Additive for 3D printing of polymeric resins

Abstract

The present disclosure provides micelles comprising a plurality of block copolymers, the micelles comprising: (i) a core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and (ii) an outer layer comprising at least a portion of a poly(aryl acrylate) block or a poly(aryl methacrylate) block of one or more block copolymers. The present disclosure also includes polymer compositions, polymer films, and devices (e.g., orthodontic appliances) comprising the same. Methods of making and using the micelles, polymer compositions, polymer films, and devices (e.g., orthodontic appliances) are also disclosed. Methods of producing polymer compositions and methods of using the compositions to make (e.g., by 3D printing) medical devices (e.g., orthodontic appliances) are also provided herein.

Description

[0001] By incorporating via reference

[0002] All publications, patents, and patent applications mentioned in this specification, including U.S. Patent Application No. 63 / 487,666, filed February 28, 2023, are incorporated herein by reference to the same extent that each individual publication, patent, or patent application is specifically and individually identified as incorporated herein by reference.

[0003] Background of this disclosure

[0004] Poly(eugenol methacrylate) and poly(eugenol acrylate) are compounds with relatively high glass transition temperatures (T0). g Rigid polymers (e.g., shear yield strength, toughness) are sought to improve various properties of these polymers because they can be used in a wide range of different fields. Therefore, new additives are needed to impart these properties and produce polymer compositions with these superior properties. This disclosure addresses these and other needs.

[0005] Overview of this disclosure

[0006] This disclosure provides micelles comprising block copolymers that impart excellent properties to polymer compositions. The block copolymers of this disclosure form micelles having a core and an outer layer. Poly(aryl methacrylate) (e.g., poly(2,6-dimethoxyphenyl methacrylate)) and poly(aryl acrylate) (e.g., poly(2,6-dimethoxyphenyl acrylate)) polymers are rigid and have high glass transition temperatures (T0). g Value); poly(alkyl acrylate) polymers (e.g., poly(butyl acrylate)) are rubbery and have low T values. g Value. When these two polymer types are covalently bonded together (e.g., in a block copolymer), microphase separation is thought to occur. When added to a polymer composition that is primarily a eugenol-rich resin, micelles with a rigid outer layer and a rubbery core may form. These micelles are thought to cause localized disruption in the polymer network, resulting in energy absorption processes such as shear yielding. Therefore, one embodiment provides a block copolymer having at least a first block and a second block, wherein:

[0007] i) The first block is a poly(aryl acrylate) or poly(aryl methacrylate) block having 10-300 repeating units or a poly(aryl methacrylate) block having 10-300 repeating units.

[0008] ii) The second block is a poly(alkyl acrylate) block having 10-300 repeating units.

[0009] Another embodiment provides a block copolymer having at least a first block and a second block, wherein:

[0010] i) The first block is a poly(aryl acrylate) block or a poly(aryl methacrylate) block containing the following substructures:

[0011]

[0012] in:

[0013] R 1 Each time it appears, it is independently either hydrogen or CH3;

[0014] n1 is an integer in the range of 10-300; and

[0015] ii) The second block is a poly(alkyl acrylate) block containing the following substructures:

[0016]

[0017] in:

[0018] R 2 Each occurrence is independently a C1-C6 alkyl group; and

[0019] n2 is an integer in the range of 10-300.

[0020] Another embodiment provides a micelle comprising a plurality of block copolymers, the micelle comprising:

[0021] i) A core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and

[0022] ii) an outer layer comprising at least a portion of a poly(aryl acrylate) block (e.g., poly(2,6-dimethoxyphenyl acrylate)) or a poly(aryl methacrylate) block (e.g., poly(2,6-dimethoxyphenyl methacrylate)) of one or more block copolymers.

[0023] Another embodiment provides a photocurable resin comprising:

[0024] i) aryl acrylate monomers, aryl methacrylate monomers, or combinations thereof; and

[0025] ii) Macromolecular initiator compounds having the following structures:

[0026]

[0027] in:

[0028] n2 is an integer in the range of 10-500.

[0029] Another embodiment provides a photocurable resin comprising: i) an aryl acrylate monomer, an aryl methacrylate monomer, or a combination thereof; ii) an alkyl acrylate monomer; and iii) an initiator.

[0030] Another embodiment provides a polymer composition comprising micelles dispersed in and in physical contact with a photopolymer network as described in this disclosure. That is, some embodiments provide a polymer composition comprising micelles containing a plurality of block copolymers, the micelles comprising:

[0031] i) a core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and

[0032] ii) An outer layer comprising at least a portion of a poly(aryl acrylate) block (e.g., poly(2,6-dimethoxyphenyl acrylate)) or a poly(aryl methacrylate) block (e.g., poly(2,6-dimethoxyphenyl methacrylate)) of one or more block copolymers.

[0033] in:

[0034] The micelles are dispersed in and in physical contact with the photopolymer network.

[0035] Another embodiment provides a polymer composition comprising micelles dispersed and covalently bonded thereto within a photopolymer network as described in this disclosure. That is, some embodiments provide a polymer composition comprising micelles containing a plurality of block copolymers, the micelles comprising:

[0036] i) A core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers;

[0037] ii) An outer layer comprising at least a portion of a poly(aryl acrylate) block (e.g., poly(2,6-dimethoxyphenyl acrylate)) or a poly(aryl methacrylate) block (e.g., poly(2,6-dimethoxyphenyl methacrylate)) of one or more block copolymers.

[0038] in:

[0039] The micelles are dispersed in and covalently bonded to a photopolymer network.

[0040] Another embodiment provides a polymer film comprising a polymer composition comprising micelles containing a plurality of block copolymers, the micelles comprising

[0041] i) A core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and

[0042] ii) An outer layer comprising at least a portion of a poly(aryl acrylate) block (e.g., poly(2,6-dimethoxyphenyl acrylate)) or a poly(aryl methacrylate) block (e.g., poly(2,6-dimethoxyphenyl methacrylate)) of one or more block copolymers.

[0043] in:

[0044] The micelles are dispersed in and in physical contact with the photopolymer network.

[0045] One embodiment provides a polymer film comprising a polymer composition including micelles containing a plurality of block copolymers, the micelles comprising:

[0046] i) A core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and

[0047] ii) An outer layer comprising at least a portion of a poly(aryl acrylate) block (e.g., poly(2,6-dimethoxyphenyl acrylate)) or a poly(aryl methacrylate) block (e.g., poly(2,6-dimethoxyphenyl methacrylate)) of one or more block copolymers.

[0048] in:

[0049] The micelles are dispersed in and covalently bonded to the photopolymer network.

[0050] Some embodiments provide a method for forming a polymer composition, the method comprising: providing a photocurable resin according to an embodiment disclosed herein; exposing the photocurable resin to a light source; and polymerizing the photocurable resin to form a polymer.

[0051] Some additional embodiments provide a method for preparing articles by an additive manufacturing process, comprising: providing a photocurable resin according to an embodiment disclosed herein; heating the photocurable resin to a processing temperature; exposing the photocurable resin to radiation; polymerizing the photocurable resin layer by layer based on a predetermined design, thereby polymerizing monomers to form a polymer composition; and manufacturing articles with the polymer composition.

[0052] One embodiment provides an orthodontic appliance comprising a polymer composition or polymer membrane as described herein. Another embodiment provides a method for repositioning a patient's teeth, comprising (1) generating a treatment plan for the patient, the plan including a plurality of intermediate dentitions for moving teeth along a treatment path from an initial dentition toward a final dentition; (2) producing an orthodontic appliance according to the embodiments disclosed herein; and (3) using the orthodontic appliance to move at least one of the patient's teeth along the treatment plan toward an intermediate dentition or a final dentition.

[0053] In various aspects, this document provides a polymer composition formed from a photopolymer network and micelles according to the present disclosure. In some aspects, the polymer composition has one or more of the following properties: (A) a flexural modulus of at least about 50 MPa, 75 MPa, 100 MPa, 150 MPa, or at least about 175 MPa; (B) an elastic modulus of at least about 500 MPa to about 1500 MPa, at least about 550 MPa to about 1000 MPa, or at least about 550 MPa to about 800 MPa; (C) an elongation at break greater than or equal to 2.5% before and after 24 hours in a humid environment at 37°C; (D) a water absorption rate of less than 20 wt% when measured after 24 hours in a humid environment at 37°C; (E) a visible light transmittance of at least 20% after 24 hours in a humid environment at 37°C; and (F) containing T g The polymer composition has a polymer phase with a temperature of at least 60°C, 80°C, 90°C, 100°C, or at least 110°C. In some aspects, the polymer composition has at least two properties selected from (A), (B), (C), (D), (E), and (F). In some aspects, the polymer composition has at least three properties selected from (A), (B), (C), (D), (E), and (F). In some aspects, the polymer composition has at least four properties selected from (A), (B), (C), (D), (E), and (F). In some aspects, the polymer composition has at least five properties selected from (A), (B), (C), (D), (E), and (F). In some aspects, the polymer composition has all properties (A), (B), (C), (D), (E), and (F).

[0054] In some aspects, the polymer composition is characterized by having a water absorption rate 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 humid environment at 37°C.

[0055] In some aspects, after 24 hours in a humid environment at 37°C, the ultimate tensile strength of the polymer composition is 10 MPa to 100 MPa, 15 MPa to 80 MPa, 20 MPa to 60 MPa, 10 MPa to 50 MPa, 10 MPa to 45 MPa, 25 MPa to 40 MPa, 30 MPa to 45 MPa, or 30 MPa to 40 MPa. In some aspects, the polymer composition is characterized by an elongation at break greater than 10%, greater than 20%, greater than 30%, 5% to 250%, or 20% to 250% or 40% to 250% before and after 24 hours in a humid environment at 37°C. In some aspects, the polymer composition is characterized by having a storage modulus of 0.1 MPa to 4000 MPa, 300 MPa to 3000 MPa, or 750 MPa to 3000 MPa after 24 hours in a humid environment at 37°C. In some aspects, after 24 hours in a humid environment at 37°C, the residual flexural stress of the polymer composition is 400 MPa or higher, 300 MPa or higher, 200 MPa or higher, 180 MPa or higher, 160 MPa or higher, 120 MPa or higher, 100 MPa or higher, 80 MPa or higher, 70 MPa or higher, or 60 MPa or higher. In some aspects, after 24 hours in a humid environment at 37°C, at least 40%, 50%, 60%, or 70% of visible light passes through the polymer composition. In some aspects, the polymer composition is biocompatible, bioinert, or both. In some aspects, the polymer composition is capable of 3D printing.

[0056] In some aspects, the polymer composition is a polymer film with a thickness of at least 100 μm and not more than 3 mm. In some aspects, an apparatus is provided herein comprising the polymer composition of this disclosure, the polymer film of this disclosure, or a combination thereof. In some aspects, the apparatus is a medical device. In some aspects, the medical device is a dental appliance. In some aspects, the dental appliance is an orthodontic appliance, a dental expander, or a dental spacer.

[0057] In various aspects, this document provides a method for forming a polymer composition, the method comprising: providing a curable resin comprising an alkyl acrylate monomer, a 2,6-dimethoxyphenyl acrylate monomer, a 2,6-dimethoxyphenyl methacrylate monomer, or a combination thereof; curing the curable resin to form a polymer network; and adding micelles of the present disclosure. In some embodiments, the addition is prior to curing. In some embodiments, the addition is post-curing. In some aspects, curing includes photocuring. In some aspects, the method further includes exposing the curable resin to a light source (e.g., infrared light, visible light, ultraviolet light, or a combination thereof).

[0058] In some aspects, the polymer composition has a melting point of at least 60°C, 80°C, 90°C, 100°C, or at least 110°C. In some aspects, the polymer composition is characterized by one or more of the following: (A) a flexural modulus of at least about 50 MPa, 75 MPa, 100 MPa, 150 MPa, or at least about 175 MPa; (B) an elastic modulus of at least about 500 MPa to about 1500 MPa, at least about 550 MPa to about 1000 MPa, or at least about 550 MPa to about 800 MPa; (C) an elongation at break greater than or equal to 2.5% before and after 24 hours in a humid environment at 37°C; (D) a water absorption rate of less than 20 wt% when measured after 24 hours in a humid environment at 37°C; (E) a visible light transmittance of at least 20% after 24 hours in a humid environment at 37°C; and / or (F) containing T g The polymer phase is at least 60°C, 80°C, 90°C, 100°C, or at least 110°C. In some aspects, the method further includes manufacturing a medical device using the polymer composition. In some aspects, the medical device is a dental appliance. In some aspects, the dental appliance is an orthodontic appliance, a dental expander, or a dental spacer.

[0059] In various aspects, this document provides a method for repositioning a patient's teeth, the method comprising: generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement; producing a dental appliance according to the present disclosure or a dental appliance comprising a polymer composition thereof; and using an orthodontic appliance to move at least one of the patient's teeth along the treatment plan toward an intermediate tooth arrangement or a final tooth arrangement.

[0060] In some aspects, the production of dental appliances includes 3D printing of dental appliances. In some aspects, the method also includes tracking the progress of a patient's teeth along a treatment path after application of the dental appliance to the patient, the tracking including comparing the current alignment of the patient's teeth with the planned alignment of the patient's teeth. In some aspects, after two weeks of treatment, more than 60% of the patient's teeth conform to the treatment plan. In some aspects, after two days, the repositioning force retained by the dental appliance for at least one of the patient's teeth is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the initial repositioning force applied to at least one of the patient's teeth. Attached Figure Description

[0061] The novel features of this disclosure are set forth in the appended claims. A better understanding of the features and advantages of this disclosure will be obtained by referring to the following detailed description and accompanying drawings, which illustrate illustrative embodiments utilizing the principles of the invention, and in the drawings: Figure 1A A tooth repositioning appliance according to some implementation schemes is shown.

[0062] Figure 1B A tooth repositioning system according to some implementation schemes is shown.

[0063] Figure 1C An orthodontic treatment method using multiple appliances is shown according to some implementation schemes.

[0064] Figure 2 A method for designing orthodontic appliances based on some implementation schemes is shown.

[0065] Figure 3 Methods for digitally planning orthodontic treatment are illustrated according to some implementation schemes.

[0066] Figure 4 The invention illustrates the generation and implementation of a treatment according to one embodiment of the present disclosure.

[0067] Figure 5 A schematic configuration of a high-temperature additive manufacturing apparatus is shown, which is used to cure the curable resin disclosed herein via a 3D printing process.

[0068] Figure 6 A cross-sectional view of a micelle formed by a block copolymer is shown, the micelle having a core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and an outer layer comprising at least a portion of a poly(aryl acrylate) (e.g., poly(2,6-dimethoxyphenyl acrylate)) block or a poly(aryl methacrylate) (e.g., poly(2,6-dimethoxyphenyl methacrylate)) block of one or more block copolymers.

[0069] Figure 7 This is a flowchart providing a general overview of methods for manufacturing and post-processing additively manufactured objects according to some embodiments of this disclosure.

[0070] Figure 8 A representative example of an additive manufacturing apparatus is shown.

[0071] Figure 9 Methods for designing orthodontic appliances according to some embodiments of this disclosure are described.

[0072] Figure 10 Methods for digitally planning orthodontic treatment and / or designing or manufacturing appliances are illustrated according to some embodiments of this disclosure.

[0073] Detailed description

[0074] This disclosure provides micelles comprising block copolymer compounds and polymer compositions comprising the same block copolymer compounds, as well as their uses (e.g., incorporation into orthodontic articles, incorporation into polymer compositions, etc.) and methods of production. The compounds described herein can address unmet needs in the production of high-T g There is a demand for high-performance polymer materials that are given greater toughness and can be used in a variety of equipment applications.

[0075] This disclosure describes the synthesis and application of block copolymers to enhance the toughness of (meth)acrylate-based photopolymer networks, particularly those compositions rich in eugenyl compounds (e.g., poly(2,6-dimethoxyphenyl acrylate) or poly(2,6-dimethoxyphenyl methacrylate)). In some embodiments, the block copolymers are self-assembled (e.g., they spontaneously form micelles).

[0076] While not wishing to be bound by theory, it is believed that adding relatively low wt% block copolymers can enhance the toughness of eugenol-rich polymer networks through interactions with diblock or triblock copolymers. Poly[(meth)acrylate eugenol ester] blocks form a "resin-loving" outer layer, while poly(alkyl acrylate) blocks (e.g., poly(n-butyl acrylate)) form a "resin-repellent" core. Overall, multiple block copolymers form micelles, with the poly(alkyl acrylate) blocks undergoing cavitation to form a rubbery core (see, for example,...). Figure 6 In some embodiments, micelles form covalent bonds with the photopolymer network (e.g., when end groups of block copolymers are added to promote additional polymerization). When additional polymerization steps occur, the micelles become fixed and provide dispersed sites within the network where local properties are effectively disrupted, thereby allowing energy absorption processes (e.g., shear yielding) to occur when the network is subjected to stress.

[0077] As used herein, "monomer component," "monomer," or grammatically equivalent terms refer to molecules (e.g., olefins or functionalized substituted olefins) having reactive functional groups capable of undergoing free radical-initiated polymerization. Such polymerization can be photoinduced, for example, generated via free radicals. In some embodiments, the monomer component is ethylene, vinyl chloride, vinyl fluoride, trichlorofluoroethylene, tetrafluoroethylene, propylene, 2-methylpropylene, styrene, acrylonitrile, methyl methacrylate, styrene, alkyl acrylates (e.g., n-butyl acrylate), 1,6-hexanediol diacrylate, 2,6-dimethoxyphenyl acrylate, 2,6-dimethoxyphenyl methacrylate, etc.

[0078] This document also provides curable compositions comprising one or more micelles of the present disclosure. Such curable (e.g., photocurable) compositions may also contain monomers and / or other components capable of further polymerization, such as reactive diluents, telechelic polymers, or, for example, toughening modifiers.

[0079] This article also provides a method for producing polymer compositions that can be used in devices such as medical devices and orthodontic appliances using micelles and compositions containing the micelles.

[0080] All terms, chemical names, expressions, and names have their common meanings well known to those skilled in the art. The terms “to comprise” and “comprising” as used herein should be understood as non-limiting, meaning that they may include components other than those explicitly named. The terms “composition” or “consisting of” mean that only the explicitly described components are included. The term “substantially composed of” limits the scope to the specified materials, elements, steps, embodiments, aspects, and limitations, except those that do not materially affect the essential and novel characteristics. For each embodiment of this disclosure, it should be understood that, with the use of any of the foregoing phrases, any specified materials, elements, steps, embodiments, aspects, and limitations may be included.

[0081] Numerical ranges should be understood as inclusive, meaning they include both the lower and upper limits indicated (e.g., the phrase "integers of 1-3" includes the integers 1, 2, and 3). Furthermore, unless explicitly indicated otherwise, the term "about" as used herein refers to and covers plus or minus 10% of the indicated numerical value. For example, "about 10%" could indicate a range of 9% to 11%, and "about 1" could include a range of 0.9 to 1.1.

[0082] As used herein, the terms “polymer,” “polymer composition,” “photopolymer network,” or their equivalents refer to a molecule composed of repeating structural units linked by covalent chemical bonds, characterized by a large number of repeating units (e.g., equal to or greater than 10 repeating units; in some embodiments, the 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, the polymer composition has a molecular weight greater than or equal to 10 kDa, 15 kDa, 20 kDa, 30 kDa, 40 kDa, 50 kDa, or 100 kDa. In some embodiments, the micelles, polymer networks, and / or polymer compositions of this disclosure are polymer products of the photoinitiator and (optionally) one or more monomer components of this disclosure. The term polymer includes homopolymers, i.e., polymers composed essentially of a single repeating monomer species. The term polymer also includes copolymers formed when two or more different types (or species) of monomers are linked in the same polymer. Copolymers may include two or more different monomer species and include random, block, alternating, segmented, grafted, tapered and other copolymers.

[0083] As used herein, the term "oligomer" generally refers to a molecule composed of repeating structural units linked by covalent chemical bonds, characterized by a number of repeating units less than the number of repeating units in a polymer (e.g., equal to or less than 20 or less than 10 repeating units) and a molecular weight lower than that of the polymer, for example, less than 5,000 Da or less than 2,000 Da, and in various cases from about 0.5 kDa to about 5 kDa. In some cases, oligomers may be polymers of one or more monomer precursors.

