Multivalent polyester based polyurethane acrylate or methacrylate oligomers formulated with different reactive diluents

Abstract

The present disclosure provides novel oligomers and polymerizable compositions comprising the same. Further provided herein are methods of producing polymers, polymer coatings, and devices. Also provided herein are methods of using polymer materials and polymer materials fabricated via additive manufacturing processes (e.g., via 3D printing), such as orthodontic appliances.

Description

[0001] MULTIVALENT POLYESTER BASED POLYURETHANE ACRYLATE OR METHACRYLATE OLIGOMERS FORMULATED WITH DIFFERENT REACTIVE DILUENTS

[0002] INCORPORATION BY REFERENCE

[0003] All publications, patents, and patent applications mentioned in this specification, including U.S. Provisional Patent Application No. 63 / 740,032, filed on December 30, 2024, are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.

[0004] BACKGROUND OF THE DISCLOSURE

[0005] There is a need in the field of orthodontic and dental appliances for materials having desirable properties (e.g., durability, wear resistance, etc.). The present disclosure addresses these issues along with providing other unexpected benefits. The present disclosure provides oligomers, polymerizable compositions, polymeric coatings, and their use in dental appliances. Further, the present disclosure provides methods for manufacturing 3D printed articles (e.g., dental aligners).

[0006] SUMMARY OF THE DISCLOSURE

[0007] Embodiments of the present disclosure provide a polymerizable composition comprising (1) an oligomer having an aliphatic polyester backbone and 2 or more (e.g., 2, 3, 4, 5, 6, etc.) polymerizable reactive groups at each terminal end of the aliphatic polyester backbone, (2) an initiator, (3) a reactive diluent, and (4) an amine synergist.

[0008] The present disclosure provides a method for preparing a 3D manufactured article, the method comprising: mixing an oligomer of the present disclosure with at least one reactive diluent. Another embodiment provides a polymer formed from the method. Also, another embodiment provides a 3D printed article produced by the method.

[0009] One embodiment provides an orthodontic appliance comprising a polymer of the disclosure. In some embodiments, the orthodontic appliance is a dental appliance. In certain embodiments, the orthodontic appliance is a dental aligner, a dental expander, or a dental spacer.

[0010] Additional embodiments provide a method for preparing an article by an additive manufacturing process, the method comprising preparing the polymerized 3D printed article by an additive manufacturing process. In some embodiments, the process comprises:

[0011] 1

[0012] #11356484.1providing a polymerizable composition;

[0013] exposing the polymerizable composition to radiation;

[0014] polymerizing the first polymerizable composition layer-by-layer based on a predefined design, thereby polymerizing the first polymerizable composition to form a polymer; and

[0015] fabricating the polymerized 3D printed article with the polymer.

[0016] Other embodiments provide a method of repositioning a patient's teeth, the method comprising: generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement; producing an orthodontic appliance or an orthodontic appliance comprising the polymer coating of the disclosure; and moving on-track, with the orthodontic appliance, at least one of the patient's teeth toward an intermediate tooth arrangement or the final tooth arrangement.

[0017] DESCRIPTION OF THE FIGURES

[0018] The novel features of the disclosure are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of this dislcosure are utilized, and the accompanying drawings of which:

[0019] FIG. 1 A illustrates a tooth repositioning appliance, in accordance with embodiments.

[0020] FIG. IB illustrates a tooth repositioning system, in accordance with embodiments. FIG. 1C illustrates a method of orthodontic treatment using a plurality of appliances, in accordance with embodiments.

[0021] FIG. 2 is a partially schematic illustration of a system for additive manufacturing configured in accordance with embodiments of the present technology.

[0022] FIG. 3 illustrates a method for digitally planning an orthodontic treatment, in accordance with embodiments.

[0023] FIG. 4 shows generating and administering treatment according to an embodiment of the present disclosure.

[0024] 2

[0025] #11356484.1FIG. 5 shows a schematic configuration of a high temperature additive manufacturing device used for curing a curable composition of the present disclosure by using a 3D printing process.

[0026] FIG. 6 illustrates a method for designing an orthodontic appliance, in accordance with embodiments.

[0027] DETAILED DESCRIPTION

[0028] Oligomers, polymers and polymer coatings of the present disclosure can be cured in air. Additionally, the polymer coatings save processing steps for 3D printed objects that use resinbased printing methods. Oligomers and polymerizable compositions of the present disclosure can be combined with various reactive diluents to meet the performance requirements for dental aligners.

[0029] The present disclosure provides useful compounds and compositions as well as methods of using (e.g., for producing polymerizable compositions, and / or polymeric material) and producing the same. The polymerizable compositions described herein can address an unmet need to produce polymeric coatings and films with advantageous properties (e.g., increased toughness, smoothness, stain resistance) useful for various device applications, while containing low amounts of leachable components that may be taken up by an individual using such device.

[0030] All terms, chemical names, expressions, and designations have their usual meanings which are well-known to those skilled in the art. As used herein, the terms "to comprise" and "comprising" are to be understood as non-limiting, z.e., other components than those explicitly named may be included. The term "consisting" or "consisting of' means that only components that are explicitly described are included. The term "consisting essentially of' limits the scope to specified materials, elements, steps, embodiments, aspects, and limitations except for those that do not materially affect basic and novel characteristics. For each embodiment of this disclosure, it is understood that any specified materials, elements, steps, embodiments, aspects, and limitations may be included with any of the phrases.

[0031] Number ranges are to be understood as inclusive, z.e., including the indicated lower and upper limits (e.g., the phrase "an integer ranging from 1-3" includes the integers 1, 2, and 3). Furthermore, the term "about," as used herein, and unless clearly indicated otherwise, refers to and encompasses plus or minus 10% of the indicated numerical value(s). For example, "about 10%" may indicate a range of 9% to 11%, and "about 1" may include the range 0.9-1.1.

[0032] 3

[0033] #11356484.1As used herein, the terms "polymer," "polymeric material," or an equivalent refers to a molecule composed of repeating structural units connected by covalent chemical bonds and characterized by a substantial number of repeating units (e.g., equal to or greater than 10 repeating units; in some embodiments, repeating units are equal to or greater than 100, 200, 250, 300, 350, 400, 450, or 500 repeating units) and a molecular weight greater than or equal to 5,000 Daltons (Da) or 5 kDa; for example, in some embodiments, a polymeric material has a molecular weight greater than or equal to 10 kDa, 15 kDa, 20 kDa, 30 kDa, 40 kDa, 50 kDa, or 100 kDa. Polymers of the present disclosure are the polymerization product of a diradical photoinitiator of this disclosure and (optionally) one or more monomer components. The term polymer includes homopolymers, i.e., polymers consisting essentially of a single repeating monomer species. The term polymer also includes copolymers which are formed when two or more different types (or species) of monomers are linked in the same polymer. Copolymers may comprise two or more different monomer species, and include random, block, alternating, segmented, grafted, tapered and other copolymers.

[0034] As used herein, the term "reactive diluent" generally refers to a substance which reduces the viscosity of another substance, such as a monomer or curable resin or polymerizable composition. A reactive diluent may become part of another substance, such as a polymer obtained by a polymerization process. In some examples, a reactive diluent is a curable monomer which, when mixed with a curable resin or polymerizable composition, reduces the viscosity of the resultant formulation, and is incorporated into the polymer that results from polymerization of the formulation.

[0035] The average molecular weight (M) is the average number of repeating units n times the molecular weight or molar mass (Mi) of the repeating unit. The number-average molecular weight (Mn) is the arithmetic mean, representing the total weight of the molecules present divided by the total number of molecules.

[0036] The term "biocompatible," as used herein, refers to a material that does not elicit an immunological rejection or detrimental effect, referred herein as an adverse immune response when it is disposed within an in vivo biological environment. For example, in embodiments a biological marker indicative of an immune response changes less than 10%, or less than 20%, or less than 25%, or less than 40%, or less than 50% from a baseline value when a human or animal is exposed to or in contact with the biocompatible material. Alternatively, immune response may be determined histologically, wherein localized immune response is assessed by visually assessing markers, including immune cells or markers that are involved in the immune response

[0037] 4

[0038] #11356484.1pathway, in and adjacent to the material. In an aspect, a biocompatible material or device does not observably change immune response as determined histologically. In some embodiments, the disclosure provides biocompatible devices configured for long-term use, such as on the order of weeks to months, without invoking an adverse immune response. Biological effects may be initially evaluated by measurement of cytotoxicity, sensitization, irritation and intracutaneous reactivity, acute systemic toxicity, pyrogenicity, subacute / sub-chronic toxicity and / or implantation. Biological tests for supplemental evaluation include testing for chronic toxicity.

[0039] "Bioinert" refers to a material that does not elicit an immune response from a human or animal when it is disposed within an in vivo biological environment. For example, a biological marker indicative of an immune response remains substantially constant (plus or minus 5% of a baseline value) when a human or animal is exposed to or in contact with the bioinert material. In some embodiments, the disclosure provides bioinert devices.

[0040] When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and sub-combinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer, or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomer and enantiomer of the compound described individually or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.

[0041] It is noted that as used herein and in the appended claims, the singular forms "a", "an", and "the" include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to "a monomer" includes a plurality of such monomers and equivalents thereof known to those skilled in the art, and so forth. As well, the terms "a" (or "an"), "one or more" and "at least one" can be used interchangeably herein. It is also to be noted that the terms "comprising", "including", and "having" can be used interchangeably.

[0042] As used herein, the term "group" or "moiety" may refer to a reactive functional group of a chemical compound. Groups of the present compounds refer to an atom or a collection of atoms that are a part of the compound. Groups of the present disclosure may be attached to other atoms

[0043] 5

[0044] #11356484.1of the compound via one or more covalent bonds. Groups may also be characterized with respect to their valence state. The present disclosure includes groups characterized as monovalent, divalent, trivalent, etc. valence states.

[0045] As used herein, the term "substituted" refers to a compound (e.g., an alkyl chain) wherein a hydrogen is replaced by another reactive functional group or atom, as described herein.

[0046] Oligomer Compounds and Polymerizable Compositions

[0047] Some embodiments provide an oligomer that is useful for inclusion in a polymerizable composition. That is, the oligomers of the present disclosure can be combined with one or more types of reactive diluents and other components (e.g., photoinitiators) to produce a useful polymerizable composition. The polymerizable compositions of the present disclosure, in turn, can be used to produced polymers or polymer films via 3D printing.

[0048] One embodiment provides a polymerizable composition comprising:

[0049] a) an oligomer having an aliphatic polyester backbone and 2 or more polymerizable reactive groups at each terminal end of the aliphatic polyester backbone;

[0050] b) an initiator;

[0051] c) a reactive diluent; and

[0052] d) an amine synergist.

[0053] Accordingly, one embodiment provides an oligomer having (a) an aliphatic polyester backbone and (b) 2 or more polymerizable reactive groups at each terminal end of the aliphatic polyester backbone.

[0054] In some embodiments, the oligomer has the following structure:

[0055]

[0056] wherein:

[0057] X1and X2are, at each occurrence independently -C(=O)-O-, -O-C(=O)-, -O-, -S-, -O-C(=O)-O-, -C(=O)-O-C(=O)-, -NH-C(=O)-O-, -O-C(=O)-NH-, -C(=O)-NH-C(=O)-, or -NH-C(=O)-NH-;

[0058] R1and R2are each independently an end group comprising two or more polymerizable reactive groups;

[0059] L1, L2, and L3are, at each occurrence, independently a C1-C12 alkylene; and n is an integer ranging from 1 to 100.

[0060] 6

[0061] #11356484.1In some embodiments, n is an integer ranging from 5 to 10, 5 to 20, 5 to 30, 10 to 20, 10 to 30, 15 to 20, 15 to 30, 20 to 30, or 25 to 30. In some embodiments, n is an integer ranging from 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, or 10 to 20. In some embodiments, n is an integer ranging from 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, or 20 to 30.

[0062] In some embodiments, the oligomer has the following structure:

[0063]

[0064] wherein:

[0065] R1and R2are each independently an end group comprising two or more polymerizable reactive groups;

[0066] L1, L2, and L3are, at each occurrence, independently a C1-C12 alkylene; and n is an integer ranging from 1 to 100.

[0067] In some embodiments, R1, R2, or both are connected to the remainder of the oligomer via a urethane or carbamate functional group (i.e., -NH-C(=O)-O- or -O-C(=O)-NH-). In some embodiments, R1, R2, or both are connected to the remainder of the oligomer via an ester functional group (i.e., -O-C(=O)- or -C(=O)-O-). In some embodiments, R1, R2, or both are connected to the remainder of the oligomer via a urea functional group (i.e., -NH-C(=0)-NH-). In some embodiments, the oxygen molecule shown in the structure of the oligomer is a part of the urethane functional group or the ester functional group.

[0068] In certain embodiments, L1is C4-C8 alkylene. In some embodiments, L1is, at each occurrence, independently Ce-Cio alkylene. In certain embodiments, L1is, at each occurrence, independently branched Ce-Cio alkylene. In some embodiments, L1at each occurrence has the following structure:

[0069]

[0070] In some embodiments, L1is unbranched and unsubstituted Ce alkylene. In certain embodiments, L1is unbranched and unsubstituted C4-C8 alkylene.

[0071] In some embodiments, L2is, at each occurrence, independently C4-C12 alkylene. In some embodiments, L2is, at each occurrence, independently unbranched and unsubstituted C4-C12 alkylene. In some embodiments, L2is, at each occurrence, unbranched and unsubstituted Cs alkylene.

[0072] 7

[0073] #11356484.1In certain embodiments, L3is, at each occurrence, independently Ce-Cio alkylene. In some embodiments, L3is, at each occurrence, independently branched Ce-Cio alkylene. In certain embodiments, L3at each occurrence has the following structure:

[0074]

[0075] In some embodiments, L1and each occurrence of L3are the same.

[0076] In some embodiments, R1, R2, or both are connected to the aliphatic polyester backbone by an ester functional group, a urea functional group, or a urethane functional group.

[0077] In certain embodiments, R1, R2, or both comprise at least one of the following structures:

[0078]

[0079] In some embodiments, R1, R2, or both have the following structure:

[0080] >

[0081]

[0082] wherein:

[0083]

[0084] is, at each occurrence, independently an optionally substituted Cs-Cs cycloalkylene, an optionally substituted phenylene, an optionally substituted phenylene-Ci-C4 alkylene, or an optionally substituted diphenylmethylene;

[0085] X3is, at each occurrence, independently -C(=O)-O-, -O-C(=O)-, -NH-, -O-, -NH- C(=O)-, -C(=0)-NH-, -S-, -S(=O), -S(=O)2-, -O-C(=O)-O-, -C(=O)-O-C(=O)-, -NH-C(=0)-0-, -0-C(=0)-NH-, -C(=0)-NH-C(=0)-, or -NH-C(=0)-NH-;

[0086] L4is, at each occurrence, independently a direct bond or C1-C4 alkylene;

[0087] #11356484.1L5is, at each occurrence, independently C1-C4 alkylene;

[0088] R3is, at each occurrence, independently hydrogen, halo, or -CH3.

[0089] In some embodiments, R1, R2, or both have the following structure:

[0090]

[0091] wherein:

[0092]

[0093] is, at each occurrence, independently an optionally substituted C3-C8 cycloalkylene, an optionally substituted phenylene, an optionally substituted phenylene-Ci-C4 alkylene, or an optionally substituted diphenylmethylene;

[0094] L4is, at each occurrence, independently a direct bond or C1-C4 alkylene;

[0095] L5is, at each occurrence, independently C1-C4 alkylene;

[0096] R3is, at each occurrence, independently hydrogen, halo, or -CH3.

[0097] In certain embodiments, R1, R2, or both have the following structure:

[0098]

[0099] In some embodiments, L4is methylene. In certain embodiments, L4is ethylene, propylene, or butylene.

[0100] In certain embodiments,

[0101]

[0102] is optionally substituted with one or more methyl

[0103] substituents. In some embodiments, ( —A) is cyclohexylene. In some embodiments, (A) has the following structure:

[0104]

[0105] In certain embodiments, -U? 4-( M?- has one of the following structures:

[0106] 9

[0107] #11356484.1

[0108]

[0109] In some embodiments, the oligomer has the following structure:

[0110]

[0111] wherein:

[0112] Rlaand R2aeach have the following structure:

[0113]

[0114] nl is an integer ranging from 1 to 50.

[0115] In some embodiments, nl is an integer ranging from 20 to 40.

[0116] In some embodiments, R1, R2, or both have the following structure:

[0117]

[0118] wherein:

[0119] L4is, at each occurrence, independently a direct bond or C1-C4 alkylene;

[0120] L5is, at each occurrence, independently C1-C4 alkylene;

[0121] 10

[0122] #11356484.1R3is, at each occurrence, independently hydrogen, halo, or -CH3.

[0123] In certain embodiments, the oligomer has a viscosity ranging from 10,000 to 50,000 cP (e.g., at 55°C, 45°C, 30°C, or 25°C). In some embodiments, the oligomer has a viscosity ranging from 10,000 to 25,000 cP (e.g., at 55°C, 45°C, 30°C, or 25°C). In certain embodiments, the oligomer has a viscosity ranging from 20,000 to 50,000 cP (e.g., at 55°C, 45°C, 30°C, or 25°C).

[0124] In some embodiments, the oligomer has a molecular weight greater than 1500 g / mol. In certain embodiments, the oligomer has a molecular weight greater than 2000 g / mol. In some embodiments, the oligomer has a molecular weight greater than 5000 g / mol. In some embodiments, the oligomer has a molecular weight greater than 7,500 g / mol. In certain embodiments, the oligomer has a molecular weight greater than 10,000 g / mol. In some embodiments, the oligomer has a molecular weight greater than 12,500 g / mol.

[0125] Methods of Preparing 3D Printed Articles

[0126] One embodiment provides a method comprising:

[0127] preparing the polymerized 3D printed article by an additive manufacturing process, the process comprising:

[0128] providing a polymerizable D printed article with the polymer.

[0129] In some embodiments, the method further comprises heating the polymerizable composition to a processing temperature. For example, the processing temperature is less than 60°C. In some specific embodiments, the processing temperature is less than 40°C, less than 35°C, less than 30°C, or less than 27°C.

[0130] In some embodiments, the method further comprises receiving a file containing instructions for fabrication of a dental appliance.

[0131] In some embodiments, the additive manufacturing process is a 3D printing process. In some embodiments, the polymerized 3D printed article is a medical device. For example, the medical device is an orthodontic appliance.

[0132] In some embodiments, the polymerizable composition further comprises an initiator. For example, the initiator comprises a photoinitiator. In some specific embodiments, the photoinitiator comprises a free radical photoinitiator. In some other specific embodiments, the photoinitiator comprises a photoionic initiator. For example, the photoionic initiator includes photobase and photoacid generators. In some embodiments, the initiator comprises a thermal initiator. For example, the thermal initiator comprises azobi si sobutyronitrile, 2,2'-azodi(2-methylbutyronitrile), 3, 3 -dimethyl- 1 -phenyltriazene (BTAM), 3,3-diethyl-l-phenyltriazene

[0133] 11

[0134] #11356484.1(BTAE), 2,2,6,6-tetramethyl-l-(phenyldiazenyl)piperidine (BTACM), benzoyl peroxide (BPO), di-tert-butyl peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide, or a combination thereof.

[0135] In some embodiments, the polymerizable composition further comprising one or more reagents selected from the group consisting of a crosslinking modifier, a glass transition temperature modifier, a toughness modifier, a polymerization catalyst, a polymerization inhibitor, a thermal stabilizer, a light stabilizer, a light blocker, a plasticizer, a surface energy modifier, a pigment, a dye, a filler, a biologically significant chemical, a carrier liquid, and combinations thereof.

