising: a first build material comprising: (i) a macrocyclic ring-opening-metathesis-polymerization (ROMP) precursor; (ii) a bridged polycyclic ring-opening-metathesis-polymerization (ROMP) precursor; (iii) an activator a second build material comprising: (iv) a curing catalyst (v) a solvent; and a support material. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor is a strained ROMP precursor. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-I): wherein W is CH2 or C=O; Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; and , together with the atoms to which it is attached and any intervening atoms, forms a 14- to 50- membered ring comprising 1-10 C=C bonds. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the macrocyclic ROMP precursor comprises a compound of Formula (R-Ia): wherein: W is CH2 or C=O; m and n are each independently an integer between 0 and 20; Ri and R2 are each independently absent, -CH2-, -O-, or -NH-; * each - is independently a single bond or a double bond having either the (E) or (Z) configuration; and * wherein at least one - is a double bond; provided that: a) when neither of Ri and R2 are absent, the sum of m + n is > 7; b) when one of Ri and R2 is absent, the sum of m + n is > 8; and c) when both of Ri and R2 are absent, the sum of m + n is > 9. In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the macrocyclic ROMP precursor comprises Compound (R-l), Compound (R-2), Compound (R-3), or Compound (R-4): In some aspects, the present disclosure provides a combination, build material, or kit disclosed herein, wherein the bridged polycyclic ROMP precursor comprises a compound of Formula (S-II): wherein: q is 0, 1 or 2; R3 and R5 are each independently absent, hydrogen, halogen, C1-C16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C1-C16 alkoxy, -C(=O)-R1A, -O-C(=O)-R1A, C6-Ci4 aryl, -O-C6-Ci4 aryl, 3- to 14-membered heterocycloalkyl, 5- to 14-membered heteroaryl, -Si(R1A)3, or -Z-(R7), wherein the Ci-16 alkyl, C2-C16 alkenyl, C3-C14 cycloalkyl, C3-C14 cycloalkenyl, C6-C14 aryl, 3-to 14-membered heterocycloalkyl, or 5- to 14-membered heteroaryl is optionally substituted with one or more