[0084] As used herein, the term "reactive diluent" generally refers to a substance that reduces the viscosity of another substance, such as a monomer or a curable resin. A reactive diluent can be part of another substance, such as a polymer obtained through a polymerization process. In some instances, a reactive diluent is a curable monomer that, when mixed with a curable resin, reduces the viscosity of the resulting formulation and is incorporated into the polymer produced by the polymerization of the formulation.

[0085] Oligomeric and polymer compositions are characterized by measurements of molecular weight and molecular weight distribution, and are distinguished from other mixtures of oligomers and polymers.

[0086] The average molecular weight (M) is the product of the average number of repeating units n and the molecular weight or molar mass of the repeating units (M). i Number-average molecular weight (M) n () is the arithmetic mean, which represents the total weight of the existing molecules divided by the total number of molecules.

[0087] As used herein, the term "biocompatibility" refers to a material that, when placed in an in vivo biological environment, does not induce immune rejection or adverse effects (referred to herein as adverse immune responses). For example, in some embodiments, when a human or animal is exposed to or comes into contact with a biocompatible material, the change in biomarkers indicating an immune response relative to baseline values ​​is less than 10%, less than 20%, less than 25%, less than 40%, or less than 50%. Alternatively, the immune response can be determined histologically, wherein a local immune response is assessed by visually evaluating markers (including immune cells or markers involved in immune response pathways) within and near the material. In one aspect, the biocompatible material or device does not significantly alter the histologically determined immune response. In some embodiments, this disclosure provides biocompatible devices configured for long-term use (e.g., over a period of about several weeks to several months) without inducing adverse immune responses. Biological effects can initially be assessed by measuring cytotoxicity, sensitization, irritation and intradermal reactivity, acute systemic toxicity, pyrogenicity, subacute / subchronic toxicity, and / or implantation. Biological tests for supplemental assessment include tests for chronic toxicity.

[0088] "Bio-inert" refers to a material that does not elicit an immune response in humans or animals when placed in an in vivo biological environment. For example, when humans or animals are exposed to or come into contact with a bio-inert material, biomarkers indicating an immune response remain substantially constant (plus or minus 5% of baseline values). In some embodiments, this disclosure provides bio-inert devices.

[0089] When a group of substituents is disclosed herein, it should be understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of members within that group, are disclosed individually. When the Markush group or other groupings are used herein, all individual members of that group, as well as all possible combinations and subcombinations of that group, are intended to be included individually in this disclosure. When a compound is described herein such that a particular isomer, enantiomer, or diastereomer of the compound is not specified in, for example, a formula or chemical name, the description is intended to include each isomer and enantiomer of the compound described individually or in any combination. Furthermore, unless otherwise indicated, all isotopic variants of the compounds disclosed herein are intended to be covered in this disclosure. Specific names of compounds are intended to be exemplary, as it is known that those skilled in the art can name the same compounds in different ways.

[0090] It should be noted that the singular forms “a,” “an,” and “the” used herein and in the appended claims include the plural referents unless the context clearly specifies otherwise. Thus, for example, reference to “a monomer” includes a variety of such monomers and their equivalents known to those skilled in the art. Furthermore, the terms “a” (or “an”), “one or more,” and “at least one” are used interchangeably herein. It should also be noted that the terms “comprising,” “including,” and “having” are used interchangeably.

[0091] As used herein, the terms "group" or "part" can refer to a reactive functional group of a compound. In the compounds of this invention, a group refers to an atom or collection of atoms that is part of the compound. Groups of this disclosure can be attached to other atoms of the compound via one or more covalent bonds. Groups can also be characterized according to their valence state. This disclosure includes groups characterized by monovalent, divalent, trivalent, and other valence states.

[0092] As used herein, the term “substituted” refers to a compound in which hydrogen is replaced by another reactive functional group or atom as described herein (e.g., an alkyl chain).

[0093] The examples used in this article symbols in This indicates that a given portion (in this case, the cyclohexyl portion) is attached to the molecule via a bond “sealed” with a wavy line.

[0094] "Alkyl" refers to a saturated, straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, having 1 to 12 carbon atoms (C1-C2). 12 Alkyl groups, having 1 to 8 carbon atoms (C1-C8 alkyl) or 1 to 6 carbon atoms (C1-C6 alkyl), or any value within these ranges, such as C4-C6 alkyl, are attached to the remainder of the molecule by single bonds, for example, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), 3-methylhexyl, 2-methylhexyl, etc. The number of carbon atoms referred to relates to the carbon backbone and carbon branches, but excludes carbon atoms belonging to any substituent. Alkyl groups may optionally be substituted unless otherwise expressly stated in the specification.

[0095] "Alkenyl" refers to an unsaturated, straight-chain or branched hydrocarbon chain group composed only of carbon and hydrogen atoms, containing one or more carbon-carbon double bonds and having 2 to 12 carbon atoms (C2-C4). 12The alkenyl group has 2 to 8 carbon atoms (C2-C8 alkenyl) or 2 to 6 carbon atoms (C2-C6 alkenyl), or any value within these ranges, and is connected to the rest of the molecule by a single bond, such as vinyl, propenyl, butenyl, pentenyl, pent-1,4-dienyl, etc. The number of carbon atoms referred to relates to the carbon backbone and carbon branches, but does not include carbon atoms belonging to any substituent. Unless otherwise expressly stated in the specification, the alkenyl group may optionally be substituted.

[0096] The term "alkynyl" refers to an unsaturated straight-chain or branched hydrocarbon group having 2 to 12 carbon atoms (C2-C4). 12 The alkynyl group has 2 to 9 carbon atoms (C2-C9 alkynyl) or 2 to 6 carbon atoms (C2-C6 alkynyl), or any value within these ranges, and has at least one carbon-carbon triple bond. Examples of the alkynyl group may be selected from ethynyl, propynyl, but-1-alkynyl, but-2-alkynyl, etc. The number of carbon atoms referred to relates to the carbon backbone and carbon branches, but does not include carbon atoms belonging to any substituent. Unless otherwise expressly stated in the specification, the alkynyl group may optionally be substituted.

[0097] "Alkoxy" refers to the formula -OR a The group, wherein R a It is an alkyl group as defined above, containing 1 to 12 carbon atoms (C1-C2). 12 Alkoxy groups, having 1 to 8 carbon atoms (C1-C8 alkoxy groups) or 1 to 6 carbon atoms (C1-C6 alkoxy groups), or any value within these ranges. Unless otherwise expressly stated in the specification, alkoxy groups may optionally be substituted.

[0098] "Cycloalkyl" refers to a non-aromatic monocyclic or polycyclic carbocyclic group consisting only of carbon and hydrogen atoms. It can include fused or bridged ring systems and has three to fifteen ring carbon atoms (C3-C4). 15 cycloalkyl groups, with three to ten cyclic carbon atoms (C3-C4). 10 Cycloalkyl groups are cyclic alkyl groups (C3-C8 cycloalkyl groups) or three to eight carbon atoms (C3-C4 cycloalkyl groups), or any value within these ranges, such as three to four carbon atoms (C3-C4 cycloalkyl groups), and are saturated or partially unsaturated and connected to the rest of the molecule by single bonds. Monocyclic groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Polycyclic groups include, for example, adamantyl, norbornyl, decahydronaphthyl, 7,7-dimethyl-bicyclo[2.2.1]heptyl, etc. Unless otherwise expressly stated in the specification, cycloalkyl groups may optionally be substituted.

[0099] Aryl groups include those having one or more 5, 6, 7, or 8-membered aromatic rings (including heterocyclic aromatic rings). The term heteroaryl specifically refers to an aryl group having at least one 5, 6, 7, or 8-membered heterocyclic aromatic ring. An aryl group may contain one or more fused aromatic rings, including one or more fused heterocyclic aromatic rings, and / or may have combinations of one or more aromatic rings fused or covalently linked to one or more non-aromatic rings. Heterocyclic aromatic rings may contain one or more N, O, or S atoms. Heterocyclic aromatic rings may include those having one, two, or three N atoms, those having one or two O atoms, and those having one or two S atoms, or combinations having one, two, or three N, O, or S atoms. Aryl groups are optionally substituted. Substituted aryl groups include those substituted with alkyl or alkenyl groups, which may themselves be optionally substituted. Specific aryl groups include phenyl, biphenyl, pyrrolyl, imidazoyl, tetrahydrofuranyl, tetrahydrothiophenyl, furanyl, thiophenyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazoyl, oxazolyl, thiazoyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, and naphthyl, all of which are optionally substituted. Substituted aryl groups include perhalogenated or hemihalogenated aryl groups, such as aryl groups where one or more hydrogen atoms are substituted by one or more fluorine, chlorine, bromine, and / or iodine atoms. Substituted aryl groups include perfluorinated or hemifluorinated aryl groups, such as aryl groups where one or more hydrogen atoms are substituted by one or more fluorine atoms. Aryl groups include, but are not limited to, groups corresponding to any of the following aromatic or heterocyclic aromatic groups: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, tetracene, tetracene dione, pyridine, quinoline, isoquinoline, indole, isoindole, pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furan, benzofuran, dibenzofuran, carbazole, acridine, acridine ketone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthracene, xanthone, flavonoids, coumarin, azulene, or anthracyclines. As used herein, groups corresponding to the groups listed above explicitly include aromatic or heterocyclic aromatic groups among the aromatic and heterocyclic aromatic groups listed herein, including monovalent, divalent, and polyvalent groups, which are provided in the compounds disclosed herein in a covalently bonded configuration at any suitable connection point. In some embodiments, the aryl group contains 5 to 30 carbon atoms. In some embodiments, the aryl group contains an aromatic or heteroaromatic six-membered ring and one or more additional five- or six-membered aromatic or heteroaromatic rings. In many embodiments, the aryl group contains five to eighteen carbon atoms in the ring. Optionally, the aryl group has one or more aromatic or heterocyclic aromatic rings having one or more electron-donating groups, electron-withdrawing groups, and / or targeting ligands provided as substituents.

[0100] Arylalkyl groups are alkyl groups substituted with one or more aryl groups, wherein the alkyl group optionally carries additional substituents, and the aryl group is optionally substituted. A specific alkylaryl group is a phenyl-substituted alkyl group, such as phenylmethyl. Alkylaryl groups can alternatively be described as aryl groups substituted with one or more alkyl groups, wherein the alkyl group optionally carries additional substituents, and the aryl group is optionally substituted. A specific alkylaryl group is an alkyl-substituted phenyl group, such as methylphenyl. Substituted arylalkyl groups include perhalogenated or semihalogenated arylalkyl groups, such as arylalkyl groups having one or more alkyl and / or aryl groups in which one or more hydrogen atoms are substituted with one or more fluorine, chlorine, bromine, and / or iodine atoms.

[0101] The terms “alkylene” and “alkylene group” are used synonymously as used herein and refer to a divalent group “-CH2-” derived from an alkyl group as defined herein. This disclosure includes compounds having one or more alkylene groups. In some compounds, the alkylene group acts as a linking group and / or a spacer group. The compounds of this disclosure may have substituted and / or unsubstituted C1-C... 20 Alkylene, C1-C 10 Alkylenes and C1-C6 alkylenes.

[0102] The terms “cycloalkylene” and “cycloalkylene group” are used synonymously as used herein and refer to a divalent group derived from a cycloalkyl group as defined herein. This disclosure includes compounds having one or more cycloalkylene groups. In some compounds, the cycloalkyl group acts as a linking group and / or a spacer group. The compounds of this disclosure may have substituted and / or unsubstituted C3-C... 20 Cycloalkylene, C3-C 10 Cycloalkylene and C3-C5 cycloalkylene.

[0103] The terms “arylene” and “arylene group” are used synonymously as used herein and refer to a divalent group derived from an aryl group as defined herein. This disclosure includes compounds having one or more arylene groups. In some embodiments, the arylene group is a divalent group derived from an aryl group by removing hydrogen atoms from two inner ring carbon atoms of the aromatic ring of the aryl group. In some compounds, the arylene group acts as a linking group and / or a spacer group. In some compounds, the arylene group acts as a chromophore, fluorophore, aromatic tendril, dye, and / or imaging group. The compounds disclosed herein include substituted and / or unsubstituted C3-C groups. 30 aryl, C3-C 20 aryl, C3-C 10 Arylenes and C1-C5 arylene compounds.

[0104] The terms “heteroarylene” and “heteroarylene group” are used synonymously as used herein and refer to a divalent group derived from a heteroarylene as defined herein. This disclosure includes compounds having one or more heteroarylene groups. In some embodiments, the heteroarylene is a divalent group derived from a heteroarylene by removing a hydrogen atom from two intracyclic carbon atoms or intracyclic nitrogen atoms of the heteroarylene ring or aromatic ring. In some compounds, the heteroarylene acts as a linking group and / or a spacer group. In some compounds, the heteroarylene acts as a chromophore, aromatic tendril, fluorophore, dye, and / or imaging group. The compounds disclosed herein include substituted and / or unsubstituted C3-C groups. 30 Heteroarylene, C3-C 20 Heteroarylene, C1-C 10 Heteroaryl and C3-C5 heteroaryl.

[0105] The terms “alkenyl” and “alkenyl group” are used synonymously as used herein and refer to a divalent group derived from an alkenyl group as defined herein. This invention includes compounds having one or more alkenyl groups. In some compounds, the alkenyl group acts as a linking group and / or a spacer group. The compounds disclosed herein include substituted and / or unsubstituted C2-C groups. 20 alkenyl, C2-C 10 Alkenyl and C2-C5 alkenyl.

[0106] As used herein, the terms “cycloalkenyl” and “cycloalkenyl group” are used synonymously and refer to a divalent group derived from a cycloalkenyl group as defined herein. This disclosure includes compounds having one or more cycloalkenyl groups. In some compounds, the cycloalkenyl group acts as a linking group and / or a spacer group. The compounds disclosed herein include substituted and / or unsubstituted C3-C... 20 Cycloalkenyl, C3-C 10 Cycloalkenyl and C3-C5 cycloalkenyl.

[0107] As used herein, the terms "ynynyl" and "ynynyl group" are used synonymously and refer to a divalent group derived from an ynyl group as defined herein. This disclosure includes compounds having one or more ynynyl groups. In some compounds, the ynynyl group acts as a linking group and / or a spacer group. The compounds disclosed herein include substituted and / or unsubstituted C2-C groups. 20 alkyne group, C2-C 10 Alynyl and C2-C5 alynyl.

[0108] The terms “halogenated” and “halogen” used in this article are used interchangeably and refer to halogen groups such as fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).

[0109] The term "heterocycle" refers to a ring structure containing at least one other type of atom besides carbon. Examples of such heteroatoms include nitrogen, oxygen, and sulfur. Heterocyclic rings include heterocyclic alicyclic rings and heterocyclic aromatic rings. Examples of heterocycles include, but are not limited to, pyrrolidinyl, piperidinyl, imidazoalkyl, tetrahydrofuranyl, tetrahydrothiophenyl, furanyl, thiophenyl, pyridinyl, quinolinyl, isoquinolinyl, pyridazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl, and tetrazolyl. The atoms of a heterocycle can be bonded to a variety of other atoms and reactive functional groups, for example, provided as substituents.

[0110] The term "alicyclic ring" refers to one or more fused rings that are not aromatic rings. Alicyclic rings include carbocyclic and heterocyclic rings.

[0111] The term "aromatic ring" refers to one or more fused rings containing at least one aromatic ring group. The term aromatic ring includes aromatic rings containing carbon, hydrogen, and heteroatoms. Aromatic rings include carbocyclic and heterocyclic aromatic rings. The aromatic ring is a component of the aryl group.

[0112] The term "fused ring" or "fused ring structure" refers to a plurality of alicyclic and / or aromatic rings provided in a fused ring configuration, such as a fused ring sharing at least two intracyclic carbon atoms and / or heteroatoms.

[0113] As used in this article, the term "alkoxyalkyl" refers to a substituent of the formula alkyl-O-alkyl.

[0114] As used herein, the term "polyhydroxyalkyl" refers to a substituent having 2 to 12 carbon atoms and 2 to 5 hydroxyl groups, such as 2,3-dihydroxypropyl, 2,3,4-trihydroxybutyl, or 2,3,4,5-tetrahydroxypentyl.

[0115] The term "polyalkoxyalkyl" as used in this article refers to the formula alkyl-(alkoxy). n - An alkoxy substituent, wherein n is an integer from 1 to 10, for example, 1 to 4, and in some embodiments is 1 to 3.

[0116] As used herein, the term "heteroalkyl" generally refers to an alkyl, alkenyl, or alkynyl group as defined herein, wherein at least one carbon atom of the alkyl group is substituted with a heteroatom. In some cases, a heteroalkyl group may contain 1 to 18 non-hydrogen atoms (carbon and heteroatom), or 1 to 12 non-hydrogen atoms, or 1 to 6 non-hydrogen atoms, or 1 to 4 non-hydrogen atoms in the chain. Heteroalkyl groups may be straight-chain or branched, saturated or unsaturated. Unsaturated heteroalkyl groups have one or more double bonds and / or one or more triple bonds. Heteroalkyl groups may be unsubstituted or substituted. Exemplary heteroalkyl groups include, but are not limited to, alkoxyalkyl groups (e.g., methoxymethyl) and aminoalkyl groups (e.g., alkylaminoalkyl and dialkylaminoalkyl). Heteroalkyl groups may optionally be substituted with one or more substituents.

[0117] The terms “carbonyl” or “oxo” used in this article, for example, in C… 1-6 In the context of carbonyl substituents, it typically refers to a carbon chain of a given length (e.g., C360). 1-6 ( ), where each carbon atom in a given carbon chain can form a carbonyl bond, provided it is chemically feasible with respect to the valence state of that carbon atom. Therefore, in some cases, "C 1-6 A "carbonyl" substituent refers to a carbon chain of 1 to 6 carbon atoms, where the terminal carbon has carbonyl functionality, or the inner carbons have carbonyl functionality (in which case the substituent can be described as a ketone). The term "carboxyl" as used herein refers to, for example, a group at C... 1-6 In the context of carboxyl substituents, it typically refers to a carbon chain of a given length (e.g., C10, C20, C30, C40, C50, C60, C7 ... 1-6 ), where the terminal carbon has carboxyl functionality, unless otherwise defined herein.

[0118] As used in this article, "poly(alkyl acrylate)" refers to polymers or polymer blocks having the following structures:

[0119] in: R is an alkyl group as defined herein; and n is an integer greater than 2.

[0120] In some embodiments, the alkyl group is saturated and unsubstituted. In some embodiments, the alkyl group is C1-C6 alkyl. In some embodiments, the alkyl group is C1-C4 alkyl. In some embodiments, the alkyl group is n-alkyl.

[0121] As used in this article, "poly(aryl acrylate)" refers to a polymer with polymer blocks having the following structure:

[0122] in: R is an aryl group as defined in this paper; and n is an integer greater than 2.

[0123] In some embodiments, the aryl group is a substituted aryl group. In some embodiments, the aryl group is a disubstituted aryl group. In some embodiments, the aryl group is a disubstituted aryl group substituted with an alkoxy substituent. In some embodiments, the aryl group is 2,6-dimethoxyphenyl.

[0124] As used in this article, "poly(aryl acrylate)" refers to a polymer with polymer blocks having the following structure:

[0125] in: R is an aryl group as defined in this paper; and n is an integer greater than 2.

[0126] In some embodiments, the aryl group is a substituted aryl group. In some embodiments, the aryl group is a disubstituted aryl group. In some embodiments, the aryl group is a disubstituted aryl group substituted with an alkoxy substituent. In some embodiments, the aryl group is 2,6-dimethoxyphenyl.

[0127] For any group containing one or more substituents described herein, it should be understood that such group does not contain any substitution or substitution pattern that is sterically impractical and / or synthetically infeasible. Furthermore, the compounds disclosed herein include all stereochemical isomers resulting from substitutions of these compounds.