[0136] In some embodiments, the one or more crosslinking modifier, glass transition temperature modifier, toughness modifier, polymerization catalyst, polymerization inhibitor, light blocker, plasticizer, surface energy modifier, pigment, dye, filler, and biologically significant chemical are solids at room temperature or up to 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, 150 °C, or equal to or greater than about 150 °C.

[0137] In some embodiments, the polymerized 3D printed article is a medical device. For example, the medical device is an orthodontic appliance. In some embodiments, the orthodontic appliance is a dental aligner, a dental expander, or a dental spacer.

[0138] Polymerizable Compositions

[0139] The present disclosure provides polymerizable compositions (also referred to as "curable resins") that can comprise a plurality (e.g., >1) of polymerizable components. A curable resin herein can be a photo-curable resin, a thermo-curable resin, or a combination thereof. As described herein, such polymerizable components can include one or more species of polymerizable compounds of the present disclosure (e.g., 1, 2, 3, or more different species), one or more species of polymerizable monomers (e.g., reactive diluents), and one or more species of telechelic oligomers and / or polymers (e.g., toughness modifiers). The curable resins provided herein can comprise lower amounts (e.g., per weight or volume) of polymerizable monomers (e.g., reactive diluents) compared to conventional resins, and instead contain one or more species of polymerizable compounds of the present disclosure. In some embodiments, however, no or only low amounts (e.g., 5% w / w or less) of a reactive diluent may be used. Resins provided herein can form polymeric materials with advantageous mechanical properties, reduced leaching of (e.g., unreacted) resin components (e.g., monomers) from the cured material, and an increased

[0140] 12

[0141] #11356484.1phase separation while providing a more continuous and uniform polymer matrix. The polymerizable composition can be a 3D printing resin or a coating.

[0142] In some embodiments, the polymer coating is a thin coating on the outside of a printed object. In some embodiments, the polymer coating is applied before any curing, after a preliminary curing step, or to a fully cured article. In some embodiments, the polymer coating fully adheres to a polymeric article or fully cured object. In some embodiments, the polymer coating provides scratch resistance, wear resistance, decreases extractables, reduces surface tackiness, eliminates the need for solvent washing or extractions, or combinations thereof.

[0143] One embodiment provides a polymerizable composition comprising (i) an initiator, (ii) the oligomer of the disclosure, and (iii) a reactive diluent. Another embodiment provides a polymerizable composition comprising (i) an initiator, (ii) the oligomer of the disclosure, (iii) a reactive diluent, and (iv) an amine synergist.

[0144] In some embodiments, the reactive diluent has the following structure:

[0145] <

[0146]

[0147] wherein:

[0148] X is O, S, NR8, or SiR9R10;

[0149] R4ais H, substituted or unsubstituted C1-3 alkyl, or halogen;

[0150] R4bis optionally substituted C1-6 alkyl, optionally substituted C1-6 heteroalkyl, optionally substituted C1-6 carbonyl, optionally substituted C1-6 carboxy, optionally substituted C3-C8 cycloalkyl, optionally substituted 3-8 membered heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0151] R5, R6, and R7are each independently H, optionally substituted C1-6 alkyl, optionally substituted C1-6 heteroalkyl, optionally substituted C1-6 alkoxy, optionally substituted C1-6 thioalkoxy, optionally substituted C1-6 carbonyl, optionally substituted C1-6 carboxy, or -Y-(Clfcjn-R11; or R6and R7together form a 4-, 5-, 6-, 7-, or 8-membered ring selected from optionally substituted C4-8 cycloalkyl, optionally substituted 4-8 membered heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;

[0152] wherein Y is O, S, NH, or C(O)O;

[0153] n is an integer from 0 to 6;

[0154] 13

[0155] #11356484.1R8, R9, and R10are independently H or optionally substituted Ci-6 alkyl; and R11is optionally substituted C3-8 cycloalkyl, optionally substituted 3-8 membered heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0156] In certain embodiments, the reactive diluent having one of the following structures:

[0157]

[0158] In some embodiments, the reactive diluent has one of the following structures:

[0159] 14

[0160] #11356484.1

[0161]

[0162] In certain embodiments, the reactive diluent has the following structure:

[0163]

[0164] In some embodiments, the reactive diluent having one of the following structures:

[0165]

[0166] In some embodiments, the polymerizable composition comprises a thermal initiator, a photoinitiator, or both. In some embodiments, the photoinitiator is a type 1 photoinitiator. In some embodiments, the composition does not include any initiator. In some embodiments, the polymerizable composition is treated with an activating agent such as heat or light. In some embodiments, the initiator increases the speed of curing step. In some embodiments, the initiator is present at a low concentration, for instance, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, less than 0.025 wt%, or less than 0.01 wt%. In some embodiments, the initiators are oligomeric and / or polymeric or attached to oligomers and / or polymers.

[0167] 15

[0168] #11356484.1In some embodiments, the amine synergist is an aliphatic amine methacylate. In some embodiments, the amine synergist has the following structure:

[0169]

[0170] wherein:

[0171] R12and R13are each independently Ci-Ce alkyl; and

[0172] R14is hydrogen or methyl.

[0173] In some embodiments, the amine synergist has one of the following structures:

[0174]

[0175] In some embodiments, short wavelengths of UV are used to initiate a polymerization. In some embodiments, a reaction is initiated with UV light at less than 410 nm, less than 405 nm, less than 400 nm, less than 375 nm, less than 360 nm, less than 350 nm, less than 330 nm, less than 300 nm. In some embodiments, a reaction is initiated with UV light ranging from 400 to 410 nm. In some embodiments, a reaction is initiated with UV light at a wavelength of 405 nm.

[0176] When photoinitiators are used, any wavelength to which the photoinitiator is sensitive to can be used and includes the whole visible spectrum and even into the IR spectrum. Thermal initiators can be activated with various forms of heat, including infrared, hot air, hot gas (e.g., in an oven), hot liquids, ultrasonic energy, and direct contact with hot materials. Typically, thermal polymerizations are performed at temperatures above 60 °C, and more preferably above 80 °C, or 100 °C, as such formulations have higher shelf and vat lives. However, in some embodiments, the curing step is performed at room temperature.

[0177] In some embodiments, the polymerizable composition is a photocurable composition. In certain embodiments, the polymerizable composition is a thermal curable composition. In some embodiments, the polymerizable composition is a combination of a photocurable composition and a thermal curable composition. In some embodiments, the polymerizable composition is a 3D printing resin. In some embodiments the polymerizable composition is a coating.

[0178] In some embodiments, the concentration of oligomer ranges from 25-65 wt%. In certain embodiments, the concentration of oligomer ranges from 5-90 wt%, 5-80 wt%, 5-70 wt%, 5-60 wt%, 5-50 wt%, 5-40 wt%, 5-30 wt%, 5-20 wt%, 5-10 wt%, 10-70 wt%, 20-70 wt%, 30-70 wt%,

[0179] 16

[0180] #11356484.140-70 wt%, 50-70 wt%, 50-60 wt%, or 30-50 wt%. In some embodiments, the concentration of oligomer ranges from 30-60 wt%.

[0181] In some embodiments, the concentration of reactive diluent ranges from 25-65 wt%. In certain embodiments, the concentration of reactive diluent ranges from 5-90 wt%, 5-80 wt%, 5-70 wt%, 5-60 wt%, 5-50 wt%, 5-40 wt%, 5-30 wt%, 5-20 wt%, 5-10 wt%, 10-70 wt%, 20-70 wt%, 30-70 wt%, 40-70 wt%, 50-70 wt%, 50-60 wt%, or 30-50 wt%. In some embodiments, the concentration of reactive diluent ranges from 30-60 wt%.

[0182] In certain embodiments, the polymerizable composition comprises 0.01-10 wt% of the initiator. In some embodiments, the polymerizable composition comprises 0.05-10 wt%, 0.1-10 wt%, 0.5-10 wt%, 1.0-10 wt%, 5-10 wt%, 7.5-10 wt%, 0.01-5 wt%, 0.01-2 wt%, 0.01-1 wt%, or 0.01-0.5 wt% of the initiator.

[0183] In some embodiments, the oligomer is present at a concentration of 10-70 wt%, the reactive diluent is present at a concentration of 25-80 wt%, and the initiator is present at a concentration of 0.5-5 wt%. In some embodiments, the oligomer is present at a concentration of 20-50 wt%, the reactive diluent is present at a concentration of 30-75 wt%, and the initiator is present at a concentration of 0.75-3 wt%.

[0184] In some embodiments, the amine synergist is present at a concentration of 0.1-5.0 wt%. In some embodiments, the amine synergist is present at a concentration of 0.25-2.0 wt%.

[0185] In some embodiments, the oligomer is present at a concentration of 10-70 wt%, the reactive diluent is present at a concentration of 25-80 wt%, the amine synergist is present at a concentration of 0.1-5.0 wt%, and the initiator is present at a concentration of 0.5-5 wt%. the oligomer is present at a concentration of 10-70 wt%, the reactive diluent is present at a concentration of 25-80 wt%, the amine synergist is present at a concentration of 0.25-2.0 wt%, and the initiator is present at a concentration of 0.5-5 wt%.

[0186] In some embodiments, the reactive diluent is a solid at room temperature, or up to 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, 150 °C, or equal to or greater than about 150 °C.

[0187] In some embodiments, the polymerizable composition (e.g. 3D printing resin) is capable of being 3D printed at a printing temperature greater than 25 °C. In certain embodiments, the printing temperature is at least 30 °C, 40 °C, 50 °C, 60 °C, 80 °C, or 100 °C. In some embodiments, the printing temperature is at least 30 °C, 40 °C, 50 °C, 60 °C, 80 °C, 100 °C, or 25-80°C. in some embodiments, the printing temperature is 25-80°C. In some embodiments, the polymerizable composition has a viscosity from 30 cP to 50,000 cP at a printing temperature. In

[0188] 17

[0189] #11356484.1some embodiments, the polymerizable composition has a viscosity from 500 cP to 5,000 cP at a printing temperature. In certain embodiments, the printing temperature is from 25 °C to 150 °C. In some embodiments, the polymerizable composition (e.g. 3D printing resin, coating) comprises less than 20 wt% hydrogen bonding units. In certain embodiments, the polymerizable composition (e.g. 3D printing resin, coating) is a liquid at a temperature from about 40 °C to about 100 °C. In certain embodiments, the polymerizable composition (e.g. 3D printing resin, coating) is a liquid at a temperature of above about 40 °C with a viscosity less than about 20 PaS. In certain embodiments, the polymerizable composition (e.g. 3D printing resin, coating) is a liquid at a temperature of above about 40 °C with a viscosity less than about 5 PaS. In some embodiments, the polymerizable composition is a liquid at a temperature of above about 40 °C with a viscosity less than about 1 PaS. In some embodiments, at least a portion of the polymerizable composition melts at a temperature between about 60 °C and about 0 °C.

[0190] In various embodiments, a 3D printing resin or polymerizable composition herein is a photo-curable resin. Such photo-curable resin described herein can further comprise one or more photoinitiators. Such photoinitiator, when activated with light of an appropriate wavelength (e.g., UV / VIS) can initiate a polymerization reaction (e.g., during photo-curing) between monomers and themselves and / or other potentially polymerizable components that may be present in the photo-curable resin, to form a polymeric material as further described herein. Generally, photoinitiators described in the present disclosure can include those that can be activated with light and initiate polymerization of the polymerizable components of the formulation. A "photoinitiator", as used herein, may generally refer to a compound that can produce radical species and / or promote radical reactions upon exposure to radiation (e.g., UV or visible light).

[0191] In some embodiments, a photo-curable resin herein further comprises 0.05 to 1 wt%, 0.05 to 2 wt%, 0.05 to 3 wt%, 0.05 to 4 wt%, 0.05 to 5 wt%, 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 3 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 6 wt%, 0.1 to 7 wt%, 0.1 to 8 wt%, 0.1 to 9 wt%, or 0.1 to 10 wt%, based on the total weight of the composition, of a photoinitiator. In some embodiments, the photoinitiator is a free radical photoinitiator. In certain embodiments, the free radical photoinitiator comprises an alpha hydroxy ketone moiety (e.g., 2-hydroxy-2-m ethylpropiophenone or 1 -hydroxy cyclohexyl phenyl ketone), an alpha-amino ketone (e.g., 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone or 2-methyl- 1 -[4-(methylthio)phenyl]-2-morpholinopropan-l-one), 4-methyl benzophenone, an azo compound (e.g., 4,4 '-Azobi s(4-cyanovaleric acid), l,l'-Azobis(cyclohexanecarbonitrile, Azobisisobutyronitrile, 2,2 '-Azobi s(2-methylpropionitrile), or 2,2'-Azobis(2-methylpropionitrile)), an inorganic peroxide, an organic

[0192] 18

[0193] #11356484.1peroxide, or any combination thereof. In some embodiments, the composition comprises a photoinitiator comprising SpeedCure TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate).

[0194] In some embodiments, a photo-curable composition comprises a photoinitiator selected from a benzophenone, a mixture of benzophenone and a tertiary amine containing a carbonyl group which is directly bonded to at least one aromatic ring, and an Irgacure (e.g., Irgacure 907 (2-methyl-l-[4-(methylthio)-phenyl]-2-morpholino-propanone-l) or Irgacure 651 (2,2-dimethoxy-l,2-diphenylethan-l-one). In some embodiments, the photoinitiator comprises an acetophenone photoinitiator (e.g, 4'-hydroxyacetophenone, 4'0phenoxyacetophenone, d'ethoxyaceto-phenone), a benzoin, a benzoin derivative, a benzil, a benzil derivative, a benzophenone (e.g, 4-benzoylbiphenyl, 3,4-(dimethylamino)benzophenone, 2-m ethylbenzophenone), a cationic photoinitiator (e.g., diphenyliodonium nitrate, (4-iodophenyl)diphenylsulfonium tritiate, triphenyl sulfonium tritiate), an anthraquinone, a quinone (e.g., camphorquinone), a phosphine oxide, a phosphinate, 9,10-phenanthrenequinone, a thioxanthone, any combination thereof, or any derivative thereof.

[0195] In some embodiments, the photoinitiator can have a absorbance between 200 and 300 nm, between 300 and 400 nm, between 400 and 500 nm, between 500 and 600 nm, between 600 and 700 nm, between 700 and 800 nm, between 800 and 900 nm, between 150 and 200 nm, between 200 and 250 nm, between 250 and 300 nm, between 300 and 350 nm, between 350 and 400 nm, between 400 and 450 nm, between 450 and 500 nm, between 500 and 550 nm, between 550 and 600 nm, between 600 and 650 nm, between 650 and 700 nm, or between 700 and 750 nm. In some embodiments, the photoinitiator has an absorbance between 300 to 500 nm.

[0196] In some embodiments, the polymerizable composition further comprises one or more reagents selected from the group consisting of a crosslinking modifier, a glass transition temperature modifier, a toughness modifier, a polymerization catalyst, a polymerization inhibitor, a light blocker, a plasticizer, a surface energy modifier, a pigment, a dye, a filler, a biologically significant chemical, a solvent, and combinations thereof.

[0197] In some embodiments, the photo-curable resin comprises 0-25 wt% of the crosslinking modifier, the crosslinking modifier having a number-average molecular weight equal to or less than 1,500 Da. In some embodiments, the photo-curable resin comprises from 0 to 10 wt%, from 0 to 9 wt%, from 0 to 8 wt%, from 0 to 7 wt%, from 0 to 6 wt%, from 0 to 5 wt%, from 0 to 4 wt%, from 0 to 3 wt%, from 0 to 2 wt%, from 0 to 1 wt%, or from 0 to 0.5 wt% of the light blocker.

[0198] 19

[0199] #11356484.1In some embodiments, a small molecule additive (e.g., plasticizer) only partially solubilizes one or more components of the photocurable resin such as less than 50 wt%, less than 20 wt%, less than 10 wt%, or less than 5 wt% of one or more of the components. In some embodiments, the solvent is a solid at room temperature or melts at temperatures greater than 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, 150 °C, or equal to or greater than about 150 °C. In some embodiments, the solvent is vanillin, menthol, cinnamic acid, tartaric acid, guaiacol, syringol, and other flavor, aroma, edible compounds, or a combination thereof.

[0200] In some embodiments, the added resin component (e.g., a crosslinking modifier, a polymerization catalyst, a polymerization inhibitor, a glass transition temperature modifier, a light blocker, a thermal stabilizer, a light stabilizer, a plasticizer, a solvent, a surface energy modifier, a pigment, a dye, a filler, or a biologically significant chemical) is functionalized so that it can be incorporated into the polymeric material so that it cannot readily be extracted from the final cured material. In certain embodiments, the polymerization catalyst, polymerization inhibitor, light blocker, plasticizer, surface energy modifier, pigment, dye, and / or filler, are functionalized to facilitate their incorporation into the cured polymeric material.

[0201] In some embodiments, a resin herein comprises a component in addition to a polymerizable compound described herein that can alter the glass transition temperature of the cured polymeric material. In such instances, a glass transition temperature modifier (also referred to herein as a Tgmodifier or a glass transition modifier) can be present in a photo-curable composition from about 0 to 50 wt%, based on the total weight of the composition. The Tgmodifier can have a high glass transition temperature, which leads to a high heat deflection temperature, which can be necessary to use a material at elevated temperatures. In some embodiments, the curable composition comprises 0 to 80 wt%, 0 to 75 wt%, 0 to 70 wt%, 0 to 65 wt%, 0 to 60 wt%, 0 to 55 wt%, 0 to 50 wt%, 1 to 50 wt%, 2 to 50 wt%, 3 to 50 wt%, 4 to 50 wt%, 5 to 50 wt%, 10 to 50 wt%, 15 to 50 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt%, 35 to 50 wt%, 0 to 40 wt%, 1 to 40 wt%, 2 to 40 wt%, 3 to 40 wt%, 4 to 40 wt%, 5 to 40 wt%, 10 to 40 wt%, 15 to 40 wt%, or 20 to 40 wt% of a Tgmodifier. In certain embodiments, the curable composition comprises 0-50 wt% of a glass transition modifier. In some instances, the number average molecular weight of the Tgmodifier is 0.4 to 5 kDa. In some embodiments, the number average molecular weight of the Tgmodifier is from 0.1 to 5 kDa, from 0.2 to 5 kDa, from 0.3 to 5 kDa, from 0.4 to 5 kDa, from 0.5 to 5 kDa, from 0.6 to 5 kDa, from 0.7 to 5 kDa, from 0.8 to 5 kDa, from 0.9 to 5 kDa, from 1.0 to 5 kDa, from 0.1 to 4 kDa, from 0.2 to 4 kDa, from 0.3 to 4 kDa, from 0.4 to 4 kDa, from 0.5 to 4 kDa, from 0.6 to 4 kDa, from 0.7 to 4 kDa, from 0.8 to 4

[0202] 20

[0203] #11356484.1kDa, from 0.9 to 4 kDa, from 1 to 4 kDa, from 0.1 to 3 kDa, from 0.2 to 3 kDa, from 0.3 to 3 kDa, from 0.4 to 3 kDa, from 0.5 to 3 kDa, from 0.6 to 3 kDa, from 0.7 to 3 kDa, from 0.8 to 3 kDa, from 0.9 to 3 kDa, or from 1 to 3 kDa.

[0204] A polymerizable compound of the present disclosure (which can, in some cases, act by itself as a Tgmodifier) and a separate Tgmodifier compound can be miscible and compatible in the methods described herein. When used in the subject compositions, the Tgmodifier may provide for high Tgand strength values, sometimes at the expense of elongation at break. In some cases, a toughness modifier may provide for high elongation at break and toughness via strengthening effects. In some embodiments, the polymerizable composition comprises high amounts of toughness modifiers, while maintaining high values for strength and Tg.