[0128] Unless otherwise defined herein, any optional substituent of alkyl, alkenyl, and aryl groups includes substitution by one or more of the following substituents, etc.: Halogens, including fluorine, chlorine, bromine, or iodine; Halogenated compounds include -CN, -OCN (cyanate esters), -NCO (isocyanate esters), -SCN (thiocyanate esters), and -NCS (isothiocyanate esters). -COOR, where R is hydrogen or alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; -COR, where R is hydrogen or alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; -CON(R)2, wherein each R is hydrogen or alkyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R can form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms; -OCON(R)2, wherein each R is hydrogen or alkyl or aryl, independently of each other R, and more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R can form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms; -N(R)2, wherein each R is hydrogen or alkyl or acyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl, phenyl or acetyl, all of which are optionally substituted; and wherein R and R can form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms; -SR, where R is hydrogen or alkyl or aryl, more specifically where R is hydrogen, methyl, ethyl, propyl, butyl or phenyl, which is optionally substituted; -SO2R or -SOR, where R is alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; -OCOOR, where R is an alkyl or aryl group; -SO2N(R)2, wherein each R is hydrogen or alkyl or aryl independently of each other R, all of which are optionally substituted, and wherein R and R can form a ring, which can contain one or more double bonds and can contain one or more additional carbon atoms; and -OR, where R is H, alkyl, aryl, or acyl, all of which are optionally substituted. In a particular instance, R may be an acyl, producing –OCOR”, where R” is hydrogen or alkyl or aryl, more specifically where R” is methyl, ethyl, propyl, butyl, or phenyl, all of which are optionally substituted.

[0129] Specific substituted alkyl groups include haloalkyl groups, particularly trihalomethyl and specifically trifluoromethyl. Specific substituted aryl groups include mono-, di-, tri-, tetra-, and pentahalosubstituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa-, and heptahalosubstituted naphthyl groups; 3- or 4-halosubstituted phenyl groups; 3- or 4-alkyl-substituted phenyl groups; 3- or 4-alkoxy-substituted phenyl groups; 3- or 4-RCO-substituted phenyl groups; and 5- or 6-halosubstituted naphthyl groups. More specifically, substituted aryl groups include acetylphenyl, particularly 4-acetylphenyl; fluorophenyl, particularly 3-fluorophenyl and 4-fluorophenyl; chlorophenyl, particularly 3-chlorophenyl and 4-chlorophenyl; methylphenyl, particularly 4-methylphenyl; and methoxyphenyl, particularly 4-methoxyphenyl.

[0130] For any of the aforementioned groups containing one or more substituents, it should be understood that such groups do not contain any substitution or substitution pattern that is spatially impractical and / or synthetically infeasible. Furthermore, as further described herein, the compounds of this disclosure may include all stereochemical isomers (and racemic mixtures) resulting from substitutions of these compounds.

[0131] One embodiment provides a block copolymer having at least a first block and a second block, wherein: i) The first block is a poly(aryl acrylate) or poly(aryl methacrylate) block having 10-300 repeating units or a poly(aryl methacrylate) block having 10-300 repeating units; ii) The second block is a poly(alkyl acrylate) block having 10-300 repeating units.

[0132] Another embodiment provides a block copolymer comprising: i) A rigid block comprising a poly(aryl acrylate) having a glass transition temperature of 100°C to 150°C; and ii) Soft blocks comprising poly(alkyl acrylate) polymers with a glass transition temperature of -75°C to -25°C.

[0133] One embodiment provides a micelle comprising a plurality of block copolymers, comprising: i) A shell core comprising at least a portion of a rigid block comprising a poly(aryl acrylate) having a glass transition temperature of 100°C to 150°C; and ii) A core comprising at least a portion of a soft block comprising a poly(alkyl acrylate) polymer having a glass transition temperature of -75°C to -25°C.

[0134] One embodiment provides a block copolymer having at least a first block and a second block, wherein: i) The first block is a poly(aryl acrylate) block or a poly(aryl methacrylate) block containing the following substructures:

[0135] in: R 1 Each time it appears, it is independently either hydrogen or CH3; n1 is an integer in the range of 10-300; and ii) The second block is a poly(alkyl acrylate) block containing the following substructures:

[0136] in: R 2 Each occurrence is independently a C1-C6 alkyl group; and n2 is an integer in the range of 10-300.

[0137] In some embodiments, the block copolymer is a diblock copolymer comprising the following substructures:

[0138] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1 and n2 are each independent integers in the range of 10-300.

[0139] In some embodiments, the block copolymer is a triblock copolymer comprising the following substructures:

[0140] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1, n2, and n3 are each independent integers in the range of 10-300.

[0141] In some embodiments, n3 is an integer in the range of 10-100. In some embodiments, the block copolymer has the following structure:

[0142] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 It is a C1-C6 alkyl, a C1-C6 hydroxyalkyl, or R 3 It has the following structure: ; R 4 It is a halogenated product; n1 and n2 are both integers in the range of 10-300.

[0143] In some implementations, n1 ranges from 10-200, 10-150, 10-100, 10-50, 10-25, 20-200, 30-200, 50-200, 100-200, or 150-200.

[0144] In some implementations, n2 ranges from 10-300, 10-250, 10-200, 10-150, 10-100, 10-50, 10-25, 20-300, 30-300, 50-300, 100-300, 150-300, 200-300, or 250-300.

[0145] In some implementations, n3 ranges from 10-300, 10-250, 10-200, 10-150, 10-100, 10-50, 10-25, 20-300, 30-300, 50-300, 100-300, 150-300, 200-300, or 250-300.

[0146] In some implementations, R 3 It is ethyl or -CH2CH2OH. In some embodiments, R 3 It has the following structure: .

[0147] In some implementation schemes, R 4 It is bromine. In some embodiments, the block copolymer has the following structure:

[0148] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 and R 4 Each is an independent halogenation; L 1 and L 3 Each of them independently has the following structure: ; L 2 It has the following structure: ;and n1, n2, n3, and n4 are each independent integers in the range of 10-300.

[0149] In some implementations, R 1It is hydrogen each time it appears. In some implementations, R 1 It is methyl in every occurrence.

[0150] In some implementations, R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl. In some embodiments, R 2 Each time it appears, it is n-butyl.

[0151] In some implementations, n1 is an integer in the range of 10-100. In some implementations, n2 is an integer in the range of 10-100.

[0152] In some implementation schemes, R 3 and R 4 All are bromine.

[0153] One embodiment provides a micelle comprising a plurality of block copolymers, the micelle comprising: i) a core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and ii) an outer layer comprising at least a portion of a poly(aryl acrylate) block (e.g., poly(2,6-dimethoxyphenyl acrylate)) or a poly(aryl methacrylate) block (e.g., poly(2,6-dimethoxyphenyl methacrylate)) of one or more block copolymers.

[0154] In some embodiments, the poly(aryl acrylate) (e.g., poly(2,6-dimethoxyphenyl acrylate)) block or the poly(aryl methacrylate) (e.g., poly(2,6-dimethoxyphenyl methacrylate)) block comprises the following substructures:

[0155] in: R 1 Each time it appears, it is independently either hydrogen or CH3; and n1 is an integer in the range of 10-300.

[0156] In some implementations, n1 is an integer in the range of 10-100, 20-200, 30-200, 100-200, or 150-200.

[0157] In some implementations, the poly(alkyl acrylate) block comprises the following substructures:

[0158] in: R 2Each occurrence is independently a C1-C6 alkyl group; and n2 is an integer in the range of 10-300.

[0159] In some implementation schemes, R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl. In some embodiments, R 2 It appears as n-butyl each time.

[0160] In some implementations, n2 is an integer in the range of 10-100, 20-300, 30-300, 100-300, or 250-300.

[0161] In some embodiments, one or more block copolymers are diblock copolymers comprising the following substructures:

[0162] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1 and n2 are each independent integers in the range of 10-300.

[0163] In some embodiments, each block copolymer is a diblock copolymer comprising the following substructures:

[0164] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1 and n2 are each independent integers in the range of 10-300.

[0165] In some implementation schemes, R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl. In some embodiments, R 2 Each occurrence is an n-butyl. In some embodiments, n1 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500. In some embodiments, n2 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500.

[0166] In some embodiments, at least one block copolymer is a triblock copolymer comprising the following substructures:

[0167] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1, n2, and n3 are each independent integers in the range of 10-300.

[0168] In some embodiments, each block copolymer is a triblock copolymer comprising the following substructures:

[0169] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1, n2, and n3 are each independent integers in the range of 10-300.

[0170] In some implementation schemes, R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl. In some embodiments, R 2 Each occurrence is n-butyl. In some embodiments, n1 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500. In some embodiments, n2 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500. In some embodiments, n3 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500.

[0171] In some embodiments, at least one block copolymer has the following structure:

[0172] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 It is a C1-C6 alkyl, a C1-C6 hydroxyalkyl, or R 3It has the following structure: ; R 4 It is a halogenated product; and n1 and n2 are both integers in the range of 10-300.

[0173] In some embodiments, each block copolymer has the following structure:

[0174] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 It is a C1-C6 alkyl, a C1-C6 hydroxyalkyl, or R 3 It has the following structure: ; R 4 It is a halogenated product; and n1 and n2 are both integers in the range of 10-300.

[0175] In some implementation schemes, R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl. In some embodiments, R 2 Each time it appears, it is n-butyl.

[0176] In some implementation schemes, R 3 It is ethyl or -CH2CH2OH. In some embodiments, R 3 It has the following structure: .

[0177] In some implementations, n1 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500. In some implementations, n2 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500.

[0178] In some implementation schemes, R 4 It is bromine.

[0179] In some embodiments, at least one block copolymer has the following structure:

[0180] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 and R 4 Each is an independent halogenation; L 1 and L 3 Each of them independently has the following structure: ; L 2 It has the following structure: ;and n1, n2, n3, and n4 are each independent integers in the range of 10-300.

[0181] In some implementations, n1, n2, n3, and n4 are each independently an integer in the range of 10-200.

[0182] In some embodiments, each block copolymer has the following structure:

[0183] in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 and R 4 Each is an independent halogenation; L 1 and L 3 Each of them independently has the following structure: ; L 2 It has the following structure: ;and n1, n2, n3, and n4 are each independent integers in the range of 10-300.

[0184] In some implementations, n1, n2, n3, and n4 are each independently an integer in the range of 10-200.

[0185] In some implementation schemes, R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl. In some embodiments, R 2 Each time it appears, it is n-butyl.

[0186] In some implementations, n1 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500. In some implementations, n2 is an integer in the range of 10-100, 20-500, 30-500, 100-500, or 250-500.

[0187] In some embodiments, the block copolymer includes a polymerizable portion (e.g., terminal acrylate, terminal methacrylate, etc.). In some embodiments, the block copolymer is non-reactive to further polymerization conditions (e.g., photopolymerization). Some embodiments provide a photocurable resin comprising the block copolymer of this disclosure. In some embodiments, the photocurable mixture is subsequently subjected to a curing step (e.g., light irradiation). In some embodiments, the photocurable resin includes an initiator (e.g., a photoinitiator, a thermal initiator, etc.).

[0188] In some embodiments, micelles are covalently bonded to a photopolymer network. In some embodiments, multiple covalent bonds are established between the micelles and the polymer network during the curing step. In some embodiments, micelles are dispersed within and in physical contact with the polymer network (e.g., non-covalently bonded). In some embodiments, micelles are added to the polymer network after the curing step. In some embodiments, micelles are added during the curing step. In some embodiments, micelles are added before the curing step (e.g., added to a photocurable resin).

[0189] In some embodiments, the photocurable resin includes a monomeric component but not a polymeric component. In some embodiments, the photocurable resin includes a monomeric component and some polymeric components (e.g., polymeric blocks extended to form block copolymers). In some embodiments, the photocurable resin comprises (i) micelles according to this disclosure; and (ii) a monomeric component, a polymeric component, or a combination thereof.

[0190] This disclosure provides a photocurable resin that may contain multiple (e.g., > 1) polymerizable components.

[0191] Some embodiments provide a photocurable resin comprising: i) aryl acrylate monomers, aryl methacrylate monomers, or combinations thereof; and ii) Macromolecular initiator compounds having the following structures:

[0192] in: n2 is an integer in the range of 10-500.

[0193] One embodiment provides a photocurable resin comprising: i) an aryl acrylate monomer, an aryl methacrylate monomer, or a combination thereof; ii) an alkyl acrylate monomer; and iii) an initiator.

[0194] The photocurable resin disclosed herein may contain one or more polymerizable monomers. Such polymerizable monomers can be used as reactive diluents. In various cases, the polymerizable monomer may contain an acrylate or methacrylate moiety for incorporation into the oligomer or polymer backbone, coupled with linear or cyclic (e.g., monocyclic, bicyclic, or tricyclic) side chain moiety. Generally, any aliphatic, alicyclic, or aromatic molecule (including liquid crystal monomers) having a monofunctional polymerizable reactive functional group can be used. In some cases, the polymerizable reactive functional group is an acrylate or methacrylate group. In some cases, the polymerizable monomer is eugenol, guaiacol, or vanillin derivatives, such as high-salicylic acid methacrylate (HSMA), eugenol methacrylate (SMA), isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), etc. The reactive diluents used herein may have low vapor pressures, as further described below. However, in some embodiments, no reactive diluent may be used or only a small amount (e.g., 5% w / w or less) may be used.

[0195] In some implementations, the polymerizable monomer includes one of the following structures:

[0196] in: Y is a polymerizable functional group (e.g., methacrylate, acrylate, etc.), and L is an alkylene linkage, a cycloalkylene linkage, or an aryl linkage.

[0197] In some implementations, the polymerizable monomer includes one of the following structures:

[0198] in: Y is a polymerizable functional group (e.g., methacrylate, acrylate, etc.), and L is an alkylene linkage, a cycloalkylene linkage, or an aryl linkage.

[0199] In some implementations, the polymerizable monomer includes one of the following structures:

[0200] in: Y is a polymerizable functional group (e.g., methacrylate, acrylate, etc.); and L is an alkylene linkage, a cycloalkylene linkage, or an aryl linkage.

[0201] In some embodiments, the polymerizable monomers of this disclosure may have low vapor pressures and high boiling points at elevated temperatures. Such low vapor pressures may be particularly advantageous for use in curable (e.g., photocurable) compositions and additive manufacturing (where elevated temperatures (e.g., 60°C, 80°C, 90°C, or higher) may be used). In various cases, the vapor pressure of the polymerizable monomer at 60°C may be at most about 12 Pa. In various cases, the vapor pressure of the polymerizable monomer at 60°C may be at most about 2 Pa to 10 Pa. In various cases, the vapor pressure of the polymerizable monomer at 60°C may be at most about 2 Pa to 5 Pa. Therefore, in some embodiments, the polymerizable monomers of this disclosure may have low mass loss at elevated temperatures. As used herein, the mass loss of a compound sustained at a certain temperature (e.g., 90°C) for a certain period of time (e.g., 2 hours) can be used as a measure of the volatility of such a compound. Herein, “substantially non-volatile” may mean a mass loss of < 1 wt% at the corresponding temperature (e.g., sustained at 90°C for 2 hours). In various cases, the mass loss of the polymerizable monomer disclosed herein after heating at a corresponding temperature of 90°C for 2 hours can be < 1 wt%. In some embodiments, the mass loss of the polymerizable monomer after heating at 90°C for 2 hours can be less than about 0.5%. In some embodiments, the mass loss of the polymerizable monomer after heating at 90°C for 2 hours can be from about 0.1% to about 0.45%. In some embodiments, the mass loss of the polymerizable monomer after heating at 90°C for 2 hours can be from about 0.05% to about 0.25%.

[0202] In some embodiments, the molecular weight of the polymerizable monomer disclosed herein may be at least about 150 Da, 200 Da, 250 Da, 300 Da, 350 Da, 400 Da, or at least about 450 Da. In some cases, the molecular weight of the polymerizable monomer is less than about 740 Da.

[0203] In some embodiments, the melting point of the polymerizable monomers can be at least about 20°C, 30°C, 40°C, 50°C, or higher. In some embodiments, the melting point of the polymerizable monomers is lower than the processing temperature used in current photopolymerization processes based on high-temperature lithography, which is typically in the range of 50-120°C, for example, 90-120°C. Therefore, the polymerizable monomers provided herein that can be used as reactive diluents can have melting points of <120°C, <90°C, <70°C, or even <50°C or <30°C, which provides low melt viscosity, thus providing a more significant viscosity reduction effect when they are used as reactive diluents for resins cured by high-temperature lithography-based polymerization. In some cases, they are liquid at room temperature, which, in addition to the advantages mentioned above, also facilitates their handling.

[0204] In various embodiments, any polymerizable monomer described herein can be a photopolymerizable monomer. In various cases, the photopolymerizable monomers of this disclosure can be components of a polymerizable composition (e.g., a photocurable resin). In some embodiments, the polymerizable composition may contain one or more polymerizable compounds in an amount from about 5% by weight (w / w) to about 20% w / w or higher. In this case, the amount of the polymerizable compound (e.g., a monomer) may be from about 5% w / w to about 7% w / w, from about 7% w / w to about 10% w / w, from about 9% w / w to about 15% w / w, or from about 12% w / w to about 18% w / w. In some cases, the amount of the polymerizable compound may be about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% w / w or higher.

[0205] The photocurable resins disclosed herein may contain one or more polymerizable monomers in amounts of about 25% w / w to about 45% w / w, about 30% w / w to about 40% w / w, or about 40% w / w to about 65% w / w. In some cases, the resins provided herein may contain less than about 65%, 45%, 40%, 35%, 30%, 25%, or less than about 20% w / w of polymerizable monomers.

[0206] The photocurable resin disclosed herein may contain one or more telechelic polymers, telechelic oligomers, or combinations thereof in amounts of about 15% w / w to about 60% w / w, about 35% w / w to about 55% w / w, about 40% w / w to about 55% w / w, or about 40% w / w to about 50% w / w.

[0207] The photocurable resin described herein may also contain one or more photoinitiators. When activated with light of an appropriate wavelength (e.g., UV / VIS), such a photoinitiator can initiate polymerization reactions between the telechelic polymer, monomers, and other potentially polymerizable components that may be present in the photocurable resin (e.g., during photocuring) to form micelles or polymer compositions as further described herein. Generally, the photoinitiators described in this disclosure can include those that can be activated by light and initiate the polymerization of polymerizable components of the formulation. As used herein, “photoinitiator” can generally refer to a compound that can generate free radicals and / or promote free radical reactions when exposed to radiation (e.g., UV or visible light).

[0208] In some embodiments, the photocurable resin described 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% of a photoinitiator, based on the total weight of the composition. In some embodiments, the photoinitiator is a free radical photoinitiator. In some embodiments, the free radical photoinitiator comprises an α-hydroxy ketone moiety (e.g., 2-hydroxy-2-methylphenylacetone or 1-hydroxycyclohexylphenyl ketone), an α-amino ketone (e.g., 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop-1-one), 4-methylbenzophenone, an azo compound (e.g., 4,4'-azobis(4-cyanopentanoic acid), 1,1'-azobis(cyclohexaneformitrile, azobisisobutyrone, 2,2'-azobis(2-methylpropionitrile), or 2,2'-azobis(2-methylpropionitrile)), an inorganic peroxide, an organic peroxide, or any combination thereof. In some embodiments, the composition comprises a SpeedCure-containing compound. TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphine ester) photoinitiator. In some embodiments, the photocurable composition comprises a photoinitiator selected from: benzophenone, benzophenone and a mixture of tertiary amines (containing a carbonyl group directly bonded to at least one aromatic ring), and Irgacure (e.g., Irgacure 907 (2-methyl-1-[4-(methylthio)-phenyl]-2-morpholino-acetone-1) or Irgacure 651 (2,2-Dimethoxy-1,2-diphenylethyl-1-one). In some embodiments, the photoinitiator includes acetophenone photoinitiators (e.g., 4'-hydroxyacetophenone, 4'-O-phenoxyacetophenone, 4'-ethoxyacetophenone), benzoin, benzoin derivatives, azobenzoyl, azobenzoyl derivatives, benzophenone (e.g., 4-benzoylbiphenyl, 3,4-(dimethylamino)benzophenone, 2-methylbenzophenone), cationic photoinitiators (e.g., diphenyliodonium nitrate, (4-iodophenyl)diphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate), anthraquinone, quinone (e.g., camphorquinone), phosphine oxide, phosphinate, 9,10-phenanthrenequinone, thioxanthone, any combination thereof, or any derivative thereof.