[0205] In some embodiments, the polymerizable composition has a viscosity less than or equal to 30,000 cP, less than or equal to 25,000 cP, less than or equal to 20,000 cP, less than or equal to 19,000 cP, less than or equal to 18,000 cP, less than or equal to 17,000 cP, less than or equal to 16,000 cP, less than or equal to 15,000 cP, less than or equal to 14,000 cP, less than or equal to 13,000 cP, less than or equal to 12,000 cP, less than or equal to 11,000 cP, less than or equal to 10,000 cP, less than or equal to 9,000 cP, less than or equal to 8,000 cP, less than or equal to 7,000 cP, less than or equal to 6,000 cP, or less than or equal to 5,000 cP at 25 °C. In some embodiments, the polymerizable composition has a viscosity less than 15,000 cP at 25 °C.

[0206] In some embodiments, the polymerizable composition has a viscosity less than or equal to 100,000 cP, less than or equal to 90,000 cP, less than or equal to 80,000 cP, less than or equal to 70,000 cP, less than or equal to 60,000 cP, less than or equal to 50,000 cP, less than or equal to 40,000 cP, less than or equal to 35,000 cP, less than or equal to 30,000 cP, less than or equal to 25,000 cP, less than or equal to 20,000 cP, less than or equal to 15,000 cP, less than or equal to 10,000 cP, less than or equal to 5,000 cP, less than or equal to 4,000 cP, less than or equal to 3,000 cP, less than or equal to 2,000 cP, less than or equal to 1,000 cP, less than or equal to 750 cP, less than or equal to 500 cP, less than or equal to 250 cP, less than or equal to 100 cP, less than or equal to 90 cP, less than or equal to 80 cP, less than or equal to 70 cP, less than or equal to 60 cP, less than or equal to 50 cP, less than or equal to 40 cP, less than or equal to 30 cP, less than or equal to 20 cP, or less than or equal to 10 cP at a printing temperature. In some embodiments, the polymerizable composition has a viscosity from 50,000 cP to 30 cP, from 40,000 cP to 30 cP, from 30,000 cP to 30 cP, from 20,000 cP to 30 cP, from 10,000 cP to 30 cP, or from 5,000 cP to 30 cP at a printing temperature. In some embodiments, the printing temperature is from 0 °C to 25 °C, from 25 °C to 40 °C, from 40 °C to 100 °C, or from 20 °C to

[0207] 21

[0208] #11356484.1150 °C. In some embodiments, the polymerizable composition has a viscosity from 30 cP to 50,000 cP at a printing temperature. In some embodiments, the printing temperature is from 20 °C to 150 °C. In yet other embodiments, the polymerizable composition has a viscosity less than 20,000 cP at a print temperature. In some embodiments, the print temperature is from 10 °C to 200 °C, from 15 °C to 175 °C, from 20 °C to 150 °C, from 25 °C to 125 °C, or from 30 °C to 100 °C. In preferred embodiments, the print temperature is from 20 °C to 150 °C.

[0209] A polymerizable composition of the present disclosure can be capable of being 3D printed at a temperature greater than 25 °C. In some cases, the printing temperature is at least about 30 °C, 40 °C, 50 °C, 60 °C, 80 °C, or 100 °C. As described herein, a photo-polymerizable monomer of this disclosure that can part of the polymerizable composition, can have a low vapor pressure and / or mass loss at the printing temperature, thereby providing improved printing conditions compared to conventional resins used in additive manufacturing.

[0210] In some embodiments, a polymerizable composition herein has a melting temperature greater than room temperature. In some embodiments, the polymerizable composition has a melting temperature greater than 20 °C, greater than 25 °C, greater than 30 °C, greater than 35 °C, greater than 40 °C, greater than 45 °C greater than 50 °C, greater than 55 °C, greater than 60 °C, greater than 65 °C, greater than 70 °C, greater than 75 °C, or greater than 80 °C. In some embodiments, the polymerizable composition has a melting temperature from 20 °C to 250 °C, from 30 °C to 180 °C, from 40 °C to 160 °C, or from 50 °C to 140 °C. In some embodiments, the polymerizable composition has a melting temperature greater than 60 °C. In other embodiments, the polymerizable composition has a melting temperature from 80 °C to 110 °C. In some instances, a polymerizable composition can have a melting temperature of about 80 °C before polymerization, and after polymerization, the resulting polymeric material can have a melting temperature of about 100 °C.

[0211] In certain instances, it may be advantageous that a polymerizable composition is in a liquid phase at an elevated temperature. As an example, a conventional polymerizable composition can comprise polymerizable components that may be viscous at a process temperature, and thus can be difficult to use in the fabrication of objects (e.g., using 3D printing). As a solution for that technical problem, the present disclosure provides polymerizable composition comprising photo-polymerizable components such as monomers described herein that can melt at an elevated temperature, e.g., at a temperature of fabrication (e.g., during 3D printing), and can have a decreased viscosity at the elevated temperature, which can make such resin more applicable and usable for uses such as 3D printing. Hence, in some embodiments,

[0212] 22

[0213] #11356484.1provided herein are polymerizable compositions that are a liquid at an elevated temperature. In some embodiments, the elevated temperature is at or above the melting temperature (Tm) of the polymerizable composition. In certain embodiments, the elevated temperature is a temperature in the range from about 40 °C to about 100 °C, from about 60 °C to about 100 °C, from about 80 °C to about 100 °C, from about 40 °C to about 150 °C, or from about 150 °C to about 350 °C. In some embodiments, the elevated temperature is a temperature above about 40 °C, above about 60 °C, above about 80 °C, or above about 100 °C. In some embodiments, a polymerizable composition herein is a liquid at an elevated temperature with a viscosity less than about 50 PaS, less than 2 about 0 PaS, less than about 10 PaS, less than about 5 PaS, or less than about 1 PaS. In some embodiments, a polymerizable composition herein is a liquid at an elevated temperature of above about 40 °C with a viscosity less than about 20 PaS. In yet other embodiments, a polymerizable composition herein is a liquid at an elevated temperature of above about 40 °C with a viscosity less than about 1 PaS.

[0214] In some embodiments, at least a portion of a polymerizable composition herein has a melting temperature below about 100 °C, below about 90 °C, below about 80 °C, below about 70 °C, or below about 60 °C. In some embodiments, at least a portion of a polymerizable composition herein melts at an elevated temperature between about 100 °C and about 20 °C, between about 90 °C and about 20 °C, between about 80 °C and about 20 °C, between about 70 °C and about 20 °C, between about 60 °C and about 20 °C, between about 60 °C and about 10 °C, or between about 60 °C and about 0 °C.

[0215] In various embodiments, a polymerizable composition herein as well as its photo-polymerizable components can be biocompatible, bioinert, or a combination thereof. In various instances, the photo-polymerizable compounds of a resin herein can have biocompatible and / or bioinert metabolic (e.g., hydrolysis) products.

[0216] A polymerizable composition of the present disclosure can comprise less than about 20 wt% or less than about 10 wt% hydrogen bonding units. In some embodiments, a polymerizable composition herein comprises less than about 15 wt%, less than about 10 wt%, less than about 9 wt%, less than about 8 wt%, less than about 7 wt%, less than about 6 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, or less than about 1 wt% hydrogen bonding units.

[0217] 23

[0218] #11356484.1Polymer or Polymeric Materials

[0219] The present disclosure provides polymeric materials (e.g., a polymeric coating). Such polymeric materials can be generated by curing a curable polymerizable composition described herein. One embodiment provides a polymer formed from the polymerizable composition(s) of any one of the embodiments disclosed herein.

[0220] A polymeric material provided herein can be biocompatible, bioinert, or a combination thereof. In various instances, a polymeric material herein is generated by photo-curing a photo-curable composition described herein. Such photo-curable compositions can comprise one or more polymerizable compounds of the present disclosure.

[0221] In some embodiments, a polymerizable composition herein can be cured by exposing such a composition or resin to electromagnetic radiation of appropriate wavelength. In various embodiments, the present disclosure provides a polymeric material (e.g., a polymeric coating) that can comprise one or more polymeric phases, wherein at least one polymeric phase of the one or more polymeric phases is a crystalline phase. In various embodiments, the present disclosure provides a polymeric material that can comprise one or more polymeric phases, wherein at least one polymeric phase of the one or more polymeric phases is an amorphous phase.

[0222] In some embodiments, the polymeric material (e.g., a polymeric coating) comprises one or more polymer types that may have formed, during curing, from the polymerizable compounds / compositions, telechelic polymers, oligomers, polymerizable monomers / reactive diluents, and / or any other polymerizable component or already be present in the resin before cure. In some instances, such one or more polymer types can include one or more of comprises a homopolymer, a linear copolymer, a block copolymer, an alternating copolymer, a periodic copolymer, a statistical copolymer, a random copolymer, a gradient copolymer, a branched copolymer, a brush copolymer, a comb copolymer, a dendrimer, or any combination thereof. In some cases, the polymeric material comprises a random copolymer. In some embodiments, the polymeric material can comprise poly(ethylene) glycol (PEG), poly(ethylene) glycol diacrylate, PEG-THF, polytetrahydrofuran, poly(tert-butyl acrylate), poly(ethylene-co-maleic anhydride), any derivative thereof, polycaprolactone, copolyesters, polyesters, polyethers, polysulfones, polyamides, polyimides, polyethylene, polypropylene, polyacrylates, polymethacrylates, polyacetals, poly(cyclic olefins), poly(lactic acid), poly(styrene), poly(butadiene), poly(vinyl chloride), or any combination thereof.

[0223] In some embodiments, the polymeric material (e.g., a polymeric coating) comprises an acrylate, an acrylamide, a methacrylamide, an acrylonitrile, a bisphenol acrylate, a carbohydrate,

[0224] 24

[0225] #11356484.1a fluorinated acrylate, a maleimide, an acrylate, 4-acetoxyphenethyl acrylate, acryloyl chloride, 4-acryloylmorpholine, 2-(acryloyloxy)ethyl]-trimethylammonium chloride, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, benzyl 2-propylacrylate, butyl acrylate, tert-butyl acrylate, 2[(butylamino)carbonyl]-oxy]ethyl acrylate, tert-butyl 2-bromoacrylate, 2-carboxyethyl acrylate, 2-chloroethyl acrylate, 2-(diethylamino)-ethyl acrylate, di(ethylene glycol) ethyl ether acrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl acrylate, dipentaerythriol penta- / hexa-acrylate, ethyl acrylate, 2-ethylacryloyl chloride, ethyl 2-(bromomethyl)acrylate, ethyl cis-(beta-cyano)acrylate, ethylene glycol dicyclopentenyl ether acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, ethyl 2-ethylacrylate, 2-ethylexyl acrylate, ethyl 2-propylacrylate, ethyl 2-(trimethylsilylmethyl)acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy ethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, isobutyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetamidoacrylate, methyl acrylate, a methylene mal onate (e.g., dibutyl methylene mal onate, dihexyl methylene malonate, or dicyclohexyl methylene malonate), a methylene malonate macromerer (e.g, a polyester of 2-methylenemal onate such as Forza B3000 XP), methyl a-bromoacrylate, methyl 2-(bromo-methyl)acrylate, methyl 2-(chloromethyl)acrylate, methyl 3-hydroxy-2-methylenebutyrate, methyl 2-(trifluoromethyl)acrylate, octadecyl acrylate, pentabromobenzyl acrylate, penta-bromophenyl acrylate, pentafluorophenyl acrylate, poly(ethylene glycol) diacrylate, poly-(ethylene glycol) methyl ether acrylate, polypropylene glycol) acrylate, epoxidized soybean oil acrylate, 3 -sulfopropyl acrylate, tetrahydrofuryl acrylate, 2-tetrahydropyranyl acrylate, 3 -(trimethoxy silyl)propyl acrylate, 3, 5, 5 -trimethylhexyl acrylate, 10-undecenyl acrylate, urethane acrylate, urethane acrylate methacrylate, tri cylcodecane diacrylate, isobomyl acrylate, a methacrylate, allyl methacrylate, benzyl methacrylate, (2-boc-amino)ethyl methacrylate, tert-butyl methacrylate, 9H-carbazole-9-ethylmethacrylate, 3-chloro-2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 1,10-decam ethylene glycol dimethacrylate, ethylene glycol dicyclopentenyl ether methacrylate, ethylene glycol methyl ether methacrylate, 2-ethylhexyl methacrylate, furfuryl methacrylate, glycidyl methacrylate, glycosyloxyethyl methacrylate, hexyl methacrylate, hydroxybutyl methacrylate, 2-hydroxy-5-N-methacrylamidobenzoic acid, isobutyl methacrylate, methacryloyl chloride, methyl methacrylate, mono-2-methacryloyloxy)ethyl succinate, 2-N-morpholinoethyl methacrylate, 1 -naphthyl methacrylate, pentabromophenyl methacrylate, phenyl methacrylate, pentabromophenyl methacrylate, TEMPO methacrylate, 3 -sulfopropyl methacrylate, tri ethylene glycol methyl ether methacrylate, 2-[(l', l', l'-trifluoro-2'-(trifluoromethyl)-2'0hdroxy)propyl]-3-norbornyl

[0226] 25

[0227] #11356484.1methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, (trimethylsilyl)methacrylate, vinyl methacrylate, isobomyl methacrylate, bisphenol A dimethacrylate, an Omnilane OC, tert-butyl acrylate, isodecyl acrylate, tri cyl codecane diacrylate, a polyfunctional acrylate, N,N'-methylenebisacrylamide, 3-(acryloyloxy)-2-hydroxypropyl) methacrylate, bis[2-(methacryloyloxy)ethyl] phosphate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diurethane dimethacrylate, N,N'-ethylenebis(acrylamide), glycerol 1,3 -diglycerolate diacrylate, 1,6-hexanediol diacrylate, hydroxypivalyl hydroxypivalate bis[6-(acryloyloxy)hexanoate], neopentyl glycol diacrylate, pentaerythritol diacrylate, 1,3,6-triacryloyl hexahydro-1, 3, 5-triazine, trimethlolpropane ethoxylate, tris[2-(acryloyloxy)ethyl] isocyanurate, any derivative thereof, or a combination thereof.

[0228] In some embodiments, the polymeric material (e.g., a polymeric coating) herein can comprise one or more reactive functional groups that can allow for further modification of the polymeric material, such as additional polymerization (e.g., post-curing). In some embodiments, polymeric material comprises a plurality of reactive functional groups, and the reactive functional groups can be located at one or both terminal ends of the polymeric material, in-chain, at a pendant (e.g., a side group attached to the polymer backbone), or any combination thereof. Non-limiting examples of reactive functional groups include free radically polymerizable functionalities, photoactive groups, groups facilitating step growth polymerization, thermally reactive groups, and / or groups that facilitate bond formation (e.g., covalent bond formation). In some embodiments, the reactive functional groups comprise an acrylate, a methacrylate, an acrylamide, a vinyl group, a vinyl ether, a thiol, an allyl ether, a norbornene, a vinyl acetate, a maleate, a fumarate, a maleimide, an epoxide, a ring-strained cyclic ether, a ring-strained thioether, a cyclic ester, a cyclic carbonate, a cyclic silane, a cyclic siloxane, a hydroxyl, an amine, an isocyanate, a blocked isocyanate, an acid chloride, an activated ester, a Diels- Alder reactive group, a furan, a cyclopentadiene, an anhydride, a group favorable toward photodimerization (e.g., an anthracene, an acenaphthalene, or a coumarin), a group that photodegrades into a reactive species (e.g., Norrish Type 1 and 2 materials), an azide, a derivative thereof, or a combination thereof.

[0229] In some embodiments, a polymeric material (e.g., a polymeric coating) has a melting temperature equal to or greater than about 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, or equal to or greater than about 150 °C.

[0230] 26

[0231] #11356484.1Properties of Polymer or Polymeric Materials

[0232] A polymeric material of this disclosure formed from the polymerization of a curable resin or polymerizable composition disclosed herein can provide advantageous characteristics compared to conventional polymeric materials. In some instances, a polymeric material can also have low amounts of water uptake and can be solvent resistant. In some cases, a polymeric material can be characterized by one or more of the properties selected from the group consisting of elongation at break, storage modulus, tensile modulus, stress remaining, glass transition temperature, water uptake, hardness, color, transparency, hydrophobicity, lubricity, surface texture, percent crystallinity, phase composition ratio, phase domain size, and phase domain size and morphology. Further, as described herein, the polymeric materials provided herein can be used for a multitude of applications, including 3D printing, to form materials having favorable properties of both elasticity and stiffness. Specifically, a polymeric material of this disclosure can provide excellent flexural modulus, elastic modulus, elongation at break, or a combination thereof.

[0233] Some embodiments provide a polymer (e.g., a polymeric coating) formed from the polymerizable composition of any one of the embodiments disclosed herein. In some embodiments, the polymer has one or more of the following characteristics:

[0234] (A) a storage modulus greater than or equal to 200 MPa;

[0235] (B) a flexural stress and / or flexural modulus of greater than or equal to 1.5 MPa remaining after 24 hours in a wet environment at 37 °C;

[0236] (C) an elongation at break greater than or equal to 5% before and after 24 hours in a wet environment at 37 °C;

[0237] (D) a water uptake of less than 25 wt% when measured after 24 hours in a wet environment at 37 °C;

[0238] (E) transmission of at least 30% of visible light through the polymeric material after 24 hours in a wet environment at 37 °C; and

[0239] (F) comprises a plurality of polymeric phases, wherein at least one polymeric phase of the one or more polymeric phases has a Tgof at least 60 °C, 80 °C, 90 °C, 100 °C, or at least 110 °C.

[0240] In some embodiments, the polymer (e.g., a polymeric coating) is characterized by a water uptake of less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt% when measured after 24 hours in a wet environment at 37 °C.

[0241] 27

[0242] #11356484.1In some embodiments, the polymer has greater than 30%, 40%, 50%, 60%, 80%, 90% or 99% conversion of double bonds to single bonds compared to the polymerizable composition, as measured by FTIR. In some embodiments, the polymer has greater than 90% conversion of double bonds to single bonds compared to the polymerizable composition, as measured by FTIR.

[0243] In certain embodiments, the polymer has an ultimate tensile strength from 10 MPa to 100 MPa, from 15 MPa to 80 MPa, from 20 MPa to 60 MPa, from 10 MPa to 50 MPa, from 10 MPa to 45 MPa, from 25 MPa to 40 MPa, from 30 MPa to 45 MPa, or from 30 MPa to 40 MPa after 24 hours in a wet environment at 37 °C.

[0244] In some embodiments, the polymer is characterized by an elongation at break greater than 10%, an elongation at break greater than 20%, an elongation at break greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break value between 40% and 250% before and after 24 hours in a wet environment at 37 °C using pull rates of 1.7 mm / min or 510 mm / min.

[0245] In certain embodiments, the polymer is characterized by a storage modulus of 0.1 MPa to 4000 MPa, a storage modulus of 300 MPa to 3000 MPa, or a storage modulus of 750 MPa to 3000 MPa after 24 hours in a wet environment at 37 °C using samples that are 500 micrometers to 1000 micrometers thick.

[0246] In some embodiments, the polymer has a flexural stress, a flexural modulus, or a flexural stress and flexural modulus of 400 MPa or more, 300 MPa or more, 200 MPa or more, 180 MPa or more, 160 MPa or more, 120 MPa or more, 100 MPa or more, 80 MPa or more, 70 MPa or more, 60 MPa or more, after 24 hours in a wet environment at 37 °C.