[0209] In some embodiments, the photoinitiator may have a maximum wavelength absorbance between 200 and 300 nm, 300 and 400 nm, 400 and 500 nm, 500 and 600 nm, 600 and 700 nm, 700 and 800 nm, 800 and 900 nm, 150 and 200 nm, 200 and 250 nm, 250 and 300 nm, 300 and 350 nm, 350 and 400 nm, 400 and 450 nm, 450 and 500 nm, 500 and 550 nm, 550 and 600 nm, 600 and 650 nm, 650 and 700 nm, or 700 and 750 nm. In some embodiments, the photoinitiator has a maximum wavelength absorbance between 300 and 500 nm.

[0210] In some embodiments, the photocurable resin of this disclosure may further comprise a crosslinking modifier (e.g., in addition to polymerizable compounds disclosed herein that can act as crosslinking agents, or where the polymerizable compound does not act as a crosslinking agent), a light-blocking agent, a solvent, a glass transition temperature regulator, or a combination thereof. In some aspects, the photocurable resin comprises 0-25 wt% of a crosslinking modifier having a number-average molecular weight equal to or less than 1,500 Da. In some aspects, the photocurable resin comprises 0 to 10 wt%, 0 to 9 wt%, 0 to 8 wt%, 0 to 7 wt%, 0 to 6 wt%, 0 to 5 wt%, 0 to 4 wt%, 0 to 3 wt%, 0 to 2 wt%, 0 to 1 wt%, or 0 to 0.5 wt% of a light-blocking agent. In some embodiments, the photocurable resin comprises a solvent. In some embodiments, the solvent comprises a nonpolar solvent. In some embodiments, the nonpolar solvent comprises pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, derivatives thereof, or combinations thereof. In some embodiments, the solvent comprises a polar aprotic solvent. In some embodiments, the polar aprotic solvent comprises tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, DMSO, propylene carbonate, derivatives thereof, or combinations thereof. In some embodiments, the solvent comprises a polar protic solvent. In some embodiments, the polar protic solvent comprises formic acid, n-butanol, isopropanol, n-propanol, tert-butanol, ethanol, methanol, acetic acid, water, derivatives thereof, or combinations thereof. In some embodiments, the photocurable resin comprises less than 90% by weight of the solvent.

[0211] In some embodiments, the added resin components (e.g., crosslinking modifiers, polymerization catalysts, polymerization inhibitors, glass transition temperature modifiers, light-blocking agents, plasticizers, solvents, surface energy modifiers, pigments, dyes, fillers, or biologically significant chemicals) are functionalized to allow them to be incorporated into the polymer material, making them difficult to extract from the ultimately cured material. In some embodiments, polymerization catalysts, polymerization inhibitors, light-blocking agents, plasticizers, surface energy modifiers, pigments, dyes, and / or fillers are functionalized to promote their incorporation into the cured polymer composition.

[0212] In some embodiments, the resin herein contains, in addition to the polymerizable compounds described herein, a component that can alter the glass transition temperature of the cured polymer composition. In this case, based on the total weight of the composition, a glass transition temperature modifier (also referred to herein as T...) g Modifiers (or glass transition modifiers) may be present in the photocurable composition in an amount of about 0 to 50 wt%. g Modifiers can have high glass transition temperatures, resulting in high heat distortion temperatures, which is necessary for the use of materials 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 T. g Modifier. In some embodiments, the curable composition contains 0-50 wt% of a glass transition modifier. In some cases, T g The modifier has a number-average molecular weight of 0.4 to 5 kDa. In some embodiments, T gThe number average molecular weight of the modifier is 0.1 to 5 kDa, 0.2 to 5 kDa, 0.3 to 5 kDa, 0.4 to 5 kDa, 0.5 to 5 kDa, 0.6 to 5 kDa, 0.7 to 5 kDa, 0.8 to 5 kDa, 0.9 to 5 kDa, 1.0 to 5 kDa, 0.1 to 4 kDa, 0.2 to 4 kDa, 0.3 to 4 kDa, 0.4 to 4 kDa, 0.5 to 4 kDa, 0.6 to 4 kDa, 0.7 to 4 kDa, 0.8 to 4 kDa, 0.9 to 4 kDa, 1 to 4 kDa, 0.1 to 3 kDa, 0.2 to 3 kDa, 0.3 to 3 kDa, 0.4 to 3 kDa, 0.5 to 3 kDa, 0.6 to 3 kDa, 0.7 to 3 kDa, 0.8 to 3 kDa, 0.9 to 3 kDa, or 1 to 3 kDa. The polymerizable compounds disclosed herein (in some cases, they can themselves act as T) g Modifier) ​​and separate T g The modifier compound may be miscible and compatible in the methods described herein. When used in compositions relating to the subject matter of this invention, T g Modifiers can provide high T g And strength values, sometimes at the cost of elongation at break. In some cases, toughness modifiers can provide high elongation at break and toughness through a reinforcing effect, and the polymerizable monomers described herein can improve the processability of formulations, for example, by acting as reactive diluents, particularly those compositions containing large amounts of toughness modifiers, while maintaining high strength and T strength. g value.

[0213] The curable (e.g., photocurable) resins described herein are characterized by having one or more properties. In some embodiments, monomers can be used as reactive diluents in the curable resins disclosed herein. Thus, in some cases, photopolymerizable monomers can reduce the viscosity of the curable resin (e.g., photocurable resin). In this case, the photopolymerizable monomer can reduce the viscosity of the curable resin by at least about 5% compared to a resin that does not contain a polymerizable monomer. In some cases, the photopolymerizable monomer can reduce the viscosity of the photocurable resin by at least about 5%, 10%, 20%, 30%, 40%, or 50%. In some cases, the viscosity of the photocurable resins disclosed herein at printing temperatures can be from about 30 cP to about 50,000 cP. In some embodiments, the photocurable resin has a viscosity at 25°C of 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. In some implementations, the resin has a viscosity of less than 15,000 cP at 25°C.In some implementations, the photocurable resin has a viscosity at the printing temperature of 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, or less than or equal to 500 cP. 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. In some embodiments, the viscosity of the photocurable resin at the printing temperature is 50,000 cP to 30 cP, 40,000 cP to 30 cP, 30,000 cP to 30 cP, 20,000 cP to 30 cP, 10,000 cP to 30 cP, or 5,000 cP to 30 cP. In some embodiments, the printing temperature is 0°C to 25°C, 25°C to 40°C, 40°C to 100°C, or 20°C to 150°C. In some embodiments, the photocurable resin has a viscosity of 30 cP to 50,000 cP at a printing temperature of 20°C to 150°C. In other embodiments, the photocurable resin has a viscosity of less than 20,000 cP at a printing temperature. In some embodiments, the printing temperature is 10°C to 200°C, 15°C to 175°C, 20°C to 150°C, 25°C to 125°C, or 30°C to 100°C. In a preferred embodiment, the printing temperature is 20°C to 150°C.

[0214] The photocurable resin disclosed herein is capable of 3D printing at temperatures above 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, the photopolymerizable monomers that can be used as part of the photocurable resin disclosed herein can have low vapor pressure and / or mass loss at the printing temperature, thereby providing improved printing conditions compared to conventional resins used in additive manufacturing.

[0215] In some embodiments, the photocurable resin described herein has a melting temperature greater than room temperature. In some embodiments, the photocurable resin 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 photocurable resin has a melting temperature of 20°C to 250°C, 30°C to 180°C, 40°C to 160°C, or 50°C to 140°C. In some embodiments, the photocurable resin has a melting temperature greater than 60°C. In other embodiments, the photocurable resin has a melting temperature of 80°C to 110°C. In some cases, the photocurable resin may have a melting temperature of about 80°C before polymerization, and after polymerization, the resulting polymer composition may have a melting temperature of about 100°C.

[0216] In some cases, it may be advantageous for photocurable resins to be in a liquid phase at elevated temperatures. For example, conventional photocurable resins may contain polymerizable components that can be viscous at processing temperatures, making them difficult to use for manufacturing objects (e.g., for 3D printing). As a solution to this technical problem, this disclosure provides photocurable resins containing photopolymerizable components (e.g., monomers described herein) that can melt at elevated temperatures (e.g., at manufacturing temperatures (e.g., during 3D printing)) and can have reduced viscosity at elevated temperatures, which can make such resins more suitable for applications such as 3D printing. Therefore, in some embodiments, what is provided herein is a photocurable resin that is liquid at elevated temperatures. In some embodiments, the elevated temperature is or above the melting temperature (T0) of the photocurable resin. m In some embodiments, the elevated temperature is a temperature in the range of about 40°C to about 100°C, about 60°C to about 100°C, about 80°C to about 100°C, about 40°C to about 150°C, or 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, the photocurable resin described herein is liquid at the elevated temperature and has a viscosity of less than about 50 PaS, less than 20 PaS, less than about 10 PaS, less than about 5 PaS, or less than about 1 PaS. In some embodiments, the photocurable resin described herein is liquid at an elevated temperature above about 40°C and has a viscosity of less than about 20 PaS. In still other embodiments, the photocurable resin described herein is liquid at an elevated temperature above about 40°C and has a viscosity of less than about 1 PaS.

[0217] In some embodiments, at least a portion of the photocurable resin 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 the photocurable resin herein melts at an elevated temperature of about 100°C to about 20°C, about 90°C to about 20°C, about 80°C to about 20°C, about 70°C to about 20°C, about 60°C to about 20°C, about 60°C to about 10°C, or about 60°C to about 0°C.

[0218] In various embodiments, the photocurable resins and their photopolymerizable components described herein can be biocompatible, bioinert, or a combination thereof. In various cases, the photopolymerizable compounds of the resins described herein may have biocompatible and / or bioinert metabolic (e.g., hydrolysis) products.

[0219] The photocurable resin disclosed herein may contain less than about 20 wt% or less than about 10 wt% of hydrogen-bonded units. In some aspects, the photocurable resin herein contains 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% of hydrogen-bonded units.

[0220] Polymers and polymer compositions

[0221] This disclosure provides polymers and polymer compositions. Such polymer compositions can be generated by curing the curable compositions or resins described herein. The polymer compositions provided herein can be biocompatible, bioinert, or a combination thereof. In various cases, the polymer compositions herein are generated by photocuring the photocurable compositions described herein.

[0222] Advantages of embodiments of this disclosure include (i) producing eugenol-based block copolymers that self-assemble into micelles / core-shell nanoparticles, thereby enhancing the toughness of eugenol-rich photopolymer networks; (ii) producing non-reactive or reactive diblock and triblock copolymers using flexible synthetic conditions with ATRP initiators; and (iii) reactive and non-reactive polymers can be covalently or non-covalently attached to the remainder of the photopolymer network.

[0223] Therefore, one embodiment provides a polymer composition comprising micelles dispersed in and in physical contact with a photopolymer network of any of the embodiments disclosed herein. Another embodiment provides a polymer composition comprising micelles dispersed in and covalently bonded to a photopolymer network of the embodiments disclosed herein.

[0224] In some embodiments, the photopolymer network comprises a poly(acrylate) polymer, a poly(methacrylate) polymer, a block copolymer comprising at least one poly(acrylate) block and at least one poly(methacrylate) block, or a combination thereof.

[0225] In some embodiments, the photopolymer network comprises more than 50 wt% poly(acrylate) polymer based on the total weight of the polymer composition. In some embodiments, the photopolymer network comprises more than 90 wt% poly(acrylate) polymer based on the total weight of the polymer composition. In some embodiments, the poly(acrylate) polymer comprises poly(2,6-dimethoxyphenylacrylate).

[0226] In some embodiments, the poly(acrylate) polymer is greater than 20 wt% poly(2,6-dimethoxyphenyl acrylate) based on the total weight of the poly(acrylate) polymer. In some embodiments, the poly(acrylate) polymer is greater than 40 wt% poly(2,6-dimethoxyphenyl acrylate) based on the total weight of the poly(acrylate) polymer.

[0227] In some embodiments, the poly(acrylate) polymer is less than 45 wt% poly(2,6-dimethoxyphenyl acrylate) based on the total weight of the poly(acrylate) polymer.

[0228] In some embodiments, the photopolymer network comprises more than 50 wt% poly(methacrylate) polymer based on the total weight of the polymer composition. In some embodiments, the photopolymer network comprises more than 90 wt% poly(methacrylate) polymer based on the total weight of the polymer composition. In some embodiments, the poly(methacrylate) polymer comprises poly(2,6-dimethoxyphenyl methacrylate).

[0229] In some embodiments, the poly(methacrylate) polymer is greater than 20 wt% poly(2,6-dimethoxyphenyl methacrylate) based on the total weight of the poly(methacrylate) polymer. In some embodiments, the poly(methacrylate) polymer is greater than 40 wt% poly(2,6-dimethoxyphenyl methacrylate) based on the total weight of the poly(methacrylate) polymer. In some embodiments, the micelle concentration is less than 10 wt% relative to the total weight of the polymer composition.

[0230] In some embodiments, the polymer composition or photopolymer network has one or more of the following properties: (A) Energy storage modulus greater than or equal to 200 MPa; (B) The remaining bending stress and / or bending modulus is greater than or equal to 1.5 MPa after 24 hours in a humid environment at 37°C; (C) The elongation at break is greater than or equal to 5% before and after 24 hours in a humid environment at 37°C; (D) The water absorption rate measured after 24 hours in a humid environment at 37°C is less than 25 wt%; (E) After 24 hours in a humid environment at 37°C, the transmittance of visible light through the polymer composition is at least 30%; and (F) comprises a plurality of polymer phases, wherein at least one of the polymer phases has a T value of at least 60°C, 80°C, 90°C, 100°C, or at least 110°C. g .

[0231] In some embodiments, the polymer composition is characterized by having a water absorption rate 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 humid environment at 37°C.

[0232] In some embodiments, the polymer composition exhibits a conversion rate of more than 60% from double bonds to single bonds, as measured by FTIR, compared to a photocurable resin.

[0233] In some embodiments, after 24 hours in a humid environment at 37°C, the ultimate tensile strength of the polymer composition is 10 MPa to 100 MPa, 15 MPa to 80 MPa, 20 MPa to 60 MPa, 10 MPa to 50 MPa, 10 MPa to 45 MPa, 25 MPa to 40 MPa, 30 MPa to 45 MPa, or 30 MPa to 40 MPa.

[0234] In some embodiments, the polymer composition is characterized by having an elongation at break greater than 10%, greater than 20%, greater than 30%, between 5% and 250%, between 20% and 250%, or between 40% and 250% before and after 24 hours in a humid environment at 37°C.

[0235] In some embodiments, the polymer composition is characterized by having 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 humid environment at 37°C.

[0236] In some embodiments, after 24 hours in a humid environment at 37°C, the flexural stress, flexural modulus, or flexural stress and flexural modulus of the polymer composition are 400 MPa or higher, 300 MPa or higher, 200 MPa or higher, 180 MPa or higher, 160 MPa or higher, 120 MPa or higher, 100 MPa or higher, 80 MPa or higher, 70 MPa or higher, or 60 MPa or higher.

[0237] In some embodiments, after 24 hours in a humid environment at 37°C, at least 40%, 50%, 60%, or 70% of visible light passes through the polymer composition.

[0238] In some embodiments, the polymer composition is biocompatible, bioinert, or a combination thereof.

[0239] One embodiment provides a polymer film comprising the polymer composition of any of the embodiments disclosed herein. In some more specific embodiments, the polymer film has a thickness of at least 100 μm and no more than 3 mm.

[0240] Some embodiments provide an orthodontic appliance comprising a polymer composition of any of the embodiments disclosed herein or a polymer membrane of any of the embodiments disclosed herein. In some embodiments, the orthodontic appliance is a dental appliance. In some more specific embodiments, the orthodontic appliance is a braces, a tooth expander, or a tooth spacer.

[0241] One embodiment provides a method for forming a polymer composition according to any embodiment of the present invention, the method comprising: Provided a photocurable resin according to any of the embodiments disclosed herein; Exposing the photocurable resin to a light source; and To polymerize a photocurable resin to form a polymer.

[0242] In some embodiments, the light source is an ultraviolet (UV) or visible light source. In some embodiments, the method also includes manufacturing orthodontic appliances using polymers.

[0243] One embodiment provides a method for forming a polymer composition according to any embodiment of the present invention, the method comprising: Provide a photocurable resin (e.g., containing a macromolecular initiator as a poly(alkylalkylate)) in any of the embodiments disclosed herein. Exposing the photocurable resin to a light source; and To polymerize a photocurable resin to form a polymer.

[0244] In some embodiments, the light source is an ultraviolet (UV) or visible light source. In some embodiments, the method also includes manufacturing orthodontic appliances using polymers.

[0245] One embodiment provides a method for preparing articles by an additive manufacturing process, comprising: Provided a photocurable resin according to any of the embodiments disclosed herein; Heat the photocurable resin to the processing temperature; Expose the photocurable resin to radiation; According to a predetermined design, a photocurable resin is polymerized layer by layer, thereby polymerizing multiple monomers and photoinitiators to form a polymer; and Products are made from polymers.

[0246] In some embodiments, the processing temperature is from about 50°C to about 120°C. In some 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 additive manufacturing process is a 3D printing process. In some embodiments, the article is a medical device. In some embodiments, the medical device is an orthodontic appliance.

[0247] One implementation provides a method for repositioning a patient's teeth, comprising: A treatment plan is generated for the patient, which includes multiple intermediate tooth arrangements to move the teeth along the treatment path from the initial tooth arrangement toward the final tooth arrangement; Orthodontic appliances manufactured according to the embodiments disclosed herein, or orthodontic appliances comprising polymer compositions of any of the embodiments disclosed herein; and Orthodontic appliances are used to move at least one of the patient's teeth along a track toward the intermediate or final teeth alignment.

[0248] In some embodiments, the production of orthodontic appliances includes 3D printing of the orthodontic appliances. In some embodiments, the method also includes tracking the progress of a patient's teeth along the treatment path after the orthodontic appliance has been applied to the patient, the tracking including comparing the current alignment of the patient's teeth with the planned alignment of the patient's teeth.

[0249] In some implementations of this method, more than 60% of patients' teeth conform to the treatment plan after two weeks of treatment.

[0250] In some implementations, the orthodontic appliance retains a repositioning force on 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 the repositioning force initially provided to at least one of the patient's teeth.

[0251] In some aspects of this article, the photocurable compositions or resins described herein can be cured by exposing such compositions or resins to electromagnetic radiation of an appropriate wavelength.

[0252] In some embodiments, the polymer composition may comprise poly(ethylene) glycol (PEG), poly(ethylene) glycol diacrylate, PEG-THF, polytetrahydrofuran, poly(tert-butyl acrylate), poly(ethylene-co-maleic anhydride), any derivative thereof, or any combination thereof.

[0253] In some embodiments, the monomeric components used to obtain the photopolymer network, micelles, or polymer composition include acrylates, acrylamide, methacrylamide, acrylonitrile, bisphenol acrylates, carbohydrates, fluorinated acrylates, maleimide, acrylates, 4-acetoxyphenethyl acrylate, acryloyl chloride, 4-acryloylmorpholine, 2-(acryloyloxy)ethyl]trimethylammonium chloride, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, 2-propylbenzyl acrylate, butyl acrylate, tert-butyl acrylate, 2-[(butamino)carbonyl]oxy]ethyl acrylate, 2-bromoacrylate tert-butyl acrylate, 2-carboxyethyl acrylate, 2-chloroethyl acrylate, 2-(diethylamino)ethyl acrylate, di(ethylene glycol)ethyl ether acrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl acrylate, and dipentaerythritol penta- / hexa-propyl acrylate. Acrylates, ethyl acrylates, 2-ethylacryloyl chloride, 2-(bromomethyl)ethyl acrylate, cis-(β-cyano)ethyl acrylate, ethylene glycol dicyclopentene ether acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, 2-ethyl ethyl acrylate, 2-ethylhexyl acrylate, 2-propyl ethyl acrylate, 2-(trimethylsilylmethyl)ethyl acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, isobutyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetaminoacrylate, methyl acrylate, methylene malonate (e.g., dibutyl methylene malonate, dihexyl methylene malonate, or dicyclohexyl methylene malonate), methylene malonate macromonomers (e.g., polyesters of 2-methylene malonate, such as Forza). B3000XP), methyl α-bromoacrylate, methyl 2-(bromomethyl)acrylate, methyl 2-(chloromethyl)acrylate, methyl 3-hydroxy-2-methylenebutyrate, methyl 2-(trifluoromethyl)acrylate, octadecyl acrylate, pentabromobenzyl acrylate, pentabromophenyl acrylate, pentafluorophenyl acrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) methyl ether acrylate, poly(propylene glycol) acrylate, epoxidized soybean oil acrylate, 3-sulfopropyl acrylate, tetrahydrofurfuryl acrylate, 2-tetrahydropyran acrylate 3-(trimethoxysilyl)propyl acrylate, 3,5,5-trimethylhexyl acrylate, 10-undecenyl acrylate, polyurethane acrylate, polyurethane acrylate methacrylate, tricyclodecane diacrylate, isobornyl acrylate, methacrylate, allyl methacrylate, benzyl methacrylate, (2-boc-amino)ethyl methacrylate, tert-butyl methacrylate, 9H-carbazole-9-ethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 1,10-Decanediol 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-methacryloylaminobenzoic acid, isobutyl methacrylate, methacryloyl chloride, methyl methacrylate, mono-2-methacryloyloxyethyl succinate, 2-N-morpholinoethyl methacrylate, 1-naphthyl methacrylate Pentabromophenyl methacrylate, phenyl methacrylate, pentabromophenyl methacrylate, TEMPO methacrylate, 3-sulfopropyl methacrylate, triethylene glycol methyl ether methacrylate, 2-[(1',1',1'-trifluoro-2'-(trifluoromethyl)-2'0hydroxy)propyl]-3-norbornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, (trimethylsilyl) methacrylate, vinyl methacrylate, isobornyl methacrylate, bisphenol A dimethacrylate, Omnilane OC, tert-butyl acrylate, isodecyl acrylate, tricyclodecane diacrylate, polyfunctional acrylates, N,N'-methylenebisacrylamide, 3-(acryloyloxy)-2-hydroxypropyl)methacrylate, bis[2-(methacryloyloxy)ethyl]phosphate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, dipolyurethane dimethacrylate, N,N'-ethylenebis(acrylamide), glycerol 1,3-glyceryl alcohol diacrylate, 1,6-hexanediol diacrylate, hydroxypentanoyl hydroxypentanoate bis[6-(acryloyloxy)hexanoate], neopentyl glycol diacrylate, pentaerythritol diacrylate, 1,3,6-triacryloyl hexahydro-1,3,5-triazine, trimethylolpropane ethoxylate, tri[2-(acryloyloxy)ethyl]isocyanurate, any derivative thereof, or combinations thereof.

[0254] The micelle or photopolymer networks described herein may contain one or more reactive functional groups, which may allow for further modification of the micelle and / or photopolymer networks, such as additional polymerization (e.g., post-curing).

[0255] Non-limiting examples of reactive functional groups include radically polymerizable functional groups, photoactive groups, groups that promote stepwise growth polymerization, thermally reactive groups, and / or groups that promote bond formation (e.g., covalent bond formation). In some embodiments, reactive functional groups include acrylates, methacrylates, acrylamides, vinyl groups, vinyl ethers, thiols, allyl ethers, norbornene, vinyl acetate, maleates, fumarates, maleimides, epoxides, ring-strained cyclic ethers, ring-strained thioethers, cyclic esters, cyclic carbonates, cyclic silanes, cyclic siloxanes, hydroxyl groups, amines, isocyanates, terminal isocyanates, acyl chlorides, reactive esters, Diels-Alder reactive groups, furans, cyclopentadiene, acid anhydrides, groups that promote photodimerization (e.g., anthracene, acenaphthene, or coumarin), groups that photodegrade into reactive substances (e.g., type I and type II Norrish materials), azides, derivatives thereof, or combinations thereof.

[0256] In some embodiments, the melting temperature of the polymer composition may be 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. In some embodiments, the resin curing may be carried out at elevated temperatures (e.g., about 90°C).

[0257] In some embodiments, the cured photopolymer network or polymer composition can be characterized by a tensile stress-strain curve showing the yield point after which the specimen continues to elongate, but with no (detectable) stress increase or only a very low stress increase. This yield point behavior typically occurs “near” the glass transition temperature, where the material is between a glassy and rubbery state and can be characterized as having viscoelastic behavior. In some embodiments, viscoelastic behavior is observed in a temperature range of about 20°C to about 40°C. The yield stress is determined at the yield point. In some embodiments, the modulus is determined by the initial slope of the stress-strain curve or by the secant modulus at 1% strain (e.g., when the stress-strain curve has no linear portion). The yield elongation is determined by the strain at the yield point. When the yield point occurs at the maximum stress, the ultimate tensile strength is less than the yield strength. For tensile specimens, strain is defined by ln(l / l0), which can be approximated as (l-l0) / l0 at small strains (e.g., less than about 10%), and elongation is l / l0, where l is the gauge length after some deformation and l0 is the initial gauge length. Mechanical properties can depend on the temperature at which the measurement is performed. The test temperature can be below the expected operating temperature of the dental instrument, for example, 35°C to 40°C. In some embodiments, the test temperature is 23 ± 2°C.

[0258] Properties of polymer compositions

[0259] Compared to conventional polymer compositions, the polymer compositions and / or photopolymer networks of this disclosure, formed by polymerizing the curable resins disclosed herein, can provide advantageous properties. In some cases, the polymer compositions and / or photopolymer networks can also exhibit low water absorption and solvent resistance. In some cases, the polymer compositions and / or photopolymer networks can be characterized by one or more properties selected from: elongation at break, storage modulus, tensile modulus, residual stress, glass transition temperature, water absorption, hardness, color, transparency, hydrophobicity, lubricity, surface texture, crystallinity percentage, phase composition ratio, phase domain size, and phase domain size and morphology. Furthermore, as described herein, the polymer compositions and / or photopolymer networks provided herein can be used in a variety of applications, including 3D printing, to form materials with good elastic and stiffness properties. Specifically, the polymer compositions and / or photopolymer networks of this disclosure can provide excellent flexural modulus, elastic modulus, elongation at break, or combinations thereof.

[0260] In various embodiments, the polymer compositions and / or photopolymer networks described herein may contain or consist of high toughness, for example by a tough polymer matrix, and the difference (or δ) between the elastic moduli measured at different strain rates (e.g., 1.7 mm / min and 510 mm / min) may be very low, for example, less than 80%, 70%, 60%, 50%, 40% or less than 30%.

[0261] In some embodiments, the polymer composition and / or photopolymer network of this disclosure may have one or more of the following properties: (A) a flexural modulus greater than or equal to 50 MPa, 100 MPa, or 200 MPa; (B) an elastic modulus greater than or equal to 150 MPa, 250 MPa, 350 MPa, 450 MPa, or 550 MPa, or about 500 to 1500 MPa, about 550 to about 1000 MPa, or about 550 MPa to about 1500 MPa; (C) an elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37°C; (D) a water absorption rate less than 25 wt% when measured after 24 hours in a humid environment at 37°C; (E) a transmittance of visible light through the polymer composition of at least 30% after 24 hours in a humid environment at 37°C; and (F) comprising a plurality of polymer phases, wherein at least one of the polymer phases has a T g The temperature is at least 60°C, 80°C, 90°C, 100°C, or at least 110°C. In some cases, the polymer compositions and / or photopolymer networks described herein have at least two, three, four, five, or all of the properties in (A), (B), (C), (D), (E), and (F).

[0262] In some cases, the polymer composition and / or photopolymer network may be characterized by having 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 humid environment at 37°C.

[0263] In some cases, after 24 hours in a humid environment at 37°C, the residual flexural stress of the polymer composition and / or photopolymer network described herein can be 400 MPa or higher, 300 MPa or higher, 200 MPa or higher, 180 MPa or higher, 160 MPa or higher, 120 MPa or higher, 100 MPa or higher, 80 MPa or higher, 70 MPa or higher, or 60 MPa or higher.

[0264] In some cases, the polymer composition and / or photopolymer network may be characterized by having an elongation at break greater than 10%, greater than 20%, greater than 30%, between 5% and 250%, between 20% and 250%, or between 40% and 250% before and after 24 hours in a humid environment at 37°C.

[0265] In some embodiments, the polymer composition and / or photopolymer network are characterized by a water absorption rate 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 humid environment at 37°C. In some cases, the polymer composition and / or photopolymer network may have a double-bond to single-bond conversion rate greater than 50%, 60%, or 70% compared to a photocurable resin, as measured by FTIR.

[0266] In some cases, after 24 hours in a humid environment at 37°C, the ultimate tensile strength of the polymer composition and / or photopolymer network can be 10 MPa to 100 MPa, 15 MPa to 80 MPa, 20 MPa to 60 MPa, 10 MPa to 50 MPa, 10 MPa to 45 MPa, 25 MPa to 40 MPa, 30 MPa to 45 MPa, or 30 MPa to 40 MPa.

[0267] In some cases, the polymer composition may have a very low amount of hydrogen bonds, which can promote a reduction in water absorption compared to conventional polymer compositions with a higher amount of hydrogen bonds. Therefore, in some cases, the polymer compositions described herein, when fully saturated at the use temperature (e.g., about 20°C, 25°C, 30°C, or 35°C), may contain 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. In some cases, the use temperature may include the temperature of the human mouth (e.g., about 35-40°C). The operating temperature can be selected from -100-250℃, 0-90℃, 0-80℃, 0-70℃, 0-60℃, 0-50℃, 0-40℃, 0-30℃, 0-20℃, 0-10℃, 20-90℃, 20-80℃, 20-70℃, 20-60℃, 20-50℃, 20-40℃, 20-30℃, or below 0℃.

[0268] In various cases, the glass transition temperature of the polymer composition can be 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.

[0269] This document also provides polymer films comprising the polymer compositions disclosed herein. In some cases, the thickness of such polymer films can be at least about 50 μm, 100 μm, 250 μm, 500 μm, 1 mm, 2 mm, and not exceeding 3 mm.

[0270] This disclosure provides devices comprising the polymer compositions and / or photopolymer networks of this disclosure. In various cases, the device may be a medical device. A medical device may be an orthodontic appliance. An orthodontic appliance may be a dental brace, a dental expander, or a dental spacer.

[0271] How to use

[0272] This disclosure provides methods for synthesizing the polymer compositions and / or photopolymer networks disclosed herein, methods for using compositions comprising such compounds (e.g., resins and polymer compositions), and methods for using the compositions in devices such as medical devices. When using photopolymerization to cure the resin, the polymerizable compounds of this disclosure (e.g., monomers or macromolecular initiators) can be used as components of materials suitable for many different industries, such as transportation (e.g., airplanes, trains, ships, automobiles, etc.), hobby, prototyping, medical, art, microfluidics, mold making, etc. In various embodiments herein, such medical devices include orthodontic appliances.

[0273] Methods for forming polymer compositions

[0274] This document also provides a method for polymerizing (e.g., photocuring) a photocurable resin to obtain a polymer composition, the photocurable resin optionally comprising one or more additional components selected from macromolecular initiators, polymerizable polymers, polymerizable oligomers, polymerizable monomers (e.g., reactive diluents), solvents, fillers, antioxidants, pigments, colorants, surface modifiers, and mixtures thereof. In some embodiments, the method includes the step of mixing the curable composition. In some embodiments, the method includes heating the curable composition. In some embodiments, the method includes initiating polymerization by heating and / or irradiating the composition.

[0275] This disclosure provides methods for producing polymer compositions and / or photopolymer networks using the curable resin described herein. In various embodiments, methods for photocuring the photocurable resin are provided herein. Therefore, in various cases, a method for forming polymer compositions and / or photopolymer networks is provided herein, comprising: (i) providing the photocurable resin of this disclosure; (ii) exposing the photocurable resin to a light source; and curing the photocurable resin to form the polymer composition and / or photopolymer network.

[0276] In some embodiments, photocuring includes a single curing step. In some embodiments, photocuring includes multiple curing steps. In still other embodiments, photocuring includes at least one curing step of exposing the curable resin to light. Exposing the curable resin to light can initiate and / or promote photopolymerization. In some cases, a photoinitiator can be used as part of the resin to accelerate and / or initiate photopolymerization. In some embodiments, the resin is exposed to UV (ultraviolet) light, visible light, IR (infrared) light, or any combination thereof. In some embodiments, a cured polymer composition is formed from the photocurable resin using at least one step including exposure to a light source, wherein the light source includes UV light, visible light, and / or IR light. In some embodiments, the light source includes wavelengths of 10 nm to 200 nm, 200 nm to 350 nm, 350 nm to 450 nm, 450 nm to 550 nm, 550 nm to 650 nm, 650 nm to 750 nm, 750 nm to 850 nm, 850 nm to 1000 nm, or 1000 nm to 1500 nm.

[0277] As described herein, the polymer compositions and / or photopolymer networks prepared by the methods provided herein may be characterized by one or more of the following: (i) a storage modulus greater than or equal to 200 MPa; (ii) a residual flexural stress greater than or equal to 1.5 MPa after 24 hours in a humid environment at 37°C; (iii) an elongation at break greater than or equal to 5% before and after 24 hours in a humid environment at 37°C; (iv) a water absorption rate less than 25 wt% when measured after 24 hours in a humid environment at 37°C; and (v) a transmittance of at least 30% of visible light transmitted through the polymer composition after 24 hours in a humid environment at 37°C. In various cases, such polymer compositions may be characterized by at least two, three, four, or all of the above properties.

[0278] This article provides methods for manufacturing medical devices (e.g., orthodontic appliances, such as orthodontic appliances, dental expanders, or dental spacers) using polymerizable compounds, curable resins, and compositions containing such compounds, as well as polymer compositions and / or photopolymer networks prepared from such resins and compositions.

[0279] Therefore, in some embodiments, the method herein further includes the step of using an additive manufacturing apparatus to manufacture an apparatus or object, wherein the additive manufacturing apparatus facilitates curing. In some embodiments, curing of the polymerizable resin produces a cured polymer composition and / or photopolymer network. In some embodiments, an additive manufacturing apparatus is used to cure the polymerizable resin to produce a cured polymer composition and / or photopolymer network. In some embodiments, the method further includes the step of cleaning the cured polymer composition and / or photopolymer network. In some embodiments, cleaning the cured polymer composition and / or photopolymer network includes washing and / or rinsing the cured polymer composition with a solvent, which can remove uncured resin and undesirable impurities from the cured polymer composition.

[0280] In some embodiments, the polymerizable resins described herein may be curable and have a melting point < 100°C, thus being liquid at temperatures typically employed in currently available additive manufacturing technologies and therefore processable. As described herein, the polymerizable monomers of this disclosure, used as components in curable resins, can have low vapor pressures at elevated temperatures compared to conventional reactive diluents or other polymerizable components used in curable resins. This low vapor pressure of the monomers described herein is particularly advantageous for use in the manufacture of curable (e.g., photocurable) compositions and additives, where elevated temperatures (e.g., 60°C, 80°C, 90°C, or higher) may be used. In various cases, the vapor pressure of the polymerizable monomers at 60°C is at most about 12 Pa, or lower, as further described herein.

[0281] In some embodiments, the methods disclosed herein for forming polymer compositions and / or photopolymer networks are part of a photopolymerization process based on high-temperature photolithography, wherein a photocurable resin, which may contain at least one photoinitiator, is heated to an elevated process temperature (e.g., from about 50°C to about 120°C, for example, from about 90°C to about 120°C). Therefore, the methods according to this disclosure for forming polymer compositions and / or photopolymer networks can provide the possibility of rapidly and easily producing devices (e.g., orthodontic appliances) using additive manufacturing (e.g., 3D printing) with the curable resins disclosed herein.

[0282] Photopolymerization can occur when the photocurable resin described herein is exposed to radiation of a wavelength sufficient to initiate polymerization (e.g., UV or visible light). The wavelength of radiation that can be used to initiate polymerization may depend on the photoinitiator used. As used herein, “light” includes any wavelength and power capable of initiating polymerization. Some light wavelengths include ultraviolet (UV) or visible light. UV light sources include UVA (wavelengths from about 400 nanometers (nm) to about 320 nm), UVB (wavelengths from about 320 nm to about 290 nm), or UVC (wavelengths from about 290 nm to about 100 nm). Any suitable source can be used, including laser sources. The source can be broadband or narrowband or a combination thereof. The light source can provide continuous or pulsed light during the process. The duration of system exposure to UV light and the intensity of the UV light can be varied to determine ideal reaction conditions.

[0283] In some embodiments, the methods disclosed herein include using additive manufacturing to produce apparatus comprising a cured polymer composition. Such apparatus can be an orthodontic appliance. An orthodontic appliance can be a dental brace, a dental expander, or a dental spacer. In some embodiments, the methods disclosed herein use additive manufacturing to produce apparatus comprising, substantially comprising, or composed of, a cured polymer composition and / or a photopolymer network. Additive manufacturing encompasses a variety of techniques for fabricating three-dimensional objects directly from a digital model using additive processes. In some aspects, continuous layers of material are deposited and “cured in situ.” Various techniques are known in the field of 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 powder material according to a desired cross-sectional shape to construct the geometry of an object. In many embodiments, fused deposition modeling involves melting and selectively depositing filaments of a thermoplastic polymer in a layer-by-layer manner to form an object. In yet another example, 3D printing can be used to manufacture the orthodontic appliances described herein. In many embodiments, 3D printing involves jetting or extruding one or more materials onto a build surface to form continuous layers of an object geometry. In some embodiments, the photocurable resin described herein can be used for inkjet or coating applications. Cured polymer compositions and / or photopolymer networks can also be manufactured via an “urn” process, which uses light to selectively cure the curable resin in an urn or reservoir. Each layer of the curable resin can be selectively exposed to light in a single exposure or by scanning a beam of light through the layer. Specific techniques that can be used herein may include stereolithography (SLA), digital light processing (DLP), and two-photon induced photopolymerization (TPIP).

[0284] In some embodiments, thermoplastic polymer filaments are included as additives at concentrations of at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, and at least 55 wt%. In some embodiments, thermoplastic polymer filaments are included as additives at concentrations of less than 60 wt%, less than 55 wt%, less than 50 wt%, less than 45 wt%, less than 40 wt%, less than 35 wt%, less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 5 wt%, or less than 1 wt%.