[0247] In certain embodiments, at least 40%, 50%, 60%, or 70% of visible light passes through the polymer after 24 hours in a wet environment at 37 °C. In some embodiments, the polymer is biocompatible, bioinert, or a combination thereof.

[0248] One embodiment provides a polymeric film comprising a polymer of any one of the embodiments disclosed herein. In some embodiments, the polymeric film has a thickness of at least 100 pm and not more than 3 or 4 mm. In some embodiments, the polymeric film has a thickness of at least 20, 40, 60, 80, 100, 120, 140, 160, 180, 200 pm and not more than 0.5, 1, 2, 3, 3.5, 4, 4.5, 5, 5.5, 6, or 7 mm.

[0249] One embodiment provides an orthodontic appliance comprising the polymer of any one of the embodiments disclosed herein or the polymeric film of any one of the embodiments herein. In some embodiments, the orthodontic appliance is a dental appliance (e.g., a dental aligner, a dental expander, or a dental spacer).

[0250] 28

[0251] #11356484.1Some embodiments provide a device comprising the polymer of any of the embodiments disclosed herein. In some embodiments, the device is a dental appliance. In some embodiments, the device is a dental aligner, a dental expander, or a dental spacer.

[0252] In various embodiments, a polymeric material herein can comprise or consist of a high toughness, e.g., through a tough polymer matrix, and the difference (or delta) between the elastic modulus measured at different strain rates (e.g., at 1.7 mm / min and 510 mm / min) can be low, e.g., lower than 80%, 70%, 60%, 50%, 40%, or lower than 30%, which can be an indication for a polymeric phase separation within the material.

[0253] In some embodiments, a polymeric material of the present disclosure can have one or more of the following characteristics: (A) a flexural modulus greater than or equal to 50 MPa, 100 MPa, or 200 MPa; (B) an elastic modulus of greater than or equal to 150 MPa, 250 MPa, 350 MPa, 450 MPa, 550 MPa, or between about 500 and 1500 MPa, from about 550 to about 1000 MPa, or from about 550 MPa to about 1500 MPa) an elongation at break greater than or equal to 5% before and after 24 hours in a wet environment at 37 °C; (D) a water uptake of less than 25 wt% when measured after 24 hours in a wet environment at 37 °C; (E) transmission of at least 30% of visible light through the polymeric material after 24 hours in a wet environment at 37 °C; and (F) comprises a plurality of polymeric phases, wherein at least one polymeric phase of the one or more polymeric phases has a Tgof at least 60 °C, 80 °C, 90 °C, 100 °C, or at least 110 °C. In some instances, a polymeric material herein has at least two, three, four, five, or all characteristics of (A), (B), (C), (D), (E) and (F).

[0254] In some instances, the polymeric material can be characterized by a storage modulus of 0.1 MPa to 4000 MPa, a storage modulus of 300 MPa to 3000 MPa, or a storage modulus of 750 MPa to 3000 MPa after 24 hours in a wet environment at 37 °C.

[0255] In some instances, the polymeric material herein can have a flexural stress remaining of 400 MPa or more, 300 MPa or more, 200 MPa or more, 180 MPa or more, 160 MPa or more, 120 MPa or more, 100 MPa or more, 80 MPa or more, 70 MPa or more, 60 MPa or more, after 24 hours in a wet environment at 37 °C.

[0256] In some instances, the polymeric material can be characterized by an elongation at break greater than 10%, an elongation at break greater than 20%, an elongation at break greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break value between 40% and 250% before and after 24 hours in a wet environment at 37 °C when measured at strain rates of 1.7 mm / min and / or 510 mm / min.

[0257] 29

[0258] #11356484.1A polymeric material can be characterized by a water uptake of less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt% when measured after 24 hours in a wet environment at 37 °C. In some cases, a polymeric material can have greater than 50%, 60%, or 70% conversion of double bonds to single bonds compared to the polymerizable composition, as measured by FTIR.

[0259] In some instances, a polymeric material can have an ultimate tensile strength from 10 MPa to 100 MPa, from 15 MPa to 80 MPa, from 20 MPa to 60 MPa, from 10 MPa to 50 MPa, from 10 MPa to 45 MPa, from 25 MPa to 40 MPa, from 30 MPa to 45 MPa, or from 30 MPa to 40 MPa after 24 hours in a wet environment at 37 °C.

[0260] In some instances, a polymeric material can have a low amount of hydrogen bonding which can facilitate a decreased uptake of water in comparison with conventional polymeric materials having greater amounts of hydrogen bonding. Thus, in some instances, a polymeric material herein can comprise less than about 10 wt%, less than about 9 wt%, less than about 8 wt%, less than about 7 wt%, less than about 6 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1 wt%, or less than about 0.5 wt% water when fully saturated at use temperature (e.g., about 20 °C, 25 °C, 30 °C, or 35 °C). In some instances, the use temperature can include the temperature of a human mouth (e.g., approximately 35-40 °C). The use temperature can be a temperature selected from -100-250 °C, 0-90 °C, 0-80 °C, 0-70 °C, 0-60 °C, 0-50 °C, 0-40 °C, 0-30 °C, 0-20 °C, 0-10 °C, 20-90 °C, 20-80 °C, 20-70 °C, 20-60 °C, 20-50 °C, 20-40 °C, 20-30 °C, or below 0 °C.

[0261] In various instances, the one or more amorphous phases of the polymeric material can have a glass transition temperature of at least about 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, or at least about 110 °C.

[0262] Further provided herein are polymeric films / coatings comprising a polymeric material of the present disclosure. In some cases, such polymeric film can have a thickness of at least about 50 pm, 100 pm, 250 pm, 500 pm, 1 mm, 2 mm and not more than 3 or 4 mm.

[0263] The present disclosure provides devices that comprise a polymeric material (e.g., a polymeric coating) of the present disclosure. As described herein, such polymeric material can comprise, incorporated in its polymeric structure, one or more species of polymerizable compound(s) of this disclosure. In various cases, the device can be a medical device. The medical device can be an orthodontic appliance. The orthodontic appliance can be a dental aligner, a dental expander, or a dental spacer.

[0264] 30

[0265] #11356484.1Methods of Use

[0266] The present disclosure provides methods for synthesizing the polymerizable compound of the present disclosure, methods of using compositions (e.g., resins and polymeric materials) comprising such compounds, as well as methods for using the compositions in devices such as medical devices. In cases in which photo-polymerization is used to cure a resin, a polymerizable compound of the present disclosure can be used as components in materials applicable many different industries such as transportation (e.g., planes, trains, boats, automobiles, etc.)., hobbyist, prototyping, medical, art and design, microfluidics, molds, among others. Such medical devices include, in various embodiments herein, orthodontic appliances.

[0267] In some embodiments, the present disclosure provides a method of 3D printing using curable resins or polymerizable compositions. In some embodiments, the method includes preparing a medical device. In some embodiments, the method includes preparing a dental retainer or dental aligner. In some embodiment the method includes preparing and / or curing a 3D printing resin.

[0268] Methods of Forming a Polymer

[0269] Further provided herein is a method of polymerizing (e.g., photo-curing) a curable composition (e.g., a photo-curable resin) comprising at least one species of a polymerizable compound described herein and optionally one or more additional components selected from the group consisting of telechelic polymers, telechelic oligomers, polymerizable monomers (e.g., reactive diluents), polymerization initiators, polymerization inhibitors, solvents, carrier liquid, fillers, antioxidants, pigments, colorants, surface modifiers, and mixtures thereof, to obtain an optionally cross-linked polymer, the method comprising a step of mixing the curable composition, optionally after heating, with a reactive diluent before inducing polymerization by heating and / or irradiating the composition; wherein the reactive diluent is selected from the polymerizable monomers and mixtures thereof.

[0270] The present disclosure provides methods for producing polymeric materials (e.g., a polymeric coating) using curable resins or polymerizable compositions described herein. In various embodiments, provided herein are methods for photo-curing a polymerizable composition. Hence, in various instances, provided herein is a method of forming a polymeric material, the method comprising: (i) providing a polymerizable composition of the present

[0271] 31

[0272] #11356484.1disclosure; (ii) exposing the polymerizable composition to radiation (e.g., a light source); and (iii) curing the polymerizable composition to form the polymeric material.

[0273] In some embodiments, the photo-curing comprises a single curing step. In some embodiments, the photo-curing comprises a plurality of curing steps. In yet other embodiments, the photo-curing comprises at least one curing step which exposes the curable resin or polymerizable composition to light. Exposing the curable resin or polymerizable composition to light can initiate and / or facilitate photo-polymerization. In some instances, a photoinitiator can be used as part of the resin to accelerate and / or initiate photo-polymerization. In some embodiments, the resin is exposed to UV (ultraviolet) light, visible light, IR (infrared) light, or any combination thereof. In some embodiments, the cured polymeric material is formed from the polymerizable composition using at least one step comprising exposure to a light source, wherein the light source comprises UV light, visible light (e.g., blue light), and / or IR light. In some embodiments, the light source comprises a wavelength from 10 nm to 200 nm, from 200 nm to 350 nm, from 350 nm to 450 nm, from 450 nm to 550 nm, from 550 nm to 650 nm, from 650 nm to 750 nm, from 750 nm to 850 nm, from 850 nm to 1000 nm, or from 1000 nm to 1500 nm.

[0274] In some instances, the polymeric material has the glass transition temperature (Tg) of at least about 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 110 °C or at least about 120 °C.

[0275] In some embodiments, a method of forming a polymeric material from a polymerizable composition described herein can further comprise initiating and / or enhancing formation of crystalline phases in the forming polymeric material. In certain embodiments, the triggering comprises cooling the cured material, adding seeding particles to the polymerizable composition, providing a force to the cured material, providing an electrical charge to the polymerizable composition, or any combination thereof. In some cases, polymer crystals can yield upon application of a strain (e.g., a physical strain, such as twisting or stretching a material). The yielding may include unraveling, unwinding, disentangling, dislocation, coarse slips, and / or fine slips in the crystallized polymer. In some embodiments, the methods disclosed herein further comprise the step of growing polymer crystals. As described further herein, polymer crystals comprise the crystallizable polymeric material.

[0276] Thus, in various embodiments, a method of forming a polymeric material from a polymerizable composition described herein can comprise inducing phase separation in the forming polymeric material (e.g., during photo-curing or during heating), wherein such phase separation can yield polymeric materials that comprise one or more amorphous phases, one or

[0277] 32

[0278] #11356484.1more crystalline phases, or both one or more amorphous phases and one or more crystalline phases.

[0279] As described herein, a polymeric material produced by the methods provided herein can be characterized by one or more of: (i) a storage modulus greater than or equal to 200 MPa; (ii) a flexural stress of greater than or equal to 1.5 MPa remaining after 24 hours in a wet environment at 37 °C; (iii) an elongation at break greater than or equal to 5% before and after 24 hours in a wet environment at 37 °C; (iv) a water uptake of less than 25 wt% when measured after 24 hours in a wet environment at 37 °C; and (v) transmission of at least 30% of visible light through the polymeric material after 24 hours in a wet environment at 37 °C. In various cases, such polymeric material can be characterized by at least 2, 3, 4, or all of these properties.

[0280] Fabrication and Use of Orthodontic Appliances

[0281] Provided herein are methods for using the polymerizable compounds, curable resins and compositions comprising such compounds, as well as polymeric materials produced from such resins and composition for the fabrication of a medical device, such as an orthodontic appliance (e.g., a dental aligner, a dental expander, or a dental spacer).

[0282] Thus, in some embodiments, a method herein further comprises the step of fabricating a device or an object using an additive manufacturing device, wherein the additive manufacturing device facilitates the curing. In some embodiments, the curing of a polymerizable composition produces the cured polymeric material. In certain embodiments, a polymerizable composition is cured using an additive manufacturing device to produce the cured polymeric material. In some embodiments, the method further comprises the step of cleaning the cured polymeric material. In certain embodiments, the cleaning of the cured polymeric material includes washing and / or rinsing the cured polymeric material with a solvent, which can remove uncured resin and undesired impurities from the cured polymeric material.

[0283] In some embodiments, a polymerizable composition herein can be curable and have melting points < 100 °C in order to be liquid and, thus, processable at the temperatures usually employed in currently available additive manufacturing techniques. As described herein, the polymerizable monomers of the present disclosure that are used as components in the polymerizable compositions can have a low vapor pressure at an elevated temperature compared to conventional reactive diluents or other polymerizable components used in polymerizable compositions. Such low vapor pressure of the monomers described herein can be particularly advantageous for use of such monomer in the curable (e.g., photocurable) compositions and

[0284] 33

[0285] #11356484.1additive manufacturing where elevated temperatures (e.g., 60 °C, 80 °C, 90 °C, or higher) may be used. In various instances, a polymerizable monomer can have a vapor pressure of at most about 12 Pa at 60 °C, or lower, as further described herein.

[0286] In some embodiments, a curable resin or polymerizable composition herein can comprise at least one photo-polymerization initiator ( / .<?., a photoinitiator) and may be heated to a predefined elevated process temperature ranging from about 50 °C to about 200 °C, such as from about 90 °C to about 120 °C, before becoming irradiated with light of a suitable wavelength to be absorbed by the photoinitiator, thereby causing activation of the photoinitiator to induce polymerization of the curable resin or polymerizable composition to obtain a cured polymeric material, which can optionally be cross-linked.

[0287] In some embodiments, the methods disclosed herein for forming a polymeric material are part of a high temperature lithography -based photo-polymerization process, wherein a polymerizable composition that can comprise at least one photo-polymerization initiator is heated to an elevated process temperature (e.g., from about 50 °C to about 150 °C, such as from about 90 °C to about 120 °C). Thus, a method for forming a polymeric material according to the present disclosure can offer the possibility of quickly and facilely producing devices, such as orthodontic appliances, by additive manufacturing such as 3D printing using polymerizable compositions as disclosed herein. In various embodiments, such curable resin or polymerizable composition is a photo-curable resin comprising one or more photo-polymerizable compounds described herein.

[0288] One embodiment provides a method of forming a polymer e.g., a second polymer) according to the embodiments disclosed herein, the method comprising:

[0289] providing a polymerizable composition according to the embodiments disclosed herein;

[0290] exposing the polymerizable composition to a light source; and

[0291] polymerizing the polymerizable composition to form the polymer.

[0292] In some embodiments, the light source is an ultraviolet (UV) or visible light source. In certain embodiments, the method further comprising fabricating an orthodontic appliance with the polymer.

[0293] One embodiment provides a method for preparing an article by an additive manufacturing process, comprising:

[0294] providing a polymerizable composition according to the embodiments disclosed herein;

[0295] 34

[0296] #11356484.1exposing the polymerizable composition to radiation (e.g., a light source); polymerizing the polymerizable composition layer-by-layer based on a predefined design, thereby polymerizing the polymerizable composition to form a polymer; and fabricating the article with the polymer.

[0297] In some embodiments, the method further comprises heating the polymerizable composition at a processing temperature. In some embodiments, the method further comprises heating the polymerizable composition to a processing temperature.

[0298] In some embodiments, the processing temperature is from about 50°C to about 150°C. In some embodiments, the processing temperature is from about 50°C to about 120°C. In certain embodiments, the processing temperature is from about 90°C to about 110°C, from about 100°C to about 120°C, from about 105°C to about 115°C, or from about 108°C to about 110°C. In some embodiments, the processing temperature is from 150 C to 300°C. In some embodiments, the additive manufacturing process is a 3D printing process.

[0299] In some embodiments, the method further comprises receiving a file containing instructions for fabrication of a dental appliance.

[0300] In some embodiments, the article is a medical device. In certain embodiments, the medical device is an orthodontic appliance.

[0301] Further embodiments provide a method of repositioning a patient's teeth, comprising: generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement;

[0302] producing an orthodontic appliance according to the embodiments disclosed herein, or an orthodontic appliance comprising the polymer according to the embodiments disclosed herein; and

[0303] moving on-track, with the orthodontic appliance, at least one of the patient's teeth toward an intermediate tooth arrangement or the final tooth arrangement.

[0304] In some embodiments, producing the orthodontic appliance comprises 3D printing of the orthodontic appliance.

[0305] In some embodiments, the method further comprises tracking progression of the patient's teeth along the treatment path after administration of the orthodontic appliance to the patient, the tracking comprising comparing a current arrangement of the patient's teeth to a planned arrangement of the patient's teeth.

[0306] 35

[0307] #11356484.1In certain embodiments, greater than 60% of the patient's teeth are on track with the treatment plan after 2 weeks of treatment. In certain embodiments, greater than 60% of the patient's teeth are on track with the treatment plan after 3 weeks of treatment. In certain embodiments, greater than 60% of the patient's teeth are on track with the treatment plan after 4-8 weeks of treatment.

[0308] In some embodiments, the orthodontic appliance has a retained repositioning force to the at least one of the patient's teeth after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of repositioning force initially provided to the at least one of the patient's teeth.

[0309] In some embodiments, the treatment plan is generated using an intraoral scan of the patient's teeth.

[0310] Photo-polymerization can occur when a polymerizable composition herein is exposed to radiation (e.g., UV or visible light) of a wavelength sufficient to initiate polymerization. The wavelengths of radiation useful to initiate polymerization may depend on the photoinitiator used. "Light" as used herein includes any wavelength and power capable of initiating polymerization. Some wavelengths of light include ultraviolet (UV) or visible. UV light sources include UVA (wavelength about 400 nanometers (nm) to about 320 nm), UVB (about 320 nm to about 290 nm) or UVC (about 290 nm to about 100 nm). Any suitable source may be used, including laser sources. The source may be broadband or narrowband, or a combination thereof. The light source may provide continuous or pulsed light during the process. Both the length of time the system is exposed to UV light and the intensity of the UV light can be varied to determine the ideal reaction conditions.

[0311] In some embodiments, the methods disclosed herein include the use of additive manufacturing to produce a device comprising the cured polymeric material. Such device can be an orthodontic appliance. The orthodontic appliance can be a dental aligner, a dental expander, or a dental spacer. In certain embodiments, the methods disclosed herein use additive manufacturing to produce a device comprising, consisting essentially of, or consisting of the cured polymeric material. Additive manufacturing includes a variety of technologies which fabricate three-dimensional objects directly from digital models through an additive process. In some embodiments, successive layers of material are deposited and "cured in place". A variety of techniques are known to the art for additive manufacturing, including selective laser sintering (SLS), fused deposition modeling (FDM) and jetting or extrusion. In many embodiments, selective laser sintering involves using a laser beam to selectively melt and fuse a layer of

[0312] 36

[0313] #11356484.1powdered material according to a desired cross-sectional shape to build up the object geometry. In many embodiments, fused deposition modeling involves melting and selectively depositing a thin filament of thermoplastic polymer in a layer-by-layer manner to form an object. In yet another example, 3D printing can be used to fabricate an orthodontic appliance herein. In many embodiments, 3D printing involves jetting or extruding one or more materials (e.g., the crystallizable resins disclosed herein) onto a build surface to form successive layers of the object geometry. In some embodiments, a polymerizable composition described herein can be used in inkjet or coating applications. Cured polymeric materials may also be fabricated by "vat" processes in which light is used to selectively cure a vat or reservoir of the curable resin or polymerizable composition. Each layer of curable resin or polymerizable composition may be selectively exposed to light in a single exposure or by scanning a beam of light across the layer. Specific techniques that can be used herein can include stereolithography (SLA), Digital Light Processing (DLP) and two photon-induced photo-polymerization (TPIP).