[0285] In some embodiments, the methods disclosed herein use continuous direct manufacturing to produce apparatus comprising a cured polymer composition and / or a photopolymer network. Such apparatus may be the orthodontic appliance described herein. In some embodiments, the methods disclosed herein may include apparatus (e.g., orthodontic appliances) comprising, substantially comprising, or composed of a cured polymer composition using continuous direct manufacturing. Non-limiting exemplary direct manufacturing processes can achieve continuous construction of object geometry by the continuous movement of a build platform during the irradiation phase (e.g., along the longitudinal or Z-direction), such that the curing depth of the irradiated photopolymer (e.g., an irradiated photocurable resin that hardens during the formation of the cured polymer composition) is controlled by the movement speed. Thus, continuous polymerization of materials (e.g., polymerizing a photocurable resin into a cured polymer composition) can be achieved on the build surface. Such a method is described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety. In another example, the continuous direct manufacturing method utilizes a "heliolithography" method, in which a liquid resin (e.g., a photocurable resin) is cured by focused radiation while a build platform is continuously rotated and raised. Thus, the geometry of an object can be continuously built along a helical build path. Such a method is described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety. Continuous liquid interface production of 3D objects has also been reported (J. Tumbleston et al., Science The document 2015, 347 (6228), 1349-1352, is incorporated herein by reference in its entirety to describe the process. Another example of a continuous direct manufacturing method may involve extruding a material consisting of a curable liquid material or resin surrounding a solid strand. The material can be extruded along a continuous three-dimensional path to form an object. Such a method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0286] In some embodiments, the methods disclosed herein may include apparatus for producing a cured polymer composition using high-temperature photolithography. Such apparatus may be orthodontic appliances as described herein. In some embodiments, the methods disclosed herein use high-temperature photolithography to produce an apparatus for producing a cured polymer composition, substantially comprising, or composed of a cured polymer composition. As used herein, “high-temperature photolithography” may refer to any photolithography-based photopolymerization process involving heating a photopolymerizable material (e.g., the photocurable resin disclosed herein). Heating may reduce the viscosity of the photocurable resin before and / or during curing. Non-limiting examples of high-temperature photolithography processes include those described in PCT Publications WO 2015 / 075094, WO 2016 / 078838, and WO2018 / 032022. In some embodiments, high-temperature lithography can involve applying heat to the material at temperatures of approximately 50°C to approximately 120°C, such as approximately 90°C to approximately 120°C, approximately 100°C to approximately 120°C, approximately 105°C to approximately 115°C, approximately 108°C to approximately 110°C, etc. The material can be heated to temperatures greater than approximately 120°C. It should be noted that other temperature ranges may be used without departing from the scope and spirit of the inventive concept described herein.

[0287] Because in some cases the polymerizable compounds of this disclosure can be copolymerized as part of a photocurable resin during polymerization according to the method of this disclosure, the result can be an optionally crosslinked polymer comprising portions of one or more polymerizable compounds as repeating units. In some cases, such polymers are crosslinked polymers, which are generally suitable for and usable in orthodontic appliances. The polymerizable compounds of this disclosure, containing multiple reactive functional groups, can provide a homogeneous and continuous polymer network with clear phase separation.

[0288] In a further embodiment, the method herein may include polymerizing a curable composition comprising at least one polymerizable compound that, upon polymerization, provides a crosslinked polymer matrix, the crosslinked polymer matrix potentially comprising portions derived from the polymerizable compound of this disclosure as repeating units. To obtain a crosslinked polymer that may be particularly suitable as an orthodontic appliance, at least one polymerizable compound used in the method according to this disclosure may be selected based on several thermomechanical properties of the resulting polymer. In some cases, the curable resin of this disclosure may comprise one or more polymerizable compounds. In some cases, the polymerizable monomer of this disclosure may also have crosslinking functional groups, thus acting not only as a reactive diluent with a low vapor pressure but also as a crosslinking agent during the polymerization of the curable resin described herein, where it contains multiple reactive functional groups (similar to the polymerizable compounds herein). In other embodiments, the resin comprises a polymerizable compound, a polymerizable monomer, and a crosslinking monomer as described herein, wherein the two monomers are distinct substances (i.e., chemical entities).

[0289] Orthodontic appliances and their uses

[0290] The micelles and / or photopolymer networks according to this disclosure can be used as components of viscous or highly viscous photocurable resins and can produce polymer compositions that can have the good thermomechanical properties (e.g., stiffness, residual stress, etc.) described herein for use in orthodontic appliances, such as for moving one or more teeth of a patient.

[0291] As described herein, this disclosure provides a method for repositioning a patient's teeth, the method comprising: (i) generating a treatment plan for the patient, the plan including 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 the polymer composition described herein; and using the dental appliance to move at least one of the patient's teeth along the treatment plan toward an intermediate tooth arrangement or a final tooth arrangement. Such a dental appliance can be manufactured using processes including 3D printing, as further described herein. The method for repositioning a patient's teeth may further include tracking the progress of the patient's teeth along the treatment path after application of the dental appliance to the patient, the tracking including comparing the current alignment of the patient's teeth with the planned alignment of the patient's teeth. In this case, after two weeks of treatment, more than 60% of the patient's teeth may conform to the treatment plan. In some cases, the dental appliance retains a repositioning force on 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 the repositioning force initially applied to at least one of the patient's teeth.

[0292] The terms “rigidity” and “stiffness” used in this article are used interchangeably, as are the corresponding terms “rigid” and “stiff”. The term “multiple teeth” as used in this article includes two or more teeth.

[0293] In many embodiments, one or more posterior teeth include one or more of molars, premolars, or canines, and one or more anterior teeth include one or more of central incisors, lateral incisors, canines, first premolars, or second premolars.

[0294] In some embodiments, the compositions and methods described herein can be used to couple one or more groups of teeth to each other. A group of one or more teeth may include 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 using the polymer shell apparatus disclosed herein.

[0295] The embodiments disclosed herein are well suited for moving one or more teeth in a first group of one or more teeth, or moving one or more teeth in a second group of one or more teeth, and combinations thereof.

[0296] The embodiments disclosed herein are well-suited for combination with one or more known commercially available tooth movement components (e.g., attachments and polymer-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, three of which are rotational and three of which are translational.

[0297] Although references have been made to devices including polymer-shell devices, the embodiments disclosed herein are well-suited for use with many tooth-receiving devices, such as those not having one or more of a polymer or shell. The device can be manufactured from one or more of a variety of materials, such as metals, glass, reinforcing fibers, carbon fibers, composite materials, reinforced composite materials, aluminum, biomaterials, and combinations thereof. The device can be formed in many ways, such as thermoforming or direct manufacturing as described herein. Alternatively or in combination, the device can be manufactured by machining, for example, by computer numerical control machining of a device made from a single piece of material.

[0298] Now turn to the accompanying drawings, where the same numbers represent the same elements in each figure. Figure 1AAn exemplary tooth repositioning appliance or orthodontic appliance 100 is shown, which can be worn by a patient to achieve incremental repositioning of individual teeth 102 in the jawbone. The appliance may include a shell (e.g., a continuous polymer shell or a segmented shell) having tooth receiving cavities that receive and resiliently reposition the teeth. The appliance or portions thereof may be manufactured indirectly using a physical model of the teeth. For example, the appliance (e.g., a polymer appliance) may be formed using a physical model of the teeth and a suitable layer of polymer composition. In some embodiments, the physical appliance is manufactured directly from a digital model of the appliance, for example, using rapid prototyping techniques. The appliance may cover all or fewer teeth present in the maxilla or mandible. The appliance may be specifically designed to accommodate a patient's teeth (e.g., the morphology of the tooth receiving cavities matches the morphology of the patient's teeth) and may be manufactured based on positive or negative models of the patient's teeth generated by impressions, scanning, etc. Alternatively, the appliance may be a general-purpose appliance configured to receive teeth but not necessarily shaped to match the morphology of a patient's teeth. In some cases, only certain teeth received by the appliance will be repositioned by the appliance, while other teeth may provide a base or anchorage area to hold the appliance in place when the appliance applies force to one or more target teeth to be repositioned. In some cases, at certain points during treatment, some, most, or even all of the teeth may be repositioned. The moved teeth may also act as a base or anchorage for securing the appliance while the patient wears it. Typically, no wires or other means are provided to secure the appliance in its proper position above the teeth. However, in some cases, it may be desirable or necessary to provide separate attachments or other anchoring elements 104 on the teeth 102 and to provide corresponding receptacles or openings 106 on the appliance 100 so that the appliance can apply selected forces to the teeth. Exemplary appliances, including those used in the Invisalign® system, are described in numerous patents and patent applications attributed to Align Technology, Inc. (including, for example, U.S. Patent Nos. 6,450,807 and 5,975,893) and on the company’s website (accessible on the World Wide Web, see, for example, the URL “invisalign.com”). Examples of dental attachments suitable for use with orthodontic appliances are also described in patents and patent applications attributed to Align Technology, Inc. (e.g., U.S. Patent Nos. 6,309,215 and 6,830,450).

[0299] Figure 1BA tooth repositioning system 110 is illustrated, comprising a plurality of appliances 112, 114, and 116. Any of the appliances described herein can be designed and / or provided as part of a set of multiple appliances used in a tooth repositioning system. Each appliance can be configured to give the tooth receiving cavity a geometry corresponding to an intermediate or final tooth alignment intended for use with that appliance. By placing a series of incrementally position-adjusting appliances on the patient's teeth, the patient's teeth can be progressively repositioned from an initial tooth alignment to a target tooth alignment. For example, the tooth repositioning system 110 may include a first appliance 112 corresponding to the initial tooth alignment, one or more intermediate appliances 114 corresponding to one or more intermediate alignments, and a final appliance 116 corresponding to the target alignment. The target tooth alignment may be the planned final tooth alignment selected for the patient's teeth at the end of all planned orthodontic treatment. Alternatively, the target alignment can be one of several intermediate alignments of the patient's teeth during orthodontic treatment. This can include a variety of different treatment scenarios, including but not limited to: recommendations for surgery, suitability for interproximal enamel reduction (IPR), scheduling of progress checks, optimal anchor placement, need for palatal expansion, and involvement of restorative dentistry (e.g., inlays, onlays, crowns, bridges, implants, veneers, etc.). Therefore, it can be understood that the target tooth alignment can be the final alignment of the patient's teeth in any planned sequence following one or more incremental repositioning phases. Similarly, the initial tooth alignment can be any initial alignment of the patient's teeth before one or more incremental repositioning phases.

[0300] Figure 1CA method 150 for orthodontic treatment using multiple appliances according to some embodiments is illustrated. Method 150 can be implemented using any of the appliances or groups of appliances described herein. In step 160, a first orthodontic appliance is applied to the patient's teeth to reposition the teeth from a first dental alignment to a second dental alignment. In step 170, a second orthodontic appliance is applied to the patient's teeth to reposition the teeth from the second dental alignment to a third dental alignment. Method 150 can be repeated as needed using any suitable number and combination of successive appliances to incrementally reposition the patient's teeth from the initial alignment to the target alignment. Appliances can be generated all at once in the same phase, or in groups or batches (e.g., at the start of a phase of treatment), or appliances can be made one at a time, and the patient can wear each appliance until no pressure is felt on the teeth from each appliance, or until the maximum amount of tooth movement expressed in a given phase has been achieved. Multiple different appliances (e.g., a group) can be designed or even manufactured before the patient wears any one of the multiple appliances. After wearing an appliance for an appropriate period, the patient can replace the current appliance with the next appliance in the series until no appliances remain. Appliances are typically not fixed to the teeth, and patients can place and replace them at any time during treatment (e.g., patient-removable appliances). The last appliance or several appliances in a series may have a geometry chosen for overcorrecting tooth alignment. For example, one or more appliances may have a geometry such that, if fully realized, it would move a single tooth beyond the selected “final” alignment. This overcorrection may be desirable to counteract potential relapse after the repositioning approach is terminated (e.g., allowing a single tooth to move back to its pre-correction position). Overcorrection can also help accelerate the treatment process (e.g., an appliance with a geometry exceeding the expected intermediate or final position may move a single tooth to that position more quickly). In this case, the appliance may be discontinued before the tooth reaches the position defined by the appliance. Furthermore, overcorrection may be intentionally performed to compensate for any inaccuracies or limitations of the appliance.

[0301] The various embodiments of the orthodontic appliances presented herein can be manufactured in a variety of ways. In some embodiments, the orthodontic appliances (or portions thereof) of this document can be produced using direct manufacturing techniques, such as additive manufacturing (also referred to herein as “3D printing”) or subtractive manufacturing techniques (e.g., milling). In some embodiments, direct manufacturing involves forming an object (e.g., an orthodontic appliance or a portion thereof) without using physical templates (e.g., molds, masks, etc.) to define the geometry of the object. Additive manufacturing technologies can be categorized as follows: (1) urn photopolymerization (e.g., stereolithography), in which an object is constructed layer by layer from a urn of liquid photopolymer resin; (2) material jetting, in which material is jetted onto a build platform using a continuous or on-demand dripping (DOD) method; (3) binder jetting, in which alternating layers of build material (e.g., powder-based material) and binder (e.g., liquid binder) are deposited by a printhead; (4) fused deposition modeling (FDM), in which material is stretched, heated, and deposited layer by layer through a nozzle; (5) powder bed melting, including but not limited to direct metal laser sintering (DMLS), electron beam melting (EBM), selective thermal sintering (SHS), selective laser melting (SLM), and selective laser sintering (SLS); (6) sheet lamination, including but not limited to layered solid fabrication (LOM) and ultrasonic additive manufacturing (UAM); and (7) directional energy deposition, including but not limited to laser engineered net-shape forming, directional light fabrication, direct metal deposition, and 3D laser cladding. For example, stereolithography can be used to directly manufacture one or more of the devices described herein. In some embodiments, stereolithography involves selectively polymerizing a photosensitive resin (e.g., a photopolymer) according to a desired cross-sectional shape using light (e.g., ultraviolet light). By sequentially polymerizing multiple object cross-sections, an object geometry can be built layer by layer. As another example, the apparatus described herein can be directly manufactured using selective laser sintering. In some embodiments, selective laser sintering involves selectively melting and fusing layers of powder material according to a desired cross-sectional shape using a laser beam to establish an object geometry. As yet another example, the apparatus described herein can be directly manufactured using fused deposition modeling. In some embodiments, fused deposition modeling involves melting and selectively depositing filaments of a thermoplastic polymer in a layer-by-layer manner to form an object. In yet another example, the apparatus described herein can be directly manufactured using material jetting. In some embodiments, material jetting involves jetting or extruding one or more materials onto a build surface to form continuous layers of an object geometry.

[0302] Alternatively or in combination, some embodiments of the appliances (or portions thereof) described herein may be manufactured using indirect manufacturing techniques, such as by thermoforming on a positive or negative mold. Indirect manufacturing of orthodontic appliances may involve producing a positive or negative mold of a patient’s dentition with a target alignment (e.g., through rapid prototyping, milling, etc.) and thermoforming one or more sheets of material on the mold to produce an appliance shell.

[0303] In some embodiments, the direct manufacturing method provided herein constructs the object geometry in a layer-by-layer manner, wherein continuous layers are formed in discrete construction steps. Alternatively or in combination, direct manufacturing methods that allow for the continuous construction of object geometry can be used, referred to herein as "continuous direct manufacturing." Various types of continuous direct manufacturing can be used. As an example, in some embodiments, the apparatus of this invention is manufactured using "continuous liquid phase printing," wherein the object is continuously constructed from a reservoir of photopolymerizable resin by forming a gradient of partially cured resin between the construction surface of the object and a polymerization inhibition "dead zone." In some embodiments, a semi-permeable membrane is used to control the transport of photopolymerization inhibitors (e.g., oxygen) into the dead zone to form a polymerization gradient. Continuous liquid phase printing can achieve manufacturing speeds approximately 25 to approximately 100 times faster than other direct manufacturing methods, and approximately 1000 times faster by incorporating a cooling system. Continuous liquid phase printing is described in U.S. Patent Publications 2015 / 0097315, 2015 / 0097316 and 2015 / 0102532, the contents of which are incorporated herein by reference in their entirety.

[0304] As another example, continuous direct manufacturing methods can achieve continuous construction of object geometry through the continuous movement of a construction platform during the irradiation phase (e.g., along the longitudinal or Z-direction), such that the hardening depth of the irradiated photopolymer is controlled by the movement speed. Therefore, continuous polymerization of the material can be achieved on the construction surface. Such a method is described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety.

[0305] In another example, a continuous direct manufacturing method may include extruding a composite material consisting of a curable liquid material surrounding a solid strand. The composite material can be extruded along a continuous three-dimensional path to form an object. Such a method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0306] In yet another example, the continuous direct manufacturing method utilizes heliolithography, in which a liquid photopolymer is solidified using focused radiation while the build platform is continuously rotated and raised. Therefore, object geometry can be continuously built along a helical build path. Such a method is described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety.

[0307] The direct manufacturing method described herein is compatible with a variety of materials, including but not limited to one or more of the following: polyesters, copolyesters, polycarbonates, thermoplastic polyurethanes, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic acid, cyclic block copolymers, polyetheretherketones, polyamides, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polyethersulfone, polypropylene terephthalate, styrene block copolymers (SBCs), silicone rubber, elastomer alloys, thermoplastic elastomers (TPEs), thermoplastic vulcanizate (TPV) elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers, thermoplastic polyamide elastomers, thermosetting materials, or combinations thereof. Materials used for direct manufacturing may be provided in uncured form (e.g., liquids, resins, powders, etc.) and may be cured (e.g., by photopolymerization, light curing, gas curing, laser curing, crosslinking, etc.) to form orthodontic appliances or portions thereof. The properties of the material before curing may differ from the properties of the material after curing. Once cured, the materials described in this paper exhibit sufficient strength, stiffness, durability, and biocompatibility for use in orthodontic appliances. The cured properties of the materials can be selected based on the desired properties of the corresponding parts of the appliance.

[0308] In some implementations, the relatively rigid portion of the orthodontic appliance can be formed by direct manufacturing using one or more of the following materials: polyester, copolyester, polycarbonate, thermoplastic polyurethane, polypropylene, polyethylene, polypropylene and polyethylene copolymer, acrylic acid, cyclic block copolymer, polyetheretherketone, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polyethersulfone and / or polypropylene terephthalate.

[0309] In some implementations, the relatively elastic portion of the orthodontic appliance can be formed by direct manufacturing using one or more of the following materials: styrene block copolymer (SBC), silicone rubber, elastomer alloy, thermoplastic elastomer (TPE), thermoplastic vulcanized rubber (TPV) elastomer, polyurethane elastomer, block copolymer elastomer, polyolefin blend elastomer, thermoplastic copolyester elastomer, and / or thermoplastic polyamide elastomer.

[0310] Machine parameters can include curing parameters. For digital light processing (DLP) based curing systems, curing parameters can include power, curing time, and / or the grayscale of the complete image. For laser-based curing systems, curing parameters can include power, speed, beam size, beam shape, and / or beam power distribution. For printing systems, curing parameters can include material droplet size, viscosity, and / or curing power. These machine parameters can be monitored and adjusted periodically (e.g., some parameters every 1-x layers and some parameters after each build) as part of process control on the manufacturing machine. Process control can be achieved by including sensors on the machine that measure power and other beam parameters per layer or every few seconds and automatically adjust them via feedback loops. For DLP machines, grayscale can be measured and calibrated before, during, and / or at the end of each build and / or at predetermined time intervals (e.g., every n builds, once per hour, once per day, once per week, etc.), depending on system stability. Furthermore, material properties and / or optical characteristics can be provided to the manufacturing machine, and the machine process control module can use these parameters to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variations in material properties. By implementing process control on manufacturing machines, variations in tool accuracy and residual stress can be reduced.

[0311] Optionally, the direct manufacturing methods described herein allow for the manufacture of appliances comprising multiple materials, referred to herein as "multimaterial direct manufacturing." In some embodiments, the multimaterial direct manufacturing method involves simultaneously forming an object from multiple materials in a single manufacturing step. For example, multiple types of materials can be selectively dispensed from different material supply sources using a multi-head extrusion apparatus to manufacture an object from multiple different materials. Such a method is 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, the multimaterial direct manufacturing method may involve forming an object from multiple materials in multiple successive manufacturing steps. For example, according to any direct manufacturing method herein, a first portion of the object may be formed from a first material, then according to the method herein, a second portion of the object may be formed from a second material, and so on, until the entire object has been formed.

[0312] Direct manufacturing offers various advantages compared to other manufacturing methods. For example, compared to indirect manufacturing, direct manufacturing allows for the production of orthodontic appliances without the use of any molds or templates to shape the appliance, thereby reducing the number of manufacturing steps involved and improving the resolution and accuracy of the final appliance geometry. Furthermore, direct manufacturing allows for precise control of the appliance's three-dimensional geometry, such as appliance thickness. Complex structures and / or auxiliary components can be integrally formed with the appliance shell in a single manufacturing step, rather than being added to the shell in separate manufacturing steps. In some embodiments, direct manufacturing is used to produce appliance geometries that are difficult to create using alternative manufacturing techniques, such as appliances with very small or fine features, complex geometries, interlocking edges, adjacent structures, shells with variable thickness and / or internal structures (e.g., to increase strength with reduced weight and material usage). For example, in some embodiments, the direct manufacturing method described herein allows for the manufacture of orthodontic appliances with feature dimensions less than or equal to about 5 µm, or in the range of about 5 µm to about 50 µm, or in the range of about 20 µm to about 50 µm.

[0313] The direct manufacturing techniques described herein can be used to produce appliances with substantially isotropic material properties, such as substantially the same or similar strength in all directions. In some embodiments, the direct manufacturing method of this invention allows the production of orthodontic appliances with strength variations in all directions not exceeding about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5%. Furthermore, compared to other manufacturing techniques, the direct manufacturing method of this invention can be used to produce orthodontic appliances at a faster rate. In some embodiments, the direct manufacturing method of this invention allows the production of orthodontic appliances within time intervals of 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 minute, or about 30 seconds. This manufacturing speed allows for rapid "chairside" production of custom appliances, for example, during routine appointments or checkups.

[0314] In some implementations, the direct manufacturing methods described herein implement process control over various machine parameters of the direct manufacturing system or apparatus to ensure the manufacture of the resulting appliance with high precision. This precision can help ensure that the desired force system is accurately transmitted to the teeth, thereby effectively inducing tooth movement. Process control can be implemented to account for process variability caused by a variety of sources, such as material properties, machine parameters, environmental variables, and / or post-processing parameters.

[0315] Material properties can vary depending on the nature and purity of the raw materials and / or process variables during the mixing process. In many embodiments, the resins or other materials used for direct manufacturing should be manufactured under strict process control to ensure minimal variation in optical properties, material properties (e.g., viscosity, surface tension), physical properties (e.g., modulus, strength, elongation), and / or thermal properties (e.g., glass transition temperature, heat distortion temperature). Process control of the material manufacturing process can be achieved by screening raw materials for physical properties and / or controlling temperature, humidity, and / or other process parameters during the mixing process. By implementing process control over the material manufacturing process, the variability of process parameters can be reduced, and the material properties of each batch of material can be made more uniform. As further discussed herein, residual variations in material properties can be compensated for through on-machine process control.

[0316] Machine parameters can include curing parameters. For digital light processing (DLP) based curing systems, curing parameters can include power, curing time, and / or the grayscale of the complete image. For laser-based curing systems, curing parameters can include power, speed, beam size, beam shape, and / or beam power distribution. For printing systems, curing parameters can include material droplet size, viscosity, and / or curing power. These machine parameters can be monitored and adjusted periodically (e.g., some parameters every 1-x layers and some parameters after each build) as part of process control on the manufacturing machine. Process control can be achieved by including sensors on the machine that measure power and other beam parameters every layer or every few seconds and automatically adjust them via feedback loops. For DLP machines, grayscale can be measured and calibrated at the end of each build. Furthermore, material properties and / or optical characteristics can be provided to the manufacturing machine, and the machine process control module can use these parameters to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variations in material properties. By implementing process control on the manufacturing machine, variations in instrument accuracy and residual stress can be reduced.

[0317] In many implementations, environmental variables (e.g., temperature, humidity, sunlight, or exposure to other energy / curing sources) are kept within a narrow range to reduce variability in appliance thickness and / or other properties. Optionally, machine parameters can be adjusted to compensate for environmental variables.

[0318] In many implementations, post-treatment of the appliance includes cleaning, post-curing, and / or support removal processes. Relevant post-treatment parameters may include the purity of the cleaning agent, cleaning pressure and / or temperature, cleaning time, post-curing energy and / or time, and / or the consistency of the support removal process. These parameters can be measured and adjusted as part of a process control scheme. Furthermore, the physical properties of the appliance can be altered by modifying post-treatment parameters. Adjusting post-treatment machine parameters can provide another way to compensate for variability in material properties and / or machine properties.

[0319] The configuration of orthodontic appliances described herein can be determined based on a patient-specific treatment plan, such as one involving the incremental repositioning of teeth through the successive application of multiple appliances. Computer-based treatment planning and / or appliance manufacturing methods can be used to facilitate appliance design and manufacturing. For example, one or more appliance components described herein can be digitally designed and manufactured using computer-controlled manufacturing equipment, such as 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 manufacturing.

[0320] Figure 2 A method 200 for designing orthodontic appliances manufactured directly according to some embodiments is shown. Method 200 can be applied to any embodiment of the orthodontic appliances described herein. Some or all of the steps of method 200 can be performed by any suitable data processing system or apparatus, for example, one or more processors configured with suitable instructions.

[0321] In step 210, a movement path is determined to move one or more teeth from an initial alignment to a target alignment. The initial alignment can be determined by modeling or scanning the patient's teeth or oral tissues, for example using wax bite techniques, direct contact scanning, X-ray imaging, tomography, ultrasound imaging, and other techniques for acquiring information about the location and structure of teeth, jaws, gingiva, and other orthodontic-related tissues. From the obtained data, a digital dataset representing the initial (e.g., pre-treatment) alignment of the patient's teeth and other tissues can be derived. Optionally, the initial digital dataset is processed to segment the tissue components to each other. For example, a data structure digitally representing a single crown can be generated. Advantageously, a digital model of the entire tooth can be generated, including the measured or extrapolated hidden surfaces and root structures, as well as the surrounding bone and soft tissue.

[0322] The target alignment of teeth (e.g., the expectation and anticipated outcome of orthodontic treatment) can be received from the clinician in the form of a prescription, calculated based on fundamental orthodontic principles, and / or inferred from the clinical prescription through calculation. By specifying the expected final position of the teeth and a digital representation of the teeth themselves, the final position and surface geometry of each tooth can be designated to form a complete model of the expected tooth alignment at the end of treatment.

[0323] After obtaining the initial and target positions for each tooth, a movement path can be defined for the movement of each tooth. In some implementations, the movement path is configured to move the tooth from its initial position to its desired target position in the fastest manner with the fewest round trips. Optionally, the tooth path can be segmented, and the segments can be calculated such that the movement of each tooth within a segment remains within threshold limits of linearity and rotational translation. In this way, the endpoints of each path segment can constitute a clinically feasible repositioning, and the set of segment endpoints can constitute a clinically feasible sequence of tooth positions such that moving from one point to the next in the sequence does not result in tooth collision.

[0324] In step 220, a force system is determined that will induce movement of one or more teeth along the movement path. The force system may include one or more forces and / or one or more torques. Different force systems result in different types of tooth movement, such as tilting, translation, rotation, squeezing, intrusion, root movement, etc. Biomechanical principles, modeling techniques, force calculation / measurement techniques, and other knowledge and methods commonly used in orthodontics can be used to determine the appropriate force system to be applied to the teeth to achieve tooth movement. Sources that may be considered when determining the force system to be applied include literature, force systems determined through experimental or virtual modeling, computer-based modeling, clinical experience, minimizing unwanted forces, etc.

[0325] Determining the force system can include constraints on permissible forces, such as permissible direction and magnitude, and the desired movement induced by the applied forces. For example, different movement strategies may be desired for different patients when fabricating a palatal expander. For instance, the amount of force required to separate the palate may depend on the patient's age, as the palatal sutures may not be fully formed in very young patients. Therefore, palatal expansion can be achieved with smaller forces in adolescent patients and other patients whose palatal sutures are not fully closed. Slower palatal movement also facilitates bone growth to fill the expanded palatal sutures. For other patients, faster expansion may be desired, which can be achieved by applying greater forces. These requirements can be combined as needed to select the structure and materials of the appliance; for example, by selecting a palatal expander capable of applying larger forces to disrupt the palatal sutures and / or cause rapid palatal expansion. Subsequent appliance stages can be designed to apply forces of varying magnitudes, such as initially applying larger forces to disrupt the palatal sutures, followed by smaller forces to maintain suture separation or gradually expand the palate and / or dental arch.

[0326] Determining the force system can also include modeling the patient's facial structures, such as the skeletal structure of the jaw and palate. For example, scan data of the palate and dental arch, such as X-ray data or 3D optical scan data, can be used to determine parameters of the patient's oral skeletal and muscular systems, thereby determining the force sufficient to provide the desired expansion of the palate and / or dental arch. In some implementations, the thickness and / or density of the palatal suture can be measured or input by a treatment professional. In other implementations, the treatment professional can select appropriate treatment based on the patient's physiological characteristics. For example, the nature of the palate can also be estimated based on factors such as the patient's age—for instance, younger adolescent patients typically require less force to expand the palatal suture than older patients because the suture is not yet fully formed.

[0327] In step 230, the design of the dental arch or palatal expander configured to generate a force system for the orthodontic appliance is determined. The design of the dental arch or palatal expander, the appliance geometry, material composition, and / or properties can be determined using a treatment or force application simulation environment. The simulation environment may include, for example, a computer modeling system, a biomechanical system, or a device. Optionally, a digital model of the appliance and / or teeth, such as a finite element model, can be generated. The finite element model can be created using computer program application software available from various vendors. To create a solid geometry model, computer-aided engineering (CAE) or computer-aided design (CAD) programs can be used, such as AutoCAD® software products offered by Autodesk, Inc., San Rafael, California. To create and analyze the finite element model, program products from multiple vendors can be used, including the finite element analysis software package from ANSYS, Inc., Fort Cannons, Pennsylvania, and the SIMULIA (Abaqus) software product from Dassault Systèmes, Waltham, Massachusetts.

[0328] Optionally, one or more dental arch or palatal expander designs can be selected for testing or force modeling. As described above, the desired tooth movement and the required or desired force system to induce the desired tooth movement can be identified. Using a simulation environment, candidate dental arch or palatal expander designs can be analyzed or modeled to determine the actual force system generated using the candidate appliances. Optionally, one or more modifications can be made to the candidate appliances, and force modeling can be further analyzed as described, for example, to iteratively determine the appliance design that generates the desired force system.

[0329] In step 240, manufacturing instructions are generated for an orthodontic appliance incorporating a dental arch or palatal expander design. The instructions may be configured to control a manufacturing system or apparatus to produce an orthodontic appliance with the specified dental arch or palatal expander design. In some embodiments, the instructions are configured to manufacture the orthodontic appliance using direct manufacturing methods (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct manufacturing, multimaterial direct manufacturing, etc.) according to the various methods presented herein. In alternative embodiments, the instructions may be configured to indirectly manufacture the appliance, for example, by thermoforming.

[0330] Method 200 may include additional steps: 1) performing an intraoral scan of the patient’s upper dental arch and palate to generate three-dimensional data of the palate and upper dental arch; 2) determining the three-dimensional shape profile of the appliance to provide the gap and tooth occlusion structure as described herein.

[0331] While the steps described above illustrate a method 200 for designing orthodontic appliances according to some embodiments, those skilled in the art will recognize variations based on the teachings herein. Some steps may include sub-steps. Some of these steps may be repeated as needed. One or more steps of method 200 may be performed using any suitable manufacturing system or apparatus (e.g., the embodiments described herein). Some steps may be optional, and the order of the steps may be changed as needed.

[0332] Figure 3 Method 300 for digitally planning orthodontic treatment and / or designing or manufacturing appliances is illustrated according to some implementation schemes. Method 300 can be applied to any treatment procedure described herein and can be performed by any suitable data processing system.

[0333] In step 310, a digital representation of the patient's teeth is received. The digital representation may include surface topographic data of the patient's oral cavity (including teeth, gum tissue, etc.). The surface topographic data can be generated by directly scanning the oral cavity, a physical model (positive or negative) of the oral cavity, or an impression of the oral cavity using a suitable scanning device (e.g., a handheld scanner, a desktop scanner, etc.).

[0334] In step 320, one or more treatment phases are generated based on the digital representation of the teeth. A treatment phase can be an incremental repositioning phase of an orthodontic treatment procedure designed to move one or more of a patient's teeth from an initial tooth alignment to a target alignment. For example, a treatment phase can be generated by determining the initial tooth alignment indicated by the digital representation, determining the target tooth alignment, and determining the movement path of one or more teeth in the initial alignment necessary to achieve the target tooth alignment. The movement path can be optimized based on minimizing the total distance moved, preventing collisions between teeth, avoiding more difficult tooth movements, or any other suitable criteria.

[0335] In step 330, at least one orthodontic appliance is manufactured based on the generated treatment phase. For example, a set of appliances may be manufactured, each shaped according to the tooth alignment specified in a treatment phase, allowing the patient to wear the appliances sequentially to incrementally reposition the teeth from the initial alignment to the target alignment. The appliance set may include one or more orthodontic appliances as described herein. Manufacturing the appliances may involve creating a digital model of the appliance for use as input to a computer-controlled manufacturing system. The appliances may be formed using direct manufacturing methods, indirect manufacturing methods, or a combination thereof, as needed.

[0336] In some cases, the staging of various arrangements or treatment phases may not be necessary for the design and / or manufacture of the device. For example... Figure 3As shown by the dashed line, the design and / or manufacture of orthodontic appliances and possible specific orthodontic treatments may include using a representation of the patient's teeth (e.g., receiving a digital representation of the patient's teeth 310), and then designing and / or manufacturing the orthodontic appliance based on the representation of the patient's teeth in the arrangement represented by the received representation.

[0337] Treatment by Track

[0338] refer to Figure 4 The following illustrates method 400 according to this disclosure. Various aspects of the method will be discussed in further detail below. The method includes receiving information and / or treatment information about a patient's orthodontic status (402), generating a case assessment (404), and generating a treatment plan for repositioning the patient's teeth (406). In short, the patient / treatment information includes data containing the initial alignment of the patient's teeth, which includes obtaining impressions or scans of the patient's teeth prior to the commencement of treatment, and may also include identifying one or more treatment goals selected by the practitioner and / or patient. The case assessment (404) can be generated to evaluate the complexity or difficulty of moving a specific tooth of the patient, either generally or specifically, corresponding to the identified treatment goals, and may also include the practitioner's experience and / or comfort in implementing the desired orthodontic treatment. However, in some cases, the assessment may include simply identifying specific treatment options of interest to the patient and / or practitioner (e.g., appointment scheduling, progress tracking, etc.). This information and / or the corresponding treatment plan includes identifying the desired final or target alignment of the patient's teeth, and successive or intermediate tooth alignments of multiple plans for moving the teeth from the initial alignment to the selected final or target alignment along the treatment path.

[0339] The method also includes generating customized treatment guidelines (408). The treatment plan may include multiple treatment phases, wherein a set of customized treatment guidelines corresponding to the phases of the treatment plan is generated. The guidelines may include detailed information about the time and / or content to be completed in a given treatment phase (e.g., specific tasks) and may be detailed enough to guide practitioners throughout the treatment phase, including less experienced practitioners or practitioners relatively unfamiliar with a particular orthodontic treatment procedure. Because the guidelines are designed to correspond specifically to the treatment plan and provide guidance on treatment information and / or activities explicitly identified in the generated treatment plan, the guidelines may be customized. The customized treatment guidelines are then provided to the practitioner to help guide the practitioner on how to deliver a given treatment phase. As mentioned above, appliances may be generated based on the arrangement of the plan and may be provided to the practitioner and ultimately administered to the patient (410). Appliances may be provided and / or administered in sets or in batches, such as 2, 3, 4, 5, 6, 7, 8, 9 or more appliances, but are not limited to any particular administration scheme. The equipment can be provided to practitioners along with a given set of guidelines, or the equipment and guidelines can be provided separately.

[0340] After treatment begins according to the plan and after appliances are applied to the patient, treatment progress is tracked by means of, for example, tooth matching to assess the current and actual alignment of the patient's teeth compared to the planned alignment (412). If it is determined that the patient's teeth are "on track" and progressing according to the treatment plan, then the treatment proceeds as planned and enters the next treatment phase (414). If the patient's teeth have essentially achieved the initially planned final alignment, then the treatment enters the final treatment phase (414). If it is determined that the patient's teeth are moving according to the treatment plan but have not yet reached the final alignment, the next set of appliances can be applied to the patient.

[0341] Table 1 below shows the threshold difference between the planned and actual tooth positions, which is selected as an indicator that the patient's teeth have progressed on track. If the patient's tooth progress reaches or is within the threshold, the progress is considered to be on track. If the patient's tooth progress exceeds the threshold, the progress is considered to be off track.

[0342] Table 1

[0343] By comparing the current position of the patient's teeth with the expected or planned position and confirming that the teeth fall within the range of parameter variations disclosed in Table 1, it is determined that the patient's teeth are on track. If the patient's teeth are determined to be on track, treatment can proceed according to the existing or original treatment plan. For example, for patients determined to be on track, one or more follow-up appliances, such as the next set of appliances, can be applied according to the treatment plan. Treatment may progress to a final stage and / or may reach a point in the treatment plan where occlusal matching is repeated to determine whether the patient's teeth are progressing as planned or whether the teeth have deviated from the track.

[0344] In some embodiments, as further disclosed herein, this disclosure provides methods for treating patients using 3D-printed orthodontic appliances. As a non-limiting example, orthodontic appliances comprising crystalline domains, polymeric crystals, and / or materials capable of forming crystalline domains or polymeric crystals can be 3D-printed and used to reposition a patient's teeth. In some embodiments, the method of repositioning multiple teeth of a patient (or, in some embodiments, a single tooth) includes: generating a treatment plan for the patient, which includes multiple intermediate tooth arrangements for moving the tooth along a treatment path from an initial arrangement to a final arrangement; producing a 3D-printed orthodontic appliance; and using the orthodontic appliance to move at least one of the patient's teeth along a track towards the intermediate or final tooth arrangement. In some embodiments, the production of the 3D-printed orthodontic appliance uses crystallizable resins further disclosed herein. For example, track-by-track performance can be determined from Table 1 above.

[0345] In some embodiments, the method further includes tracking the progress of the patient's teeth along the treatment path after the application of an orthodontic appliance. In some embodiments, tracking includes comparing the current alignment of the patient's teeth with the planned alignment. As a non-limiting example, after the initial application of the orthodontic appliance, after a period of time (e.g., two weeks), the current alignment of the patient's teeth (e.g., at two weeks of treatment) can be compared with the planned alignment. In some embodiments, progress can also be tracked by comparing the current alignment of the patient's teeth with the initial configuration of the patient's teeth. This time period 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, this time period can be at least 3 days to at most 4 weeks, at least 3 days to at most 3 weeks, at least 3 days to at most 2 weeks, at least 4 days to at most 4 weeks, at least 4 days to at most 3 weeks, or at least 4 days to at most 2 weeks. In some implementations, this time period can be restarted after the application of a new orthodontic appliance.

[0346] In some implementations, after a period of time using the orthodontic appliances further disclosed herein, 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 conform to the treatment plan. In some implementations, this time 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.

[0347] As further disclosed herein, the orthodontic appliances disclosed herein possess advantageous properties, such as increased durability and the ability to maintain repositioning forces on a patient's teeth for an extended period. In some embodiments of the methods disclosed above, the 3D-printed orthodontic appliance has retained repositioning forces (i.e., the repositioning forces after the orthodontic appliance is applied to or worn by the patient for a period of time), and the retained repositioning force on at least one of the patient's teeth after that 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 forces initially applied to at least one of the patient's teeth (i.e., when the orthodontic appliance was first applied). In some implementations, the time 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 more than 4 weeks. In some implementations, the repositioning force applied to at least one tooth of the patient exists for a period of less than 24 hours, about 24 hours to about 2 months, about 24 hours to about 1 month, about 24 hours to about 3 weeks, about 24 hours to about 14 days, about 24 hours to about 7 days, about 24 hours to about 3 days, about 3 days to about 2 months, about 3 days to about 1 month, about 3 days to about 3 weeks, about 3 days to about 14 days, about 3 days to about 7 days, about 7 days to about 2 months, about 7 days to about 1 month, about 7 days to about 3 weeks, about 7 days to about 2 weeks, or more than 2 months. In some implementations, the repositioning force applied to at least one tooth of the patient exists for a period of about 24 hours, about 3 days, about 7 days, about 14 days, about 2 months, or more than 2 months.