[0314] In some embodiments, the methods disclosed herein use continuous direct fabrication to produce a device comprising the cured polymeric material. Such device can be an orthodontic appliance as described herein. In certain embodiments, the methods disclosed herein can comprise the use of continuous direct fabrication to produce a device (e.g., an orthodontic appliance) comprising, consisting essentially of, or consisting of the cured polymeric material. A non-limiting exemplary direct fabrication process can achieve continuous build-up of an object geometry by continuous movement of a build platform (e.g., along the vertical or Z-direction) during an irradiation phase, such that the hardening depth of the irradiated photo-polymer (e.g., an irradiated polymerizable composition, hardening during the formation of a cured polymeric material) is controlled by the movement speed. Accordingly, continuous polymerization of material (e.g., polymerization of a polymerizable composition into a cured polymeric material) on the build surface can be achieved. Such methods are described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety. In yet another example, a continuous direct fabrication method utilizes a "heliolithography" approach in which a liquid resin (e.g., a polymerizable composition) is cured with focused radiation while the build platform is continuously rotated and raised. Accordingly, the object geometry can be continuously built up along a spiral build path. Such methods are described in U.S. Patent Publication No.

[0315] 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety.

[0316] Continuous liquid interface production of 3D objects has also been reported (J. Tumbleston et al., Science, 2015, 347 (6228), pp 1349-1352), which reference is hereby incorporated by

[0317] 37

[0318] #11356484.1reference in its entirety for description of the process. Another example of continuous direct fabrication method can involve extruding a material composed of a curable liquid material or resin surrounding a solid strand. The material can be extruded along a continuous three-dimensional path to form the object. Such methods are described in U.S. Patent Publication No.

[0319] 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0320] In some embodiments, the methods disclosed herein can comprise the use of high temperature lithography to produce a device comprising the cured polymeric material. Such device can be an orthodontic appliance as described herein. In certain embodiments, the methods disclosed herein use high temperature lithography to produce a device comprising, consisting essentially of, or consisting of the cured polymeric material. "High temperature lithography," as used herein, may refer to any lithography -based photo-polymerization processes that involve heating photo-polymerizable material(s) (e.g., a polymerizable composition disclosed herein). The heating may lower the viscosity of the polymerizable composition before and / or during curing. Non-limiting examples of high-temperature lithography processes include those processes described in WO 2015 / 075094, WO 2016 / 078838 and WO 2018 / 032022. In some implementations, high-temperature lithography may involve applying heat to material to temperatures from about 50°C to about 120°C, such as from about 90°C to about 120°C, from about 100°C to about 120°C, from about 105°C to about 115°C, from about 108°C to about 110°C, etc. The material may be heated to temperatures greater than about 120°C. It is noted other temperature ranges may be used without departing from the scope and substance of the inventive concepts described herein.

[0321] Since, in some cases, the polymerizable compounds of the present disclosure can, as part of a polymerizable composition, become co-polymerized in the polymerization process of a method according to the present disclosure, the result can be an optionally cross-linked polymer comprising moieties of one or more species of polymerizable compound(s) as repeating units. In some cases, such polymer is a cross-linked polymer which, typically, can be suitable and useful for applications in orthodontic appliances. The polymerizable compounds of this disclosure comprising a plurality of reactive functional groups can provide uniform and continuous polymeric networks with clear phase separation.

[0322] In further embodiments, a method herein can comprise polymerizing a curable composition which comprises at least one polymerizable compound, which, upon polymerization, can furnish a cross-linked polymer matrix which can comprise moieties originating from the polymerizable compound(s) of the present disclosure as repeating units. To obtain cross-linked

[0323] 38

[0324] #11356484.1polymers which can be particularly suitable as orthodontic appliances, the at least one polymerizable species used in the method according to the present disclosure can be selected regarding several thermomechanical properties of the resulting polymers. In some instances, a curable resin or polymerizable composition of the present disclosure can comprise one or more species of polymerizable compounds. In some cases, a polymerizable monomer of the present disclosure can also have cross-linking functionalities, in instances where it contains a plurality of reactive functional groups (like the polymerizable compounds herein), and thus not only act as a reactive diluent with low vapor pressure, but also as a cross-linking agent during polymerization of a curable resin or polymerizable composition described herein. In other embodiments, a resin comprises a polymerizable compound as described herein, a polymerizable monomer, and a cross-linking monomer, wherein both monomers are different species ( / .<?., chemical entities).

[0325] Orthodontic Appliances and Uses Thereof

[0326] The polymerizable compounds according to the present disclosure can be used as components for viscous or highly viscous polymerizable compositions and can result in polymeric materials that can have favorable thermomechanical properties as described herein (e.g., stiffness, stress remaining, etcf for use in orthodontic appliances, for example, for moving one or more teeth of a patient.

[0327] As described herein, the present disclosure provides a method of repositioning a patient's teeth, the method comprising: (i) generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement; (ii) producing a dental appliance comprising a polymeric material described herein; and moving on-track, with the dental appliance, at least one of the patient's teeth toward an intermediate tooth arrangement or the final tooth arrangement. Such dental appliance can be produced using processes that include 3D printing, as further described herein. The method of repositioning a patient's teeth can further comprise tracking progression of the patient's teeth along the treatment path after administration of the dental appliance to the patient, the tracking comprising comparing a current arrangement of the patient's teeth to a planned arrangement of the patient's teeth. In such instances, greater than 60% of the patient's teeth can be on track with the treatment plan after 2 weeks of treatment. In some instances, the dental appliance has a retained repositioning force to the at least one of the patient's teeth after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least

[0328] 39

[0329] #11356484.150%, at least 60%, or at least 70% of repositioning force initially provided to the at least one of the patient's teeth.

[0330] As used herein, the terms "rigidity" and "stiffness" can be used interchangeably, as are the corresponding terms "rigid" and "stiff." As used herein a "plurality of teeth" encompasses two or more teeth.

[0331] In many embodiments, one or more posterior teeth comprises one or more of a molar, a premolar, or a canine, and one or more anterior teeth comprising one or more of a central incisor, a lateral incisor, a cuspid, a first bicuspid or a second bicuspid.

[0332] In some embodiments, the compositions and methods described herein can be used to couple groups of one or more teeth to each other. The groups of one or more teeth may comprise a first group of one or more anterior teeth and a second group of one or more posterior teeth. The first group of teeth can be coupled to the second group of teeth with the polymeric shell appliances as disclosed herein.

[0333] The embodiments disclosed herein are well suited for moving one or more teeth of the first group of one or more teeth or moving one or more of the second group of one or more teeth, and combinations thereof.

[0334] The embodiments disclosed herein are well suited for combination with one or more known commercially available tooth moving components such as attachments and polymeric shell appliances. In many embodiments, the appliance and one or more attachments are configured to move one or more teeth along a tooth movement vector comprising six degrees of freedom, in which three degrees of freedom are rotational and three degrees of freedom are translation.

[0335] The present disclosure provides orthodontic systems and related methods for designing and providing improved or more effective tooth moving systems for eliciting a desired tooth movement and / or repositioning teeth into a desired arrangement.

[0336] Although reference is made to an appliance comprising a polymeric shell appliance, the embodiments disclosed herein are well suited for use with many appliances that receive teeth, for example appliances without one or more of polymers or shells. The appliance can be fabricated with one or more of many materials such as metal, glass, reinforced fibers, carbon fiber, composites, reinforced composites, aluminum, biological materials, and combinations thereof, for example. In some cases, the reinforced composites can comprise a polymer matrix reinforced with ceramic or metallic particles, for example. The appliance can be shaped in many ways, such as with thermoforming or direct fabrication as described herein, for example. Alternatively, or in

[0337] 40

[0338] #11356484.1combination, the appliance can be fabricated with machining such as an appliance fabricated from a block of material with computer numeric control machining. In some cases, the appliance is fabricated using a polymerizable compound according to the present disclosure, for example, using the monomers as reactive diluents for curable resins or polymerizable compositions.

[0339] Turning now to the drawings, in which like numbers designate like elements in the various figures, FIG. 1A illustrates an exemplary tooth repositioning appliance or aligner 100 that can be worn by a patient to achieve an incremental repositioning of individual teeth 102 in the jaw. The appliance can include a shell (e.g., a continuous polymeric shell or a segmented shell) having teeth-receiving cavities that receive and resiliently reposition the teeth. An appliance or portion(s) thereof may be indirectly fabricated using a physical model of teeth. For example, an appliance (e.g., polymeric appliance) can be formed using a physical model of teeth and a sheet of suitable layers of polymeric material. In some embodiments, a physical appliance is directly fabricated, e.g., using rapid prototyping fabrication techniques, from a digital model of an appliance. An appliance can fit over all teeth present in an upper or lower jaw, or less than all the teeth. The appliance can be designed specifically to accommodate the teeth of the patient (e.g., the topography of the tooth-receiving cavities matches the topography of the patient's teeth) and may be fabricated based on positive or negative models of the patient's teeth generated by impression, scanning, and the like. Alternatively, the appliance can be a generic appliance configured to receive the teeth, but not necessarily shaped to match the topography of the patient's teeth. In some cases, only certain teeth received by an appliance will be repositioned by the appliance while other teeth can provide a base or anchor region for holding the appliance in place as it applies force against the tooth, or teeth targeted for repositioning. In some cases, some, most, or even all the teeth will be repositioned at some point during treatment. Teeth that are moved can also serve as a base or anchor for holding the appliance as it is worn by the patient. Typically, no wires or other means will be provided for holding an appliance in place over the teeth. In some cases, however, it may be desirable or necessary to provide individual attachments or other anchoring elements 104 on teeth 102 with corresponding receptacles or apertures 106 in the appliance 100 so that the appliance can apply a selected force on the tooth. Exemplary appliances, including those utilized in the Invisalign® System, are described in numerous patents and patent applications assigned to Align Technology, Inc. including, for example, in U.S. Patent Nos. 6,450,807, and 5,975,893, as well as on the company's website, which is accessible on the World Wide Web (see, e.g., the url "invisalign.com"). Examples of tooth-mounted attachments suitable for use with orthodontic appliances are also described in

[0340] 41

[0341] #11356484.1patents and patent applications assigned to Align Technology, Inc., including, for example, U.S. Patent Nos. 6,309,215 and 6,830,450.

[0342] FIG. IB illustrates a tooth repositioning system 110 including a plurality of appliances 112, 114, 116. Any of the appliances described herein can be designed and / or provided as part of a set of a plurality of appliances used in a tooth repositioning system. Each appliance may be configured so a tooth-receiving cavity has a geometry corresponding to an intermediate or final tooth arrangement intended for the appliance. The patient's teeth can be progressively repositioned from an initial tooth arrangement to a target tooth arrangement by placing a series of incremental position adjustment appliances over the patient's teeth. For example, the tooth repositioning system 110 can include a first appliance 112 corresponding to an initial tooth arrangement, one or more intermediate appliances 114 corresponding to one or more intermediate arrangements, and a final appliance 116 corresponding to a target arrangement. A target tooth arrangement can be a planned final tooth arrangement selected for the patient's teeth at the end of all planned orthodontic treatment. Alternatively, a target arrangement can be one of some intermediate arrangements for the patient's teeth during the course of orthodontic treatment, which may include various different treatment scenarios, including, but not limited to, instances where surgery is recommended, where interproximal reduction (IPR) is appropriate, where a progress check is scheduled, where anchor placement is best, where palatal expansion is desirable, where restorative dentistry is involved (e.g., inlays, onlays, crowns, bridges, implants, veneers, and the like), etc. As such, it is understood that a target tooth arrangement can be any planned resulting arrangement for the patient's teeth that follows one or more incremental repositioning stages. Likewise, an initial tooth arrangement can be any initial arrangement for the patient's teeth that is followed by one or more incremental repositioning stages.

[0343] FIG. 1C illustrates a method 150 of orthodontic treatment using a plurality of appliances, in accordance with embodiments. The method 150 can be practiced using any of the appliances or appliance sets described herein. In step 160, a first orthodontic appliance is applied to a patient's teeth to reposition the teeth from a first tooth arrangement to a second tooth arrangement. In step 170, a second orthodontic appliance is applied to the patient's teeth to reposition the teeth from the second tooth arrangement to a third tooth arrangement. The method 150 can be repeated as necessary using any suitable number and combination of sequential appliances to incrementally reposition the patient's teeth from an initial arrangement to a target arrangement. The appliances can be generated all at the same stage or in sets or batches (e.g., at the beginning of a stage of the treatment), or the appliances can be fabricated one at a time, and

[0344] 42

[0345] #11356484.1the patient can wear each appliance until the pressure of each appliance on the teeth can no longer be felt or until the maximum amount of expressed tooth movement for that given stage has been achieved. A plurality of different appliances (e.g., a set) can be designed and even fabricated prior to the patient wearing any appliance of the plurality. After wearing an appliance for an appropriate period, the patient can replace the current appliance with the next appliance in the series until no more appliances remain. The appliances are generally not affixed to the teeth and the patient may place and replace the appliances at any time during the procedure (e.g., patient-removable appliances). The final appliance or several appliances in the series may have a geometry or geometries selected to overcorrect the tooth arrangement. For instance, one or more appliances may have a geometry that would (if fully achieved) move individual teeth beyond the tooth arrangement that has been selected as the "final." Such over-correction may be desirable to offset potential relapse after the repositioning method has been terminated (e.g., permit movement of individual teeth back toward their pre-corrected positions). Over-correction may also be beneficial to speed the rate of correction (e.g., an appliance with a geometry that is positioned beyond a desired intermediate or final position may shift the individual teeth toward the position at a greater rate). In such cases, the use of an appliance can be terminated before the teeth reach the positions defined by the appliance. Furthermore, over-correction may be deliberately applied to compensate for any inaccuracies or limitations of the appliance.

[0346] The various embodiments of the orthodontic appliances presented herein can be fabricated in a wide variety of ways. In some embodiments, the orthodontic appliances herein (or portions thereof) can be produced using direct fabrication, such as additive manufacturing techniques (also referred to herein as "3D printing") or subtractive manufacturing techniques (e.g., milling). In some embodiments, direct fabrication involves forming an object (e.g., an orthodontic appliance or a portion thereof) without using a physical template (e.g., mold, mask etc. to define the object geometry. Additive manufacturing techniques can be categorized as follows: (1) vat photo-polymerization (e.g., stereolithography), in which an object is constructed layer by layer from a vat of liquid photo-polymer resin / polymerizable composition; (2) material jetting, in which material is jetted onto a build platform using either a continuous or drop on demand (DOD) approach; (3) binder jetting, in which alternating layers of a build material (e.g., a powder-based material) and a binding material (e.g., a liquid binder) are deposited by a print head; (4) fused deposition modeling (FDM), in which material is drawn though a nozzle, heated, and deposited layer by layer; (5) powder bed fusion, including but not limited to direct metal laser sintering (DMLS), electron beam melting (EBM), selective heat sintering (SHS), selective

[0347] 43

[0348] #11356484.1laser melting (SLM), and selective laser sintering (SLS); (6) sheet lamination, including but not limited to laminated object manufacturing (LOM) and ultrasonic additive manufacturing (UAM); and (7) directed energy deposition, including but not limited to laser engineering net shaping, directed light fabrication, direct metal deposition, and 3D laser cladding. For example, stereolithography can be used to directly fabricate one or more of the appliances herein. In some embodiments, stereolithography involves selective polymerization of a photosensitive resin (e.g., a photo-polymer or polymerizable composition) according to a desired cross-sectional shape using light (e.g., ultraviolet light). The object geometry can be built up in a layer-by-layer fashion by sequentially polymerizing a plurality of object cross-sections. As another example, the appliances herein can be directly fabricated using selective laser sintering. In some embodiments, selective laser sintering involves using a laser beam to selectively melt and fuse a layer of powdered material according to a desired cross-sectional shape to build up the object geometry. Yet another example, the appliances herein can be directly fabricated by fused deposition modeling. In some embodiments, fused deposition modeling involves melting and selectively depositing a thin filament of thermoplastic polymer in a layer-by-layer manner to form an object. In yet another example, material jetting can be used to directly fabricate the appliances herein. In some embodiments, material jetting involves jetting or extruding one or more materials onto a build surface to form successive layers of the object geometry.

[0349] Alternatively, or in combination, some embodiments of the appliances herein (or portions thereof) can be produced using indirect fabrication techniques, such as by thermoforming over a positive or negative mold. Indirect fabrication of an orthodontic appliance can involve producing a positive or negative mold of the patient's dentition in a target arrangement (e.g., by rapid prototyping, milling, etc.) and thermoforming one or more sheets of material over the mold to generate an appliance shell.

[0350] In some embodiments, the direct fabrication methods provided herein build up the object geometry in a layer-by-layer fashion, with successive layers being formed in discrete build steps. Alternatively, or in combination, direct fabrication methods that allow for continuous build-up of an object geometry can be used, referred to herein as "continuous direct fabrication." Various types of continuous direct fabrication methods can be used. As an example, in some embodiments, the appliances herein are fabricated using "continuous liquid interphase printing," in which an object is continuously built up from a reservoir of photo-polymerizable resin by forming a gradient of partially cured resin between the building surface of the object and a polymerization-inhibited "dead zone." In some embodiments, a semi-permeable membrane is

[0351] 44

[0352] #11356484.1used to control transport of a photo-polymerization inhibitor (e.g., oxygen) into the dead zone to form the polymerization gradient. Continuous liquid interphase printing can achieve fabrication speeds about 25 times to about 100 times faster than other direct fabrication methods, and speeds about 1000 times faster can be achieved with the incorporation of cooling systems. Continuous liquid interphase printing is described in U.S. Patent Publication Nos. 2015 / 0097315, 2015 / 0097316, and 2015 / 0102532, the disclosures of each of which are incorporated herein by reference in their entirety.

[0353] As another example, a continuous direct fabrication method can achieve continuous build-up of an object geometry by continuous movement of the build platform e.g., along the vertical or Z-direction) during the irradiation phase, such that the hardening depth of the irradiated photo-polymer is controlled by the movement speed. Accordingly, continuous polymerization of material on the build surface can be achieved. Such methods are described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety.

[0354] In another example, a continuous direct fabrication method can involve extruding a composite material composed of a curable liquid material surrounding a solid strand. The composite material can be extruded along a continuous three-dimensional path to form the object. Such methods are described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0355] In yet another example, a continuous direct fabrication method utilizes a "heliolithography" approach in which the liquid photo-polymer is cured with focused radiation while the build platform is continuously rotated and raised. Accordingly, the object geometry can be continuously built up along a spiral build path. Such methods are described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety.

[0356] The direct fabrication approaches provided herein are compatible with a wide variety of materials, including but not limited to one or more of the following: a polyester, a co-polyester, a polycarbonate, a thermoplastic polyurethane, a polypropylene, a polyethylene, a polypropylene and polyethylene copolymer, an acrylic, a cyclic block copolymer, a polyetheretherketone, a polyamide, a polyethylene terephthalate, a polybutylene terephthalate, a polyetherimide, a polyethersulfone, a polytrimethylene terephthalate, a styrenic block copolymer (SBC), a silicone rubber, an elastomeric alloy, a thermoplastic elastomer (TPE), a thermoplastic vulcanizate (TPV) elastomer, a polyurethane elastomer, a block copolymer elastomer, a polyolefin blend elastomer,

[0357] 45

[0358] #11356484.1a thermoplastic co-polyester elastomer, a thermoplastic polyamide elastomer, a thermoset material, or combinations thereof. The materials used for direct fabrication can be provided in an uncured form (e.g., as a liquid, resin, powder, etc.} and can be cured (e.g., by photopolymerization, light curing, gas curing, laser curing, cross-linking, etc. to form an orthodontic appliance or a portion thereof. The properties of the material before curing may differ from the properties of the material after curing. Once cured, the materials herein can exhibit sufficient strength, stiffness, durability, biocompatibility, etc. for use in an orthodontic appliance. The postcuring properties of the materials used can be selected according to the desired properties for the corresponding portions of the appliance.

[0359] In some embodiments, relatively rigid portions of the orthodontic appliance can be formed via direct fabrication using one or more of the following materials: a polyester, a copolyester, a polycarbonate, a thermoplastic polyurethane, a polypropylene, a polyethylene, a polypropylene and polyethylene copolymer, an acrylic, a cyclic block copolymer, a polyetheretherketone, a polyamide, a polyethylene terephthalate, a polybutylene terephthalate, a polyetherimide, a polyethersulfone, and / or a polytrimethylene terephthalate.

[0360] In some embodiments, relatively elastic portions of the orthodontic appliance can be formed via direct fabrication using one or more of the following materials: a styrenic block copolymer (SBC), a silicone rubber, an elastomeric alloy, a thermoplastic elastomer (TPE), a thermoplastic vulcanizate (TPV) elastomer, a polyurethane elastomer, a block copolymer elastomer, a polyolefin blend elastomer, a thermoplastic co-polyester elastomer, and / or a thermoplastic polyamide elastomer.

[0361] Machine parameters can include curing parameters. For digital light processing (DLP)-based curing systems, curing parameters can include power, curing time, and / or grayscale of the full image. For laser-based curing systems, curing parameters can include power, speed, beam size, beam shape and / or power distribution of the beam. For printing systems, curing parameters can include material drop size, viscosity, and / or curing power. These machine parameters can be monitored and adjusted on a regular basis (e.g., some parameters at every 1-x layers and some parameters after each build) as part of the process control on the fabrication machine. Process control can be achieved by including a sensor on the machine that measures power and other beam parameters every layer or every few seconds and automatically adjusts them with a feedback loop. For DLP machines, gray scale can be measured and calibrated before, during, and / or at the end of each build, and / or at predetermined time intervals (e.g., every nthbuild, once per hour, once per day, once per week, etc.}, depending on the stability of the system. In

[0362] 46

[0363] #11356484.1addition, material properties and / or photo-characteristics can be provided to the fabrication machine, and a machine process control module can use these parameters to adjust machine parameters (e.g., power, time, gray scale, etc.) to compensate for variability in material properties. By implementing process controls for the fabrication machine, reduced variability in appliance accuracy and residual stress can be achieved.

[0364] Optionally, the direct fabrication methods described herein allow for fabrication of an appliance including multiple materials, referred to herein as "multi -material direct fabrication." In some embodiments, a multi-material direct fabrication method involves concurrently forming an object from multiple materials in a single manufacturing step. For instance, a multi-tip extrusion apparatus can be used to selectively dispense multiple types of materials from distinct material supply sources to fabricate an object from a plurality of different materials. Such methods are described in U.S. Patent No. 6,749,414, the disclosure of which is incorporated herein by reference in its entirety. Alternatively, or in combination, a multi -material direct fabrication method can involve forming an object from multiple materials in a plurality of sequential manufacturing steps. For instance, a first portion of the object can be formed from a first material in accordance with any of the direct fabrication methods herein, then a second portion of the object can be formed from a second material in accordance with methods herein, and so on, until the entirety of the object has been formed.

[0365] Direct fabrication can provide various advantages compared to other manufacturing approaches. For instance, in contrast to indirect fabrication, direct fabrication permits production of an orthodontic appliance without utilizing any molds or templates for shaping the appliance, thus reducing the number of manufacturing steps involved and improving the resolution and accuracy of the final appliance geometry. Additionally, direct fabrication permits precise control over the three-dimensional geometry of the appliance, such as the appliance thickness. Complex structures and / or auxiliary components can be formed integrally as a single piece with the appliance shell in a single manufacturing step, rather than being added to the shell in a separate manufacturing step. In some embodiments, direct fabrication is used to produce appliance geometries that would be difficult to create using alternative manufacturing techniques, such as appliances with very small or fine features, complex geometric shapes, undercuts, interproximal structures, shells with variable thicknesses, and / or internal structures (e.g., for improving strength with reduced weight and material usage). For example, in some embodiments, the direct fabrication approaches herein permit fabrication of an orthodontic appliance with feature sizes of

[0366] 47

[0367] #11356484.1less than or equal to about 5 pm, or within a range from about 5 pm to about 50 pm, or within a range from about 20 gm to about 50 gm.

[0368] The direct fabrication techniques described herein can be used to produce appliances with substantially isotropic material properties, e.g., substantially the same or similar strengths along all directions. In some embodiments, the direct fabrication approaches herein permit production of an orthodontic appliance with a strength that varies by no more than about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% along all directions. Additionally, the direct fabrication approaches herein can be used to produce orthodontic appliances at a faster speed compared to other manufacturing techniques. In some embodiments, the direct fabrication approaches herein allow for production of an orthodontic appliance in a time interval less than or equal to about 1 hour, about 30 minutes, about 25 minutes, about 20 minutes, about 15 minutes, about 10 minutes, about 5 minutes, about 4 minutes, about 3 minutes, about 2 minutes, about 1 minutes, or about 30 seconds. Such manufacturing speeds allow for rapid "chair-side" production of customized appliances, e.g., during a routine appointment or checkup.

[0369] In some embodiments, the direct fabrication methods described herein implement process controls for various machine parameters of a direct fabrication system or device in order to ensure that the resultant appliances are fabricated with a high degree of precision. Such precision can be beneficial for ensuring accurate delivery of a desired force system to the teeth in order to effectively elicit tooth movements. Process controls can be implemented to account for process variability arising from multiple sources, such as the material properties, machine parameters, environmental variables, and / or post-processing parameters.

[0370] Material properties may vary depending on the properties of raw materials, purity of raw materials, and / or process variables during mixing of the raw materials. In many embodiments, resins or other materials for direct fabrication should be manufactured with tight process control to ensure little variability in photo-characteristics, material properties (e.g., viscosity, surface tension), physical properties (e.g., modulus, strength, elongation) and / or thermal properties (e.g., glass transition temperature, heat deflection temperature). Process control for a material manufacturing process can be achieved with screening of raw materials for physical properties and / or control of temperature, humidity, and / or other process parameters during the mixing process. By implementing process controls for the material manufacturing procedure, reduced variability of process parameters and more uniform material properties for each batch of material can be achieved. Residual variability in material properties can be compensated with process control on the machine, as discussed further herein.

[0371] 48

[0372] #11356484.1Machine parameters can include curing parameters. For digital light processing (DLP)-based curing systems, curing parameters can include power, curing time, and / or grayscale of the full image. For laser-based curing systems, curing parameters can include power, speed, beam size, beam shape and / or power distribution of the beam. For printing systems, curing parameters can include material drop size, viscosity, and / or curing power. These machine parameters can be monitored and adjusted on a regular basis (e.g., some parameters at every 1-x layers and some parameters after each build) as part of the process control on the fabrication machine. Process control can be achieved by including a sensor on the machine that measures power and other beam parameters every layer or every few seconds and automatically adjusts them with a feedback loop. For DLP machines, gray scale can be measured and calibrated at the end of each build. In addition, material properties and / or photo-characteristics can be provided to the fabrication machine, and a machine process control module can use these parameters to adjust machine parameters (e.g., power, time, gray scale, etc.) to compensate for variability in material properties. By implementing process controls for the fabrication machine, reduced variability in appliance accuracy and residual stress can be achieved.

[0373] In many embodiments, environmental variables (e.g., temperature, humidity, Sunlight or exposure to other energy / curing source) are maintained in a tight range to reduce variability in appliance thickness and / or other properties. Optionally, machine parameters can be adjusted to compensate for environmental variables.

[0374] In many embodiments, post-processing of appliances includes cleaning, post-curing, and / or support removal processes. Relevant post-processing parameters can include purity of cleaning agent, cleaning pressure and / or temperature, cleaning time, post-curing energy and / or time, and / or consistency of support removal process. These parameters can be measured and adjusted as part of a process control scheme. In addition, appliance physical properties can be varied by modifying the post-processing parameters. Adjusting post-processing machine parameters can provide another way to compensate for variability in material properties and / or machine properties.

[0375] The configuration of the orthodontic appliances herein can be determined according to a treatment plan for a patient, e.g., a treatment plan involving successive administration of a plurality of appliances for incrementally repositioning teeth. Computer-based treatment planning and / or appliance manufacturing methods can be used in order to facilitate the design and fabrication of appliances. For instance, one or more of the appliance components described herein can be digitally designed and fabricated with the aid of computer-controlled

[0376] 49

[0377] #11356484.1manufacturing devices (e.g., computer numerical control (CNC) milling, computer-controlled rapid prototyping such as 3D printing, etc.). The computer-based methods presented herein can improve the accuracy, flexibility, and convenience of appliance fabrication.

[0378] FIG. 2 illustrates a representative example of a system 200 for additive manufacturing configured in accordance with embodiments of the present technology. The system 200 can be used to fabricate any embodiment of the objects described herein. For example, the system 200 can be used to produce an object using an additive manufacturing process (e.g., 3D printing).

[0379] The system 200 includes a printer assembly 202 configured to fabricate an additively manufactured object 204 (“object 204”) using any of the additive manufacturing processes described herein. The printer assembly 202 is configured to deposit a curable material 206 (e.g., a polymeric resin, polymerizable composition, or other solidifiable precursor material) on a build platform 208 (e.g., a tray, plate, film, sheet, or other planar substrate) to form the object 204. In the illustrated embodiment, the printer assembly 202 includes a carrier film 210 configured to deliver the curable material 206 to the build platform 208. The carrier film 210 can be a flexible loop of material having an outer surface and an inner surface. The outer surface of the carrier film 210 can adhere to and carry a thin layer of the curable material 206. The inner surface of the carrier film 210 can contact one or more rollers 212 that rotate to move the carrier film 210 in a continuous loop trajectory, e.g., along the direction indicated by arrow 214.

[0380] The printer assembly 202 can also include a material source 216 (shown schematically) configured to apply the curable material 206 to the carrier film 210. In the illustrated embodiment, the material source 216 is located at the upper portion of the printer assembly 202. In other embodiments, however, the material source 216 can be at a different location in the printer assembly 202. The material source 216 can include nozzles, ports, reservoirs, etc., that deposit the curable material 206 onto the outer surface of the carrier film 210. The material source 216 can also include one or more blades (e.g., doctor blades, recoater blades) that smooth the deposited curable material 206 into a relatively thin, uniform layer. For example, the curable material 206 can be formed into a layer having a thickness within a range from 200 microns to 300 microns, or any other desired thickness.

[0381] The curable material 206 can be conveyed by the carrier film 210 toward the build platform 208. In the illustrated embodiment, the build platform 208 is located below the printer assembly 202. In other embodiments, however, the build platform 208 can be positioned at a different location in the printer assembly 202. The distance between the carrier film 210 and build platform 208 can be adjustable so that the curable material 206 at can be brought into direct

[0382] 50

[0383] #11356484.1contact with the surface of the build platform 208 (when printing the initial layer of the object 204) or with the surface of the object 204 (when printing subsequent layers of the object 204). For example, the build platform 208 can include or be coupled to a motor (not shown) that raises and / or lowers the build platform 208 to the desired height during the manufacturing process.

[0384] The printer assembly 202 includes an energy source 218 (e.g., a projector or light engine) that outputs energy 220 (e.g., light, such as UV light) having a wavelength configured to partially or fully cure the curable material 206. The carrier film 210 can be partially or completely transparent to the wavelength of the energy 220 to allow the energy 220 to pass through the carrier film 210 and onto the portion of the curable material 206 above the build platform 208. Optionally, a transparent plate 222 can be disposed between the energy source 218 and the carrier film 210 to guide the carrier film 210 into a specific position (e.g., height) relative to the build platform 208. During operation, the energy 220 can be patterned or scanned in a suitable pattern onto the curable material 206, thus forming a layer of cured material onto the build platform 208 and / or on a previously formed portion of the object 204. The geometry of the cured material can correspond to the desired cross-sectional geometry for the object 204. The parameters for operating the energy source 218 (e.g., energy intensity, energy dosage, exposure time, exposure pattern, exposure wavelength, energy density, power density) can be set based on instructions from a controller 224, as described in further detail below.

[0385] Once the object cross-section has been formed, the build platform 208 can be lowered by a predetermined amount to separate the cured material from the carrier film 210. The remaining curable material 206 can be carried by the carrier film 210 away from the build platform 208 and back toward the material source 216. The material source 216 can deposit additional curable material 206 onto the carrier film 210 and / or smooth the curable material 206 to re-form a uniform layer of curable material 206 on the carrier film 210. The curable material 206 can then be recirculated back to the build platform 208 to fabricate an additional layer of the object 204. This process can be repeated to iteratively build up individual object layers on the build platform 208 until the object 204 is complete. The object 204 and build platform 208 can then be removed from the system 200 for post-processing.

[0386] In some embodiments, the system 200 is used in a high temperature lithography process utilizing a highly viscous curable material 206 (e.g., a highly viscous resin). Accordingly, the printer assembly 202 can include one or more heat sources (heating plates, infrared lamps, etc.) for heating the curable material 206 to lower the viscosity to a range suitable for additive manufacturing. For example, the printer assembly 202 can include a first heat source 226a

[0387] 51

[0388] #11356484.1positioned against the segment of the carrier film 210 before the build platform 208, and a second heat source 226b positioned against the segment of the carrier film 210 after the build platform 208. Alternatively, or in combination, the printer assembly 202 can include heat sources at other locations.

[0389] The system 200 also includes a controller 224 (shown schematically) that is operably coupled to the printer assembly 202 and build platform 208 to control the operation thereof. The controller 224 can be or include a computing device including one or more processors and memory storing instructions for performing the additive manufacturing operations described herein. For example, the controller 224 can receive a digital data set (e.g., a three-dimensional model) representing the object 204 to be fabricated, determine a plurality of object cross-sections to build up the object 204 from the curable material 206, and can transmit instructions to the energy source 218 to output energy 220 to form the object cross-sections. As described above and in greater detail below, the controller 224 can control the energy application parameters of the energy source 218, such as the energy intensity, energy dosage, exposure time, exposure pattern, energy wavelength, and / or energy type of the energy 220 applied to the curable material 206. Optionally, the controller 224 can also determine and control other operational parameters, such as the positioning of the build platform 208 (e.g., height) relative to the carrier film 210, the movement speed and direction of the carrier film 210, the amount of curable material 206 deposited by the material source 216, the thickness of the material layer on the carrier film 210, and / or the amount of heating applied to the curable material 206.

[0390] Although FIG. 2 illustrates a representative example of a system 200 for additive manufacturing, this is not intended to be limiting, and the methods described herein can be implemented using other types of additive manufacturing systems, such as material jetting systems, binder jetting systems, material extrusion systems, powder bed fusion systems, sheet lamination systems, or directed energy deposition systems.

[0391] FIG. 3 illustrates a method 300 for digitally planning an orthodontic treatment and / or design or fabrication of an appliance, in accordance with embodiments. The method 300 can be applied to any of the treatment procedures described herein and can be performed by any suitable data processing system.

[0392] In step 310, a digital representation of a patient's teeth is received. The digital representation can include surface topography data for the patient's intraoral cavity (including teeth, gingival tissues, etc.). The surface topography data can be generated by directly scanning the intraoral cavity, a physical model (positive or negative) of the intraoral cavity, or an

[0393] 52

[0394] #11356484.1impression of the intraoral cavity, using a suitable scanning device (e.g., a handheld scanner, desktop scanner, etc.).

[0395] In step 320, one or more treatment stages are generated based on the digital representation of the teeth. The treatment stages can be incremental repositioning stages of an orthodontic treatment procedure designed to move one or more of the patient's teeth from an initial tooth arrangement to a target arrangement. For example, the treatment stages can be generated by determining the initial tooth arrangement indicated by the digital representation, determining a target tooth arrangement, and determining movement paths of one or more teeth in the initial arrangement necessary to achieve the target tooth arrangement. The movement path can be optimized based on minimizing the total distance moved, preventing collisions between teeth, avoiding tooth movements that are more difficult to achieve, or any other suitable criteria.

[0396] In step 330, at least one orthodontic appliance is fabricated based on the generated treatment stages. For example, a set of appliances can be fabricated, each shaped according to a tooth arrangement specified by one of the treatment stages, such that the appliances can be sequentially worn by the patient to incrementally reposition the teeth from the initial arrangement to the target arrangement. The appliance set may include one or more of the orthodontic appliances described herein. The fabrication of the appliance may involve creating a digital model of the appliance to be used as input to a computer-controlled fabrication system. The appliance can be formed using direct fabrication methods, indirect fabrication methods, or combinations thereof, as desired.

[0397] In some instances, staging of various arrangements or treatment stages may not be necessary for design and / or fabrication of an appliance. As illustrated by the dashed line in FIG.

[0398] 3, design and / or fabrication of an orthodontic appliance, and perhaps a particular orthodontic treatment, may include use of a representation of the patient's teeth (e.g., receive a digital representation of the patient's teeth 310), followed by design and / or fabrication of an orthodontic appliance based on a representation of the patient's teeth in the arrangement represented by the received representation.

[0399] FIG. 6 illustrates a method 600 for designing an orthodontic appliance to be produced by direct fabrication, in accordance with embodiments. The method 600 can be applied to any embodiment of the orthodontic appliances described herein. Some or all of the steps of the method 600 can be performed by any suitable data processing system or device, e.g., one or more processors configured with suitable instructions.

[0400] 53

[0401] #11356484.1In step 610, in intraoral scan is performed. In step 620, the information from the intraoral scan is used to determine a movement path to move one or more teeth from an initial arrangement to a target arrangement is determined. The initial arrangement can also be determined from a mold but is preferably obtained using an intraoral scan of the patient's teeth or mouth tissue (e.g., using wax bites, direct contact scanning, x-ray imaging, tomographic imaging, sonographic imaging, and other techniques for obtaining information about the position and structure of the teeth, jaws, gums and other orthodontically relevant tissue). From the obtained data, a digital data set can be derived that represents the initial (e.g., pretreatment) arrangement of the patient's teeth and other tissues. Optionally, the initial digital data set is processed to segment the tissue constituents from each other. For example, data structures that digitally represent individual tooth crowns can be produced. Advantageously, digital models of entire teeth can be produced, including measured or extrapolated hidden surfaces and root structures, as well as surrounding bone and soft tissue.

[0402] The target arrangement of the teeth (e.g., a desired and intended result of orthodontic treatment) can be received from a clinician in the form of a prescription, can be calculated from basic orthodontic principles, and / or can be extrapolated computationally from a clinical prescription. With a specification of the desired final positions of the teeth and a digital representation of the teeth themselves, the final position and surface geometry of each tooth can be specified to form a complete model of the tooth arrangement at the desired end of treatment.

[0403] Having both an initial position and a target position for each tooth, step 630 is used to determine a series of arrangements for teeth to move along ("a movement path"), which can be defined for the motion of each tooth. In some embodiments, the movement paths are configured to move the teeth in the quickest fashion with the least amount of round-tripping to bring the teeth from their initial positions to their desired target positions. The tooth paths can optionally be segmented, and the segments can be calculated so that each tooth's motion within a segment stays within threshold limits of linear and rotational translation. In this way, the end points of each path segment can constitute a clinically viable repositioning, and the aggregate of segment end points can constitute a clinically viable sequence of tooth positions, so that moving from one point to the next in the sequence does not result in a collision of teeth.

[0404] In step 640, a determination of dental appliance(s) to implement the movement path is made. The determination is made using knowledge related to a force system that can be used to produce movement of one or more teeth along the movement path. A force system can include one or more forces and / or one or more torques. Different force systems can result in different

[0405] 54

[0406] #11356484.1types of tooth movement, such as tipping, translation, rotation, extrusion, intrusion, root movement, etc. Biomechanical principles, modeling techniques, force calculation / measurement techniques, and the like, including knowledge and approaches commonly used in orthodontia, may be used to determine the appropriate force system to be applied to the tooth to accomplish the tooth movement. In determining the force system to be applied, sources may be considered including literature, force systems determined by experimentation or virtual modeling, computer-based modeling, clinical experience, minimization of unwanted forces, etc.

[0407] The determination of the force system can include constraints on the allowable forces, such as allowable directions and magnitudes, as well as desired motions to be brought about by the applied forces. For example, in fabricating palatal expanders, different movement strategies may be desired for different patients. For example, the amount of force needed to separate the palate can depend on the age of the patient, as very young patients may not have a fully formed suture. Thus, in juvenile patients and others without fully closed palatal sutures, palatal expansion can be accomplished with lower force magnitudes. Slower palatal movement can also aid in growing bone to fill the expanding suture. For other patients, a more rapid expansion may be desired, which can be achieved by applying larger forces. These requirements can be incorporated as needed to choose the structure and materials of appliances; for example, by choosing palatal expanders capable of applying large forces for rupturing the palatal suture and / or causing rapid expansion of the palate. Subsequent appliance stages can be designed to apply different amounts of force, such as first applying a large force to break the suture, and then applying smaller forces to keep the suture separated or gradually expand the palate and / or arch.

[0408] The determination of the force system can also include modeling of the facial structure of the patient, such as the skeletal structure of the jaw and palate. Scan data of the palate and arch, such as X-ray data or 3D optical scanning data, for example, can be used to determine parameters of the skeletal and muscular system of the patient's mouth, to determine forces sufficient to provide a desired expansion of the palate and / or arch. In some embodiments, the thickness and / or density of the mid-palatal suture may be measured, or input by a treating professional. In other embodiments, the treating professional can select an appropriate treatment based on physiological characteristics of the patient. For example, the properties of the palate may also be estimated based on factors such as the patient's age — for example, young juvenile patients will typically require lower forces to expand the suture than older patients, as the suture has not yet fully formed.

[0409] 55

[0410] #11356484.1Accordingly, an optional additional step for 640 may be determining a configuration of an arch or palate expander design for an orthodontic appliance to produce the force system. Determination of the arch or palate expander design, appliance geometry, material composition, and / or properties can be performed using a treatment or force application simulation environment. A simulation environment can include, e.g., computer modeling systems, biomechanical systems, or apparatus, and the like. Optionally, digital models of the appliance and / or teeth can be produced, such as finite element models. The finite element models can be created using computer program application software available from a variety of vendors. For creating solid geometry models, computer aided engineering (CAE) or computer aided design (CAD) programs can be used, such as the AutoCAD® software products available from Autodesk, Inc., of San Rafael, CA. For creating finite element models and analyzing them, program products from several vendors can be used, including finite element analysis packages from ANSYS, Inc., of Canonsburg, PA, and SIMULIA(Abaqus) software products from Dassault Systemes of Waltham, MA.

[0411] Optionally, one or more arch or palate expander designs can be selected for testing or force modeling. As noted above, a desired tooth movement, as well as a force system required or desired for eliciting the desired tooth movement, can be identified. Using the simulation environment, a candidate arch or palate expander design can be analyzed or modeled for determination of an actual force system resulting from use of the candidate appliance. One or more modifications can optionally be made to a candidate appliance, and force modeling can be further analyzed as described, e.g., to iteratively determine an appliance design that produces the desired force system.

[0412] In step 650, instructions for fabrication of the orthodontic appliance optionally incorporating an arch or palate expander design are generated. The instructions can be configured to control a fabrication system or device to produce the orthodontic appliance with the specified arch or palate expander design. In some embodiments, the instructions are configured for manufacturing the orthodontic appliance using direct fabrication (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct fabrication, multi -material direct fabrication, etc.), in accordance with the various methods presented herein. In alternative embodiments, the instructions can be configured for indirect fabrication of the appliance, e.g., by thermoforming.

[0413] Method 600 may comprise additional steps: 1) The upper arch and palate of the patient is scanned intraorally to generate three-dimensional data of the palate and upper arch; 2) The three-

[0414] 56

[0415] #11356484.1dimensional shape profile of the appliance is determined to provide a gap and teeth engagement structures as described herein.

[0416] Although the above steps show a method 600 of designing an orthodontic appliance in accordance with some embodiments, a person of ordinary skill in the art will recognize some variations based on the teaching described herein. Some of the steps may comprise sub-steps. Some of the steps may be repeated as often as desired. One or more steps of the method 600 may be performed with any suitable fabrication system or device, such as the embodiments described herein. Some of the steps may be optional, and the order of the steps can be varied as desired.

[0417] On-Track Treatment

[0418] Referring to FIG. 4, a process 400 according to the present disclosure is illustrated.

[0419] Individual embodiments of the process are discussed in further detail below. The process includes receiving information regarding the orthodontic condition of the patient and / or treatment information (402), generating an assessment of the case (404), and generating a treatment plan for repositioning a patient's teeth (406). Briefly, a patient / treatment information includes data comprising an initial arrangement of the patient's teeth, which includes obtaining an impression or scan of the patient's teeth prior to the onset of treatment and can further include identification of one or more treatment goals selected by the practitioner and / or patient. A case assessment can be generated (404) to assess the complexity or difficulty of moving the particular patient's teeth in general or specifically corresponding to identified treatment goals and may further include practitioner experience and / or comfort level in administering the desired orthodontic treatment. In some cases, however, the assessment can include simply identifying treatment options (e.g., appointment planning, progress tracking, etc.) that are of interest to the patient and / or practitioner. The information and / or corresponding treatment plan includes identifying a final or target arrangement of the patient's teeth that is desired, as well as a plurality of planned successive or intermediary tooth arrangements for moving the teeth along a treatment path from the initial arrangement toward the selected final or target arrangement.

[0420] The process further includes generating customized treatment guidelines (408). The treatment plan may include multiple phases of treatment, with a customized set of treatment guidelines generated that correspond to a phase of the treatment plan. The guidelines can include detailed information on timing and / or content (e.g., specific tasks) to be completed during a given phase of treatment and can be of sufficient detail to guide a practitioner, including a less experienced practitioner or practitioner relatively new to the orthodontic treatment process,

[0421] 57

[0422] #11356484.1through the phase of treatment. Since the guidelines are designed to specifically correspond to the treatment plan and provide guidelines on activities specifically identified in the treatment information and / or generated treatment plan, the guidelines can be customized. The customized treatment guidelines are then provided to the practitioner to help instruct the practitioner as how to deliver a given phase of treatment. As set forth above, appliances can be generated based on the planned arrangements and can be provided to the practitioner and ultimately administered to the patient (410). The appliances can be provided and / or administered in sets or batches of appliances, such as 2, 3, 4, 5, 6, 7, 8, 9, or more appliances, but are not limited to any administrative scheme. Appliances can be provided to the practitioner concurrently with a given set of guidelines, or appliances and guidelines can be provided separately.

[0423] After the treatment according to the plan begins and following administration of appliances to the patient, treatment progress tracking, e.g., by teeth matching, is done to assess a current and actual arrangement of the patient's teeth compared to a planned arrangement (412). If the patient's teeth are determined to be "on-track" and progressing according to the treatment plan, then treatment progresses as planned and treatment progresses to the next stage of treatment (414). If the patient's teeth have substantially reached the initially planned final arrangement, then treatment progresses to the final stages of treatment (414). Where the patient's teeth are determined to be tracking according to the treatment plan, but have not yet reached the final arrangement, the next set of appliances can be administered to the patient.

[0424] The threshold difference values of a planned position of teeth to actual positions selected as indicating that a patient's teeth have progressed on-track are provided below in TABLE 1. If a patient's teeth have progressed at or within the threshold values, the progress is on-track. If a patient's teeth have progressed beyond the threshold values, the progress is off-track.

[0425] Table 1.

[0426]

[0427] 58

[0428] #11356484.1

[0429]

[0430] 59

[0431] #11356484.1

[0432]

[0433] The patient's teeth are determined to be on track by comparison of the teeth in their current positions with teeth in their expected or planned positions, and by confirming the teeth are within the parameter variance disclosed in TABLE 1. If the patient's teeth are determined to be on track, then treatment can progress according to the existing or original treatment plan. For example, a patient determined to be progressing on track can be administered one or more subsequent appliances according to the treatment plan, such as the next set of appliances.

[0434] Treatment can progress to the final stages and / or can reach a point in the treatment plan where bite matching is repeated for a determination of whether a patient's teeth are progressing as planned or if the teeth are off track.

[0435] In some embodiments, as further disclosed herein, this disclosure provides methods of treating a patient using a 3D printed orthodontic appliance. As a non-limiting example, orthodontic appliances comprising crystalline domains, polymer crystals, and / or materials that can form crystalline domains or polymer crystals can be 3D printed and used to reposition a patient's teeth. In certain embodiments, the method of repositioning a patient's teeth (or, in some embodiments, a singular tooth) comprises: generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial arrangement toward a final arrangement; producing a 3D printed orthodontic appliance; and moving on-track, with the orthodontic appliance, at least one of the patient's teeth 60

[0436] #11356484.1toward an intermediate arrangement or a final tooth arrangement. In some embodiments, producing the 3D printed orthodontic appliance uses the crystallizable resins disclosed further herein. On-track performance can be determined, e.g., from TABLE 1, above.

[0437] In some embodiments, the method further comprises tracking the progression of the patient's teeth along the treatment path after administration of the orthodontic appliance. In certain embodiments, the tracking comprises comparing a current arrangement of the patient's teeth to a planned arrangement of the teeth. As a non-limiting example, following the initial administration of the orthodontic appliance, a period of time passes (e.g., two weeks), a comparison of the now-current arrangement of the patient's teeth (z.e., at two weeks of treatment) can be compared with the teeth arrangement of the treatment plan. In some embodiments, the progression can also be tracked by comparing the current arrangement of the patient's teeth with the initial configuration of the patient's teeth. The period of time can be, for example, greater than 3 days, greater than 4 days, greater than 5 days, greater than 6 days, greater than 7 days, greater than 8 days, greater than 9 days, greater than 10 days, greater than 11 days, greater than 12 days, greater than 13 days, greater than 2 weeks, greater than 3 weeks, greater than 4 weeks, or greater than 2 months. In some embodiments, the period can be from at least 3 days to at most 4 weeks, from at least 3 days to at most 3 weeks, from at least 3 days to at most 2 weeks, from at least 4 days to at most 4 weeks, from at least 4 days to at most 3 weeks, or from at least 4 days to at most 2 weeks. In certain embodiments, the period can restart following the administration of a new orthodontic appliance.

[0438] In some embodiments, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of the patient's teeth are on track with the treatment plan after a period of time of using an orthodontic appliance as disclosed further herein. In some embodiments, the period is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks.

[0439] As disclosed further herein, orthodontic appliances disclosed herein have advantageous properties, such as increased durability, and an ability to retain resilient forces to a patient's teeth for a prolonged period. In some embodiments of the method disclosed above, the 3D printed orthodontic appliance has a retained repositioning force (z.e., the repositioning force after the orthodontic appliance has been applied to or worn by the patient over a period of time), and the

[0440] 61

[0441] #11356484.1retained repositioning force to at least one of the patient's teeth after the period of time is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of the repositioning force initially provided to the at least one of the patient's teeth (z.e., with initial application of the orthodontic appliance). In some embodiments, the period is 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks. In some embodiments, the repositioning force applied to at least one of the patient's teeth is present for a time period of less than 24 hours, from about 24 hours to about 2 months, from about 24 hours to about 1 month, from about 24 hours to about 3 weeks, from about 24 hours to about 14 days, from about 24 hours to about 7 days, from about 24 hours to about 3 days, from about 3 days to about 2 months, from about 3 days to about 1 month, from about 3 days to about 3 weeks, from about 3 days to about 14 days, from about 3 days to about 7 days, from about 7 days to about 2 months, from about 7 days to about 1 month, from about 7 days to about 3 weeks, from about 7 days to about 2 weeks, or greater than 2 months. In some embodiments, the repositioning force applied to at least one of the patient's teeth is present for about 24 hours, for about 3 days, for about 7 days, for about 14 days, for about 2 months, or for more than 2 months.

[0442] In some embodiments, the orthodontic appliances disclosed herein can provide on-track movement of at least one of the patient's teeth. On-track movement has been described further herein, e.g., at TABLE 1. In some embodiments, the orthodontic appliances disclosed herein can be used to achieve on-track movement of at least one of the patient's teeth to an intermediate tooth arrangement. In some embodiments, the orthodontic appliances disclosed herein can be used to achieve on-track movement of at least one of the patient's teeth to a final tooth arrangement.

[0443] In some embodiments, prior to moving, with the orthodontic appliance, at least one of the patient's teeth toward an intermediate arrangement or a final tooth arrangement, the orthodontic appliance has characteristics which are retained following the use of the orthodontic appliance. In some embodiments, prior to the moving step, the orthodontic appliance comprises a first flexural modulus. In certain embodiments, after the moving step, the orthodontic appliance comprises a second flexural modulus. In some embodiments, the second flexural modulus is at least 99%, at least 98%, at least 97%, at least 96%, at least 95%, at least 94%, at least 93%, at least 92%, at least 91%, at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, at least 50%, or at least 40% of the first flexural modulus. In some

[0444] 62

[0445] #11356484.1embodiments, the second flexural modulus is greater than 50% of the first flexural modulus. In some embodiments, this comparison is performed following a period of time in which the appliance is applied. In some embodiments, the period is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks.

[0446] In some embodiments, prior to the moving step, the orthodontic appliance comprises a first elongation at break. In certain embodiments, after the moving step, the orthodontic appliance comprises a second elongation at break. In some embodiments, the second elongation at break is at least 99%, at least 98%, at least 97%, at least 96%, at least 95%, at least 94%, at least 93%, at least 92%, at least 91%, at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, at least 50%, or at least 40% of the first elongation at break. In some embodiments, the second elongation at break is greater than 50% of the first elongation at break. In some embodiments, this comparison is performed following a period in which the appliance is applied. In some embodiments, the period is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks.

[0447] As provided herein, the methods disclosed can use the orthodontic appliances further disclosed herein. The orthodontic appliances can be directly fabricated using, e.g., the crystallizable resins disclosed herein. In certain embodiments, the direct fabrication comprises cross-linking the crystallizable resin.

[0448] The appliances formed from the crystallizable resins disclosed herein provide improved durability, strength, and flexibility, which in turn improve the rate of on-track progression in treatment plans. In some embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated with the orthodontic appliances disclosed herein (e.g., an aligner) are classified as on-track in a given treatment stage. In certain embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated with the orthodontic appliances disclosed herein (e.g., an aligner) have greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, or greater than 95% of their tooth movements classified as on-track.

[0449] As disclosed further herein, the cured polymeric material contains favorable characteristics that, at least in part, stem from the presence of polymeric crystals. These cured polymeric materials can have increased resilience to damage, can be tough, and can have

[0450] 63

[0451] #11356484.1decreased water uptake when compared to similar polymeric materials. The cured polymeric materials can be used for devices within the field of orthodontics, as well as outside the field of orthodontics. For example, the cured polymeric materials disclosed herein can be used to make devices for use in aerospace applications, automobile manufacturing, the manufacture of prototypes, and / or devices for use in durable parts production.

[0452] Experimental Methods

[0453] All chemicals were purchased from commercial sources and were used without further purification, unless otherwise stated.

[0454] JH NMR and13C NMR spectra were recorded on a BRUKER AC-E-200 FT-NMR spectrometer or a BRUKER Avance DRX-400 FT-NMR spectrometer. The chemical shifts are reported in ppm (s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet). The solvents used were deuterated chloroform (CDCh, 99.5% deuteration) and deuterated DMSO (de-DMSO, 99.8% deuteration).

[0455] In some embodiments, the stress relaxation of a material or device can be measured by monitoring the time-dependent stress resulting from a steady strain. The extent of stress relaxation can also depend on the temperature, relative humidity and other applicable conditions (e.g., presence of water). In embodiments, the test conditions for stress relaxation are a temperature of 37 ± 2 °C at 100% relative humidity or a temperature of 37 ± 2 °C in water.

[0456] The dynamic viscosity of a fluid indicates its resistance to shearing flows. The SI unit for dynamic viscosity is the Poiseuille (Pa s). Dynamic viscosity is commonly given in units of centipoise, where 1 centipoise (cP) is equivalent to 1 mPa s. Kinematic viscosity is the ratio of the dynamic viscosity to the density of the fluid; the SI unit is m2 / s. Devices for measuring viscosity include viscometers and rheometers. For example, an MCR 301 rheometer from Anton Paar may be used for rheological measurement in rotation mode (PP-25, 50 s-1, 50-115°C, 3 °C / min).

[0457] Determining the water content when fully saturated at use temperature can comprise exposing the polymeric material to 100% humidity at the use temperature (e.g., 40 °C) for a period of 24 hours, then determining water content by methods known in the art, such as by weight.

[0458] In some embodiments, the presence of a crystalline phase and an amorphous phase provide favorable material properties to the polymeric materials. Property values of the cured polymeric materials can be determined, for example, by using the following methods:

[0459] 64

[0460] #11356484.1stress relaxation properties can be assessed using an RSA-G2 instrument from TA Instruments, with a 3-point bending, according to ASTM D790; for example, stress relaxation can be measured at 30°C and submerged in water, and reported as the remaining load after 24 hours, as either the percent (%) of initial load, and / or in MPa;

[0461] storage modulus can be measured at 37°C and is reported in MPa;

[0462] Tgof the cured polymeric material can be assessed using dynamic mechanical analysis (DMA) and is provided herein as the tan 6 peak;

[0463] tensile modulus, tensile strength, elongation at yield and elongation at break can be assessed according to ISO 527-2 5B; and tensile strength at yield, elongation at break, tensile strength, and Young's modulus can be assessed according to ASTM D1708.

[0464] Additive manufacturing or 3D printing processes for generating a device herein (e.g., an orthodontic appliance) can be conducted using a Hot Lithography apparatus prototype from Cubicure (Vienna, Austria), which can substantially be configured as schematically shown in FIG. 5. In such cases, a photo-curable composition (e.g., resin) according to the present disclosure can be filled into the transparent material vat of the apparatus shown in FIG. 5, which vat can be heated to 90-110 °C. The building platform can be heated to 90-110 °C, too, and lowered to establish holohedral contact with the upper surface of the curable composition. By irradiating the composition with 375 nm UV radiation using a diode laser from Soliton, which can have an output power of 70 mW, which can be controlled to trace a predefined prototype design, and alternately raising the building platform, the composition can be cured layer by layer by a photopolymerization process according to the disclosure, resulting in a polymeric material according to present disclosure.

[0465] This disclosure relates to photo-cured semicrystalline polyester oligomers formulated with both aromatic and aliphatic monomers. These compositions demonstrated excellent durability, high flexural modules, and good stain resistance. Notably, both flexural modulus and stain resistance improved significantly when the oligomer functionality was higher than two. This formulation is particularly well-suited for 3D printing applications, especially in the fabrication of dental appliances.

[0466] However, the thermal stability of these printed polyester formulations remains a challenge when Type I photo initiators, such as acylphosphine-based initiators, are employed. We found after by thermal aging (e.g., 60 C for 1 week) or water aging (40C for 1-2 weeks), the material durability is reduced.

[0467] 65

[0468] #11356484.1To address this limitation, we have developed an effective method that leverages the synergistic interaction between amines and Type I photoinitiators, significantly enhancing the thermal stability of the cured material.

[0469] We demonstrate the novel synergistic effect from acylphosphine photoinitiator with amine synergist for polyester-based 3D printed parts.

[0470] Aliphatic amine additives were previously used for some unique benefits. Aliphatic amines work as a weak chain transfer agent to boost mechanical properties of 3D printed parts. However, > 2 wt% is required to achieve significant effect. The combination of Type I photoinitiator with amines could lead to an increase of the rate of surface cure, due to reduction in oxygen inhibition effects in UV coating or ink formulation. Despite the benefits of amine additives being disclosed in some forms, the benefit to stabilized 3D printed parts containing aliphatic polyester components has not been reported. In addition, much lower loading (< 2 wt%) of amine additives can sufficiently improve shelf stability of printed parts.

[0471] The present disclosure addresses the critical shelf-life concern for 3D printing parts containing polyester compositions in combination with acrylphosphine photoinitiators.

[0472] UV-cured polyester-based resins can exhibit poor thermal stability, particularly when conventional Type I photoinitiators are used. For instance, samples stored at ambient conditions become brittle within six months. In accelerated aging tests (e.g., 2 weeks at 60 °C), a similar reduction of material durability is observed. This presents a significant challenge to product shelf stability (e.g., lack of durability), despite the clear advantage of Type I photoinitiators (e.g., fast cure kinetics, low color).

[0473] This issue does not occur in resins formulated with other polyols, such as polyether or polycarbonate. Therefore, the degradation appears to stem from interactions between BAPO-derived fragments and the polyester oligomer after UV curing. To address this, various antioxidants were evaluated during formulation, but none of them were effective. However, when non-acylphosphine oxide photoinitiators were used, the cured polyester resins remained stable under accelerated aging, confirming the specific role of BAPO in the degradation mechanism.

[0474] This represents a unique technical challenge and poses a significant limitation to the broader use of polyester resins, despite their many advantages including high mechanical strength, abrasion resistance, and chemical durability.

[0475] It was unexpectedly discovered that incorporating reactive aliphatic amine additives (i.e., amine synergist) can effectively inhibit the degradation caused by BAPO fragments. While the

[0476] 66

[0477] #11356484.1precise mechanism remains unclear, it is believed that these amines either accelerate BAPO fragmentation or neutralize the degradation-causing fragments. By adding less than 2 wt% in formulation, these amine synergists do not compromise the liquid resin’s shelflife or affect the final properties of cure materials.

[0478] As used herein, the abbreviations refer to the chemicals as indicated below.

[0479]

[0480] "DMAEMA" - an amine synergist

[0481]

[0482] "Omnirad 379" or non-acylphosphine oxide - an amine synergist

[0483]

[0484] "LTDMA" (R is hydrogen or -CH3)

[0485] EXAMPLE 1

[0486] SYNTHESIS OF SUPPLEMENTED FILM

[0487] Film was cast at 60-80°C and two films were cast for each composition tested (film prepared at 65°C was dark yellow in color). Thermal annealing was performed at 100°C over a two-hour ramp period. Aging of samples was performed using die cut dog bones and samples were aged at 40°C in water up to 4 weeks. Samples were prepared using the following components.

[0488]

[0489] values for each component are weight percentages

[0490] 67

[0491] #11356484.1After aging, samples were tested using a tensile test (D1708, 510 mm / min) at time points of 0 (before aging), 1 week, 2 weeks, 3 weeks, and 4 weeks. Results of the testing showed that samples prepared using DMAEMA (samples 1 and 2) resolved issues with aging instability. The sample prepared using an amide additive (sample 4) had no effect. Sample prepared with the non-acylphosphine oxide (sample 3) does not have a thermal instability issue. A slight increase in modulus may result from leachable extraction in water or additional reactions.

[0492] 68

[0493] #11356484.1

Claims

1. CLAIMS1. A polymerizable composition comprising:a) an oligomer having an aliphatic polyester backbone and 2 or more polymerizable reactive groups at each terminal end of the aliphatic polyester backbone;b) an initiator;c) a reactive diluent; andd) an amine synergist.

2. The polymerizable composition of claim 1, wherein the oligomer has the following structure:wherein:X1and X2are, at each occurrence independently -C(=O)-O-, -O-C(=O)-, -O-, -S-, -O-C(=O)-O-, -C(=O)-O-C(=O)-, -NH-C(=O)-O-, -O-C(=O)-NH-, -C(=O)-NH-C(=O)-, or -NH-C(=O)-NH-;R1and R2are each independently an end group comprising two or more polymerizable reactive groups;L1, L2, and L3are, at each occurrence, independently a C1-C12 alkylene; andn is an integer ranging from 1 to 100.

3. The polymerizable composition of any one of claims 1-2, wherein the oligomer has the following structure:wherein:R1and R2are each independently an end group comprising two or more polymerizable reactive groups;L1, L2, and L3are, at each occurrence, independently a C1-C12 alkylene; andn is an integer ranging from 1 to 100.69#11356484.

14. The polymerizable composition of any one of claims 2-3, wherein L1is C4-Cs alkylene.

5. The polymerizable composition of any one of claims 2-4, wherein L1is, at each occurrence, independently Ce-Cio alkylene.

6. The polymerizable composition of any one of claims 2-5, wherein L1is, at each occurrence, independently branched Ce-Cio alkylene.

7. The polymerizable composition of any one of claims 2-6, wherein L1at each occurrence has the following structure:

8. The polymerizable composition of any one of claims 2-7, wherein L1is unbranched and unsubstituted Ce alkylene.

9. The polymerizable composition of any one of claims 2-8, wherein L1is unbranched and unsubstituted C4-Cs alkylene.

10. The polymerizable composition of any one of claims 2-9, wherein L2is, at each occurrence, independently C4-C12 alkylene.

11. The polymerizable composition of any one of claims 2-10, wherein L2is, at each occurrence, independently unbranched and unsubstituted C4-C12 alkylene.

12. The polymerizable composition of any one of claims 2-11, wherein L2is, at each occurrence, unbranched and unsubstituted Cs alkylene.

13. The polymerizable composition of any one of claims 2-12, wherein L3is, at each occurrence, independently Ce-Cio alkylene.#11356484.

114. The polymerizable composition of any one of claims 2-13, wherein L3is, at each occurrence, independently branched Ce-Cio alkylene.

15. The polymerizable composition of any one of claims 2-14, wherein L3at each occurrence has the following structure:

16. The polymerizable composition of any one of claims 2-15, wherein L1and each occurrence of L3are the same.

17. The polymerizable composition of any one of claims 2-16, wherein R1, R2, or both comprise at least one of the following structures:

18. The polymerizable composition of any one of claims 2-17, wherein R1, R2, or both have the following structure:wherein:71#11356484.1Ais, at each occurrence, independently an optionally substituted Cs-Cs cycloalkylene, an optionally substituted phenylene, an optionally substituted phenylene-Ci-C4 alkylene, or an optionally substituted diphenylmethylene;X3is, at each occurrence, independently -C(=O)-O-, -O-C(=O)-, -O-, -S-, -O-C(=O)-O-, -C(=O)-O-C(=O)-, -NH-C(=O)-O-, -O-C(=O)-NH-, -C(=O)-NH-C(=O)-, or -NH-C(=O)-NH-;L4is, at each occurrence, independently a direct bond or C1-C4 alkylene;L5is, at each occurrence, independently C1-C4 alkylene;R3is, at each occurrence, independently hydrogen, halo, or -CH3.

19. The polymerizable composition of any one of claims 2-18, wherein R1, R2, or both have the following structure:wherein:is, at each occurrence, independently an optionally substituted C3-C8 cycloalkylene, an optionally substituted phenylene, an optionally substituted phenylene-Ci-C4 alkylene, or an optionally substituted diphenylmethylene;L4is, at each occurrence, independently a direct bond or C1-C4 alkylene;L5is, at each occurrence, independently C1-C4 alkylene;R3is, at each occurrence, independently hydrogen, halo, or -CH3.

20. The polymerizable composition of any one of claims 2-19, wherein R1, R2, or both have the following structure:#11356484.

121. The polymerizable composition of any one of claims 18-20, wherein L4is methylene.(A 22. The polymerizable composition of any one of claims 18-21, wherein ' is optionally substituted with one or more methyl substituents.(A 23. The polymerizable composition of any one of claims 18-22, wherein ' is cyclohexylene.(A;24. The polymerizable composition of any one of claims 18-23, wherein has the following structure:

25. The polymerizable composition of any one of claims 18-24, whereinhas one of the following structures:

26. The polymerizable composition of any one of claims 18-25, whereinhas one of the following structures:73#11356484.

127. The polymerizable composition of any one of claims 1-26, wherein the oligomer has the following structure:wherein:Rlaand R2aeach have the following structure:nl is an integer ranging from 1 to 50.

28. The polymerizable composition of claim 27, wherein nl is an integer ranging from 20 to 40.

29. The polymerizable composition of any one of claims 1-28, wherein the oligomer has a viscosity ranging from 10,000 to 50,000 cP.

30. The polymerizable composition of any one of claims 1-28, wherein the oligomer has a viscosity ranging from 10,000 to 25,000 cP.

31. The polymerizable composition of any one of claims 1-28, wherein the oligomer has a viscosity ranging from 20,000 to 50,000 cP.

32. The polymerizable composition of any one of claims 1-31, wherein the oligomer has a molecular weight greater than 1500 g / mol.

33. The polymerizable composition of any one of claims 1-32, wherein the oligomer has a molecular weight greater than 2000 g / mol.74#11356484.

134. The polymerizable composition of any one of claims 1-33, wherein the oligomer has a molecular weight greater than 5000 g / mol.

35. The polymerizable composition of any one of claims 1-34, wherein the oligomer has a molecular weight greater than 7,500 g / mol.

36. The polymerizable composition of any one of claims 1-35, wherein the oligomer has a molecular weight greater than 10,000 g / mol.

37. The polymerizable composition of any one of claims 1-36, wherein the oligomer has a molecular weight greater than 12,500 g / mol.

38. The polymerizable composition of any one of claims 1-37, wherein the amine synergist is an aliphatic amine methacylate.

39. The polymerizable composition of any one of claims 1-37, wherein the amine synergist has one of the following structures:The polymerizable composition of any one of claims 1-39, wherein the reactive diluent has the following structure:wherein:X is O, S, NR8, or SiR9R10;R4ais H, substituted or unsubstituted C1-3 alkyl, or halogen;75#11356484.1R4bis optionally substituted Ci-6 alkyl, optionally substituted Ci-6 heteroalkyl, optionally substituted Ci-6 carbonyl, optionally substituted Ci-6 carboxy, optionally substituted C3-C8 cycloalkyl, optionally substituted 3-8 membered heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;R5, R6, and R7are each independently H, optionally substituted Ci-6 alkyl, optionally substituted Ci-6 heteroalkyl, optionally substituted Ci-6 alkoxy, optionally substituted Ci-6 thioalkoxy, optionally substituted Ci-6 carbonyl, optionally substituted Ci-6 carboxy, or -Y-(CH2)n-Ru; or R6and R7together form a 4-, 5-, 6-, 7-, or 8-membered ring selected from optionally substituted C4-8 cycloalkyl, optionally substituted 4-8 membered heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;wherein Y is O, S, NH, or C(O)O;n is an integer from 0 to 6;R8, R9, and R10are independently H or optionally substituted C1-6 alkyl; andR11is optionally substituted C3-8 cycloalkyl, optionally substituted 3-8 membered heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

41. The polymerizable composition of any one of claims 1-39, wherein the reactive diluent having one of the following structures:76#11356484.

142. The polymerizable composition of any one of claims 38-41, wherein the initiator comprises a photoinitiator.

43. The polymerizable composition claim 42, wherein the photoinitiator is a type 1 photoinitiator.

44. The polymerizable composition of any one of claims 42-43, wherein the photoinitiator comprises a free radical photoinitiator.

45. The polymerizable composition of any one of claims 1-44, wherein the initiator comprises a thermal initiator.

46. The polymerizable composition of claim 45, wherein the thermal initiator comprises azobi si sobutyronitrile, 2, 2'-azodi(2 -methylbutyronitrile), or a combination thereof.

47. The polymerizable composition of any one of claims 1-46, wherein the polymerizable composition is a photocurable composition.

48. The polymerizable composition of any one of claims 1-47, wherein the concentration of oligomer ranges from 25-65 wt%.

49. The polymerizable composition of any one of claims 1-48, wherein the concentration of oligomer ranges from 30-60 wt%.

50. The polymerizable composition of any one of claims 1-49, wherein the concentration of reactive diluent ranges from 25-65 wt%.

51. The polymerizable composition of any one of claims 1-50, wherein the concentration of reactive diluent ranges from 30-60 wt%.

52. The polymerizable composition of any one of claims 1-51, wherein the polymerizable composition comprises 0.01-10 wt% of the initiator.77#11356484.

153. The polymerizable composition of any one of claims 1-52, wherein the oligomer is present at a concentration of 10-70 wt%, the reactive diluent is present at a concentration of 25-80 wt%, the amine synergist is present at a concentration of 0.1-5.0 wt%, and the initiator is present at a concentration of 0.5-5 wt%.

54. The polymerizable composition of any one of claims 1-53, further comprising one or more reagents selected from the group consisting of a crosslinking modifier, a glass transition temperature modifier, a toughness modifier, a polymerization catalyst, a polymerization inhibitor, a light blocker, a plasticizer, a surface energy modifier, a pigment, a dye, a filler, a biologically significant chemical, a solvent, and combinations thereof.

55. The polymerizable composition of any one of claims 1-54, wherein the polymerizable composition is capable of being 3D printed at a printing temperature greater than 25 °C.

56. The polymerizable composition of claim 1-55, wherein the printing temperature is at least 30 °C, 40 °C, 50 °C, 60 °C, 80 °C, 100 °C, or 25-80°C.

57. The polymerizable composition of any one of claims 1-56, wherein the polymerizable composition has a viscosity from 500 cP to 5,000 cP at a printing temperature.

58. The polymerizable composition of any one of claims 1-57, wherein the polymerizable composition is a liquid at a temperature from about 40 °C to about 100 °C.

59. The polymerizable composition of any one of claims 1-58, wherein the polymerizable composition is a liquid at a temperature of above about 40 °C with a viscosity less than about 5 PaS.

60. The polymerizable composition of any one of claims 1-59, wherein at least a portion of the polymerizable composition melts at a temperature between about 60 °C and about 0 °C.78#11356484.

161. A polymer formed from the polymerizable composition of any one of claims 1- 60.

62. The polymer of claim 61, wherein the polymer is characterized by a water uptake of less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.25 wt%, or less than 0.1 wt% when measured after 24 hours in a wet environment at 37 °C.

63. The polymer of any one of claims 61-62, wherein the polymer has greater than 90% conversion of double bonds to single bonds compared to the polymerizable composition, as measured by FTIR.

64. The polymer of any one of claims 61-63, wherein the polymer has an ultimate tensile strength from 10 MPa to 100 MPa, from 15 MPa to 80 MPa, from 20 MPa to 60 MPa, from 10 MPa to 50 MPa, from 10 MPa to 45 MPa, from 25 MPa to 40 MPa, from 30 MPa to 45 MPa, or from 30 MPa to 40 MPa after 24 hours in a wet environment at 37 °C.

65. The polymer of any one of claims 61-64, wherein the polymer is characterized by an elongation at break greater than 10%, an elongation at break greater than 20%, an elongation at break greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break value between 40% and 250% before and after 24 hours in a wet environment at 37 °C.

66. The polymer of any one of claims 61-65, wherein the polymer is characterized by a storage modulus of 0.1 MPa to 4000 MPa, a storage modulus of 300 MPa to 3000 MPa, or a storage modulus of 750 MPa to 3000 MPa after 24 hours in a wet environment at 37 °C.

67. The polymer of any one of claims 61-66, wherein the polymer has a flexural stress, a flexural modulus, or a flexural stress and flexural modulus of 400 MPa or more, 300 MPa or more, 200 MPa or more, 180 MPa or more, 160 MPa or more, 120 MPa or more, 100 MPa or more, 80 MPa or more, 70 MPa or more, 60 MPa or more, after 24 hours in a wet environment at 37 °C.79#11356484.

168. The polymer of any one of claims 61-67, wherein at least 40%, 50%, 60%, or 70% of visible light passes through the polymer after 24 hours in a wet environment at 37 °C.

69. The polymer of any one of claims 61-68, wherein the polymer is biocompatible, bioinert, or a combination thereof.

70. A polymeric film comprising a polymer of any one of claims 61-69.

71. The polymeric film of claim 70, wherein the polymeric film has a thickness of at least 100 pm and not more than 3 mm.

72. An orthodontic appliance comprising the polymer of any one of claims 61-70 or the polymeric film of any one of claims 70-71.

73. The orthodontic appliance of claim 72, wherein the orthodontic appliance is a dental appliance.

74. The orthodontic appliance of claim 73, wherein the orthodontic appliance is a dental aligner, a dental expander, or a dental spacer.

75. A method of forming a polymer, the method comprising:providing a polymerizable composition of any one of claims 1-60;exposing the polymerizable composition to a light source; andpolymerizing the polymerizable composition to form the polymer.

76. The method of claim 75, wherein the light source is an ultraviolet (UV) or visible light source.

77. The method of any one of claims 75-76, further comprising fabricating an orthodontic appliance with the polymer.80#11356484.

178. A method for preparing an article by an additive manufacturing process, comprising:providing a polymerizable composition of any one of claims 1-60;exposing the polymerizable composition to radiation;polymerizing the polymerizable composition layer-by-layer based on a predefined design, thereby polymerizing the polymer composition to form a polymer; andfabricating the article with the polymer.

79. The method of claim 78, wherein the method further comprises heating the polymerizable composition at a processing temperature.

80. The method of claim 79, wherein the processing temperature is from about 50°C to about 120°C.

81. The method of claim 79, wherein the processing temperature is from about 90°C to about 110°C, from about 100°C to about 120°C, from about 105°C to about 115°C, or from about 108°C to about 110°C.

82. The method of any one of claims 78-81, wherein the method further comprises receiving a file containing instructions for fabrication of a dental appliance.

83. The method of any one of claims 78-82, wherein the additive manufacturing process is a 3D printing process.

84. The method of any one of claims 78-83, wherein the article is a medical device.

85. The method of claim 84, wherein the medical device is an orthodontic appliance.

86. A method of repositioning a patient's teeth, comprising:generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement;81#11356484.1producing an orthodontic appliance according to any one of claims 72-74, or an orthodontic appliance comprising the polymer of any one of claims 61-69; andmoving on-track, with the orthodontic appliance, at least one of the patient's teeth toward an intermediate tooth arrangement or the final tooth arrangement.

87. The method of claim 86, wherein producing the orthodontic appliance comprises 3D printing of the orthodontic appliance.

88. The method of any one of claims 86-87, further comprising tracking progression of the patient's teeth along the treatment path after administration of the orthodontic appliance to the patient, the tracking comprising comparing a current arrangement of the patient's teeth to a planned arrangement of the patient's teeth.

89. The method of any one of claims 86-88, wherein greater than 60% of the patient's teeth are on track with the treatment plan after 2 weeks of treatment.

90. The method of any one of claims 86-89, wherein the orthodontic appliance has a retained repositioning force to the at least one of the patient's teeth after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of repositioning force initially provided to the at least one of the patient's teeth.

91. The method of any one of claims 86-90, wherein the treatment plan is generated using an intraoral scan of the patient's teeth.82#11356484.1

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