[0348] In some embodiments, the orthodontic appliances disclosed herein can provide tracked movement of at least one tooth of a patient. Tracked movement has been further described herein, for example, in Table 1. In some embodiments, the orthodontic appliances disclosed herein can be used to achieve tracked movement of at least one tooth of a patient toward intermediate tooth alignment. In some embodiments, the orthodontic appliances disclosed herein can be used to achieve tracked movement of at least one tooth of a patient toward final tooth alignment.

[0349] In some embodiments, before using an orthodontic appliance to move at least one of a patient's teeth toward a central or final alignment, the orthodontic appliance has features that are retained after use. In some embodiments, the orthodontic appliance includes a first flexural modulus before the movement step. In some embodiments, the orthodontic appliance includes a second flexural modulus after the movement step. 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 embodiments, the second flexural modulus is greater than 50% of the first flexural modulus. In some embodiments, the comparison is performed after a period of time following the application of the appliance. In some implementation schemes, the time 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 more than 4 weeks.

[0350] In some embodiments, the orthodontic appliance includes a first elongation at break before the migration step. In some embodiments, the orthodontic appliance includes a second elongation at break after the migration step. 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, the comparison is performed after a period of time following the application of the appliance. In some embodiments, this 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 more than 4 weeks.

[0351] As provided herein, the disclosed methods can be used with orthodontic appliances further disclosed herein. Orthodontic appliances can be directly manufactured using, for example, light-curable resins disclosed herein.

[0352] Appliances formed from the light-curable resins disclosed herein offer improved durability, strength, and flexibility, which in turn increases the speed of planned progress in treatment. In some embodiments, patients treated with more than 60%, 70%, 80%, 90%, or 95% of the orthodontic appliances (e.g., braces) disclosed herein are classified as progressing on track at each treatment phase. In some embodiments, among patients treated with more than 60%, 70%, 80%, 90%, or 95% of the orthodontic appliances (e.g., braces) disclosed herein, tooth movement of more than 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% is classified as progressing on track.

[0353] In some embodiments, the cured polymer composition may have increased damage resistance, be more durable, and have reduced water absorption compared to similar polymer compositions. The cured polymer composition can be used in devices within the orthodontic field, as well as in devices outside of orthodontics. For example, the cured polymer compositions disclosed herein can be used to manufacture devices for aerospace applications, automotive manufacturing, prototyping, and / or for the production of durable parts.

[0354] Experimental methods

[0355] Unless otherwise stated, all chemicals were purchased from commercial sources and used without further purification.

[0356] Record on a BRUKER AC-E-200 FT-NMR spectrometer or a BRUKER Avance DRX-400 FT-NMR spectrometer 1 H NMR and 13 C10 NMR spectra. Chemical shifts are reported in ppm (s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet). The solvents used were deuterated chloroform (CDCl3, 99.5% deuterated) and deuterated DMSO (d6-DMSO, 99.8% deuterated).

[0357] In some embodiments, stress relaxation of a material or device can be measured by monitoring time-related stress caused by steady-state strain. The degree of stress relaxation can also depend on temperature, relative humidity, and other applicable conditions (e.g., the presence of water). In some 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.

[0358] The dynamic viscosity of a fluid indicates its resistance to shear flow. The SI unit for dynamic viscosity is poiseuille (Pa·s). Dynamic viscosity is usually given in centipoise, where 1 centipoise (cP) equals 1 mPa·s. Kinematic viscosity is the ratio of dynamic viscosity to fluid density; the SI unit is m³ / s. 2 / s. Devices used to measure viscosity include viscometers and rheometers. For example, the Anton Paar MCR 301 rheometer can be used for rheological measurements in rotational mode (PP-25, 50 s⁻¹, 50-115°C, 3°C / min).

[0359] Determining the water content at full saturation at the operating temperature may include exposing the polymer composition to 100% humidity for 24 hours at the operating temperature (e.g., 40°C) and then determining the water content by methods known in the art, such as by weight.

[0360] The material properties of cured polymer compositions can be determined using the following methods: Stress relaxation properties can be evaluated according to ASTM D790 using the TA Instruments RSA-G2 instrument with three-point bending; for example, stress relaxation can be measured at 30°C and immersed in water, and reported as the remaining load after 24 hours, as a percentage (%) of the initial load and / or in MPa. The energy storage modulus can be measured at 37°C and reported in MPa. T of cured polymer composition g The dynamic mechanical analysis (DMA) can be used for evaluation, and is presented in this paper as a tanδ peak; Tensile modulus, tensile strength, yield elongation and elongation at break can be evaluated according to ISO 527-2 5B; and yield tensile strength, elongation at break, tensile strength and Young's modulus can be evaluated according to ASTM D1708.

[0361] The additive manufacturing or 3D printing method used to generate the apparatus (e.g., orthodontic appliances) described herein can be performed using a thermolithography apparatus prototype from Cubicure (Vienna, Austria). In this case, a photocurable resin (e.g., resin) according to the present disclosure can be filled into a transparent material urn of the apparatus and heated to 90-110°C. The build platform can also be heated to 90-110°C and lowered to establish full contact with the upper surface of the curable composition. The composition can be cured layer by layer by a photopolymerization process according to the present disclosure by irradiating the composition with 375 nm UV radiation using a diode laser from Soliton (which can have an output power of 70 mW, can be controlled to track a predetermined prototyping design, and alternately raise the build platform).

[0362] To synthesize the block copolymers disclosed herein, hydroxyaryl compounds (e.g., 2,6-dimethoxyphenol) are functionalized with acrylates or methacrylates, thereby providing a means for controlled radical block copolymerization with alkyl acrylates (e.g., n-butyl acrylate). Monomers are added sequentially during polymerization to produce multiblock copolymers (e.g., diblock, triblock, etc.), depending on the initiator structure (see, for example, reaction schemes 1 and 2).

[0363] Reaction Scheme 1 - Synthesis of AB-Diblock Copolymer

[0364] Where R 1 R 2 R 3 n1 and n2 are as disclosed in this document.

[0365] Reaction Scheme 2 - Synthesis of ABA-Triblock Copolymer

[0366] Where R 1 R 2 n1, n2, n3 and n4 are as disclosed herein.

[0367] If the block copolymer contains hydroxyl functional groups at the ends of the blocks (either by selecting a hydroxyl-functionalized initiator or by introducing a few equivalents of hydroxyl-functionalized monomer at the end of the polymerization reaction), they can be modified with one or more methacrylates after polymerization to obtain a reactive block copolymer (see, for example, reaction scheme 3).

[0368] Reaction Scheme 3 - Post-functionalization of hydroxyl-terminated AB-diblock polymers with methacrylate terminal groups

[0369] Where R 1 R 2 n1 and n2 are as disclosed in this document.

[0370] Conversely, these reactive or functionalized block copolymers can covalently bond with the rest of the photopolymer network.

[0371] Example

[0372] The following examples are given to illustrate various embodiments of the invention and are not intended to limit this disclosure in any way. These examples and the methods described herein represent some embodiments and are exemplary, and are not intended to limit the scope of the invention. Variations and other uses within the spirit of the invention as defined by the claims will be apparent to those skilled in the art.

[0373] Example 1

[0374] Synthesis of 2,6-dimethoxyphenyl acrylate

[0375] In a 1 L round-bottom flask equipped with a magnetic stir bar, 2,6-dimethoxyphenol (50 g, 0.324 mol, 1 equivalent) was dissolved in dichloromethane (324 mL). Triethylamine (67.8 mL, 0.489 mol, 1.5 equivalent) was then added to the flask, and the reaction mixture was cooled in an ice-water bath. Acryloyl chloride (31.6 mL, 0.389 mol, 1.2 equivalent) was added dropwise. Gas release was observed. The reaction mixture was stirred overnight at room temperature. Water (300 mL) was then added, and the layers separated. The organic layer was washed again with water (300 mL) and then concentrated under vacuum. The crude material was purified by rapid silica gel column chromatography, eluting with a hexane solution of 15% to 25% ethyl acetate to give the desired product (60 g, 95% yield) as a clear, colorless liquid.

[0376] Example 2

[0377] Synthesis of poly(n-butyl acrylate) monofunctional macromolecular initiator

[0378] Add butyl acrylate (22.1 g, 154 mmol, 100 equivalents), ethyl α-bromoisobutyrate (300 mg, 1.54 mmol, 1 equivalent), N,N,N',N”,N”-pentamethyldiethylenetriamine (321 µL, 1.54 mmol, 1 equivalent), and anisole (2 mL) to a 100 mL Schlenk tube equipped with a magnetic stir bar. Seal the tube with a diaphragm and purge the contents with nitrogen for 30 minutes. Then, under positive nitrogen pressure, add copper(I) bromide (221 mg, 1.54 mmol, 1 equivalent). Stir the reaction mixture for 5 minutes and then transfer it to an oil bath at 70 °C to begin polymerization. Polymerization is carried out by periodically removing aliquots from the reaction mixture. 1 ¹H NMR analysis was used to monitor the reaction progress. Finally, after 2 hours, the flask was moved to an ice-water bath and opened to air to stop the polymerization.

[0379] Example 3

[0380] Synthesis of poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate)

[0381] Poly(n-butyl acrylate) (Example 2, 6.25 g, 0.481 mmol, 1 equivalent), 2,6-dimethoxyphenyl acrylate (Example 1, 10 g, 48.1 mmol, 100 equivalent), N,N,N',N”,N”-pentamethyldiethylenetriamine (50 µL, 0.24 mmol, 0.5 equivalent), and anisole (10 mL) were added to a 100 mL Schlenk tube equipped with a magnetic stir bar. The tube was sealed with a diaphragm, and the contents were purged with nitrogen for 30 minutes. Then, copper(I) bromide (34.5 mg, 0.240 mmol, 0.5 equivalent) was added to the container under positive nitrogen pressure. The reaction mixture was transferred to an oil bath at 80°C to begin polymerization. Polymerization was carried out by periodically measuring aliquots taken from the reaction mixture. 1 ¹H NMR analysis was used to monitor the reaction progress. Finally, the reaction flask was moved to an ice-water bath and opened to air to stop the polymerization. The mixture was dissolved in dichloromethane at room temperature, passed through neutral alumina, and precipitated twice in methanol to give poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate).

[0382] The following was verified using gel permeation chromatography (GPC): after chain elongation with 2,6-dimethoxyphenyl acrylate, the macromolecular initiator (the desired product in Example 2; the starting material) was elongated to form the desired product poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate).

[0383] Example 4

[0384] Synthesis of poly(n-butyl acrylate) bifunctional macromolecular initiator

[0385] To a 100 mL Schlenk tube equipped with a magnetic stir bar, add n-butyl acrylate (18.7 g, 146 mmol, 70 equivalents), ethane-1,2-dimethylbis(2-bromo-2-methylpropionate) (750 mg, 2.08 mmol, 1 equivalent), N,N,N',N”,N”-pentamethyldiethylenetriamine (218 μL, 1.04 mmol, 0.5 equivalents), and anisole (2 mL). Seal the tube with a diaphragm and purge the contents with nitrogen for 30 minutes. Then, under positive nitrogen pressure, add copper(I) bromide (149 mg, 1.04 mmol, 0.5 equivalents). Stir the reaction mixture for 5 minutes and then transfer it to an oil bath at 80 °C to begin polymerization. Polymerization is achieved by periodically measuring aliquots taken from the reaction mixture. 1 ¹H NMR analysis was used to monitor the reaction progress. Finally, after 19 hours, the flask was moved to an ice-water bath and exposed to air to stop the polymerization.

[0386] Example 5

[0387] Synthesis of poly(2,6-dimethoxyphenyl acrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate)

[0388] Poly(n-butyl acrylate) (1.27 g, 0.096 mmol, 1 equivalent), 2,6-dimethoxyphenyl acrylate (Example 1, 2.00 g, 9.62 mmol, 100 equivalent), N,N,N',N'”,N”-pentamethyldiethylenetriamine (10.0 µL, 0.048 mmol, 0.5 equivalent), and anisole (2 mL) were added to a 25 mL Schlenk tube equipped with a magnetic stir bar. The tube was sealed with a diaphragm, and the contents were purged with nitrogen for 30 minutes. Then, copper(I) bromide (6.90 mg, 0.048 mmol, 0.5 equivalent) was added to the container under positive nitrogen pressure. The reaction mixture was transferred to an oil bath at 80°C to begin polymerization. Polymerization was carried out by periodically measuring aliquots taken from the reaction mixture. 1¹H NMR analysis was used to monitor the reaction progress. Finally, the reaction flask was moved to an ice-water bath and opened to air to stop the polymerization. The mixture was dissolved in dichloromethane at room temperature, passed through neutral alumina, and precipitated twice in methanol to give poly(2,6-dimethoxyphenyl acrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate).

[0389] The following was verified using gel permeation chromatography (GPC): After chain elongation with 2,6-dimethoxyphenyl acrylate, the macromolecular initiator (the desired product in Example 4; the starting material) was elongated to form the desired product poly(2,6-dimethoxyphenyl acrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate).

[0390] Example 6

[0391] Synthesis of poly(2,6-dimethoxyphenyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl methacrylate)

[0392] Poly(n-butyl acrylate) (2.00 g, 0.235 mmol, 1 equivalent), 2,6-dimethoxyphenyl methacrylate (2.09 g, 9.41 mmol, 40 equivalent), N,N,N',N',N'-pentamethyldiethylenetriamine (197 µL, 0.941 mmol, 4 equivalent), and anisole (4 mL) were added to a 100-mL Schlenk tube equipped with a magnetic stir bar. The tube was sealed with a diaphragm, and the contents were purged with nitrogen for 30 minutes. Then, copper(I) chloride (46.6 mg, 0.471 mmol, 2 equivalent) was added to the container under positive nitrogen pressure. The reaction mixture was transferred to an oil bath at 80°C to begin polymerization. Polymerization was carried out by periodically measuring aliquots taken from the reaction mixture. 1 ¹H NMR analysis was used to monitor the reaction progress. Finally, the reaction flask was moved to an ice-water bath and opened to air to stop the polymerization. The mixture was dissolved in dichloromethane at room temperature, passed through neutral alumina, and precipitated twice in methanol to give poly(2,6-dimethoxyphenyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl methacrylate).

[0393] The following was verified using gel permeation chromatography (GPC): after chain elongation with 2,6-dimethoxyphenyl methacrylate, the macromolecular initiator (the desired product in Example 4; the starting material) was elongated to form the desired product poly(2,6-dimethoxyphenyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl methacrylate).

[0394] Example 7

[0395] Analysis of polymer compositions

[0396] DSC thermal analysis plots of poly(2,6-dimethoxyphenyl acrylate) were obtained. When the temperature was plotted against the (normalized) heat flow (W / g), a glass transition temperature (Tg) close to 127 °C was observed. g ).

[0397] DSC thermal analysis plots of poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate) were also obtained. When temperature was plotted against (normalized) heat flux (W / g), a glass transition temperature (Tg) close to -49 °C was observed for the poly(n-butyl acrylate) block. g ), while for poly(2,6-dimethoxyphenyl acrylate) blocks, a T value close to 134°C was observed. g .

[0398] Example 8

[0399] Polymer materials prepared using 5 wt% self-assembled block copolymers

[0400] Adding 5 wt% of a diblock or triblock copolymer containing poly(2,6-dimethoxyphenyl acrylate) to the base formulation resulted in a decrease in elongation at break. Replacing the triblock poly(2,6-dimethoxyphenyl acrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl acrylate) with a sufficiently high molecular weight poly(2,6-dimethoxyphenyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(2,6-dimethoxyphenyl methacrylate) resulted in higher elongation at break, and a slightly lower tensile modulus and final flexural modulus.

[0401] Figure 7This is a flowchart providing a general overview of a method 700 for manufacturing and post-processing additively manufactured objects according to embodiments of the present technology. Method 700 can be used to produce a variety of different types of additively manufactured objects, such as orthodontic appliances (e.g., braces, palatal expanders, attachments, attachment templates, retainers), restorative objects (e.g., crowns, veneers, implants), and / or other dental appliances (e.g., oral sleep apnea appliances, oral protectors). Further examples of orthodontic appliances and related methods applicable to the present technology are described below.

[0402] Method 700 begins with module 702, producing an additively manufactured object. Any suitable additive manufacturing technique known to those skilled in the art can be used to produce the additively manufactured object. Additive manufacturing (also referred to herein as “3D printing”) encompasses a variety of techniques for creating 3D objects directly from digital models using additive processes. In some embodiments, additive manufacturing involves depositing a precursor material (e.g., a photopolymerizable resin) onto a build platform. The precursor material may be cured, polymerized, melted, sintered, fused, and / or otherwise solidified to form a portion of an object and / or combine that portion with previously formed portions of the object. In some embodiments, the additive manufacturing techniques provided herein build the object geometry in a layer-by-layer manner, wherein successive layers are formed in discrete build steps. Alternatively or in combination, the additive manufacturing techniques described herein may allow for the continuous construction of the object geometry.

[0403] Examples of additive manufacturing techniques applicable to the methods described herein include, but are not limited to, the following: (1) urn photopolymerization, in which an object is constructed layer by layer from a urn of liquid photopolymer resin, including techniques such as stereolithography (SLA), digital light processing (DLP), continuous liquid interface production (CLIP), two-photon induced photopolymerization (TPIP), and volumetric additive manufacturing; (2) material jetting, in which material is jetted onto a build platform using a continuous or drop-on-demand (DOD) method; and (3) binder jetting, in which alternating layers of build material (e.g., powder-based material) and binder material (e.g., liquid binder) are deposited by a printhead. (4) Fused deposition modeling (FDM), in which materials are stretched, heated and deposited layer by layer through a nozzle, and direct ink writing (DIW); (5) Powder bed fusion, including direct metal laser sintering (DMLS), electron beam melting (EBM), selective thermal sintering (SHS), selective laser melting (SLM) and selective laser sintering (SLS); (6) Thin sheet lamination, including layered solid manufacturing (LOM) and ultrasonic additive manufacturing (UAM); and (7) Directional energy deposition, including laser engineered net forming, directional light manufacturing, direct metal deposition and 3D laser cladding.

[0404] For example, urn photopolymerization can be used to manufacture additively manufactured objects, where light is used to selectively cure a curable material (e.g., a polymer resin) in an urn or reservoir. Each layer of the curable material can be selectively exposed to light in a single exposure (e.g., DLP) or by scanning a beam of light through the layers (e.g., SLA). Urn polymerization can be performed in a "top-down" or "bottom-up" manner, depending on the relative positions of the urn, the light source, and the build platform.

[0405] For example, high-temperature lithography (also known as "thermal lithography") can be used to manufacture additively manufactured objects. High-temperature lithography can include any photopolymerization process involving heating a photopolymerizable material (e.g., a polymer resin). For example, high-temperature lithography can involve heating the material to temperatures of at least 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C. In some embodiments, the material is heated to temperatures in the ranges of 50°C to 120°C, 90°C to 120°C, 100°C to 120°C, 105°C to 115°C, or 108°C or 110°C. Heating can reduce the viscosity of the photopolymerizable material before and / or during curing. Therefore, high-temperature lithography can be used to manufacture objects from materials with high viscosity and / or poor flowability, which may exhibit better mechanical properties (e.g., stiffness, strength, stability) upon curing compared to other types of materials. For example, high-temperature lithography can be used to manufacture objects from materials with a viscosity of at least 5 Pa⁻¹, 10 Pa⁻¹, 15 Pa⁻¹, 20 Pa⁻¹, 30 Pa⁻¹, 40 Pa⁻¹, or 50 Pa⁻¹ at 20 °C. Representative examples of high-temperature lithography processes that can be incorporated into the methods herein are described in international publications WO 2015 / 075094, WO 2016 / 078838, WO 2018 / 032022, WO 2020 / 070639, WO 2021 / 130657, and WO 2021 / 130661, the contents of which are incorporated herein by reference in their entirety.

[0406] In another example, selective laser sintering (SLS) can be used to manufacture additively manufactured objects. This process involves selectively melting and fusing layers of powder material using a laser beam according to a desired cross-sectional shape to construct the object's geometry. As another example, fused deposition modeling (FDM) can be used to manufacture additively manufactured objects. This process involves melting and selectively depositing filaments of thermoplastic polymers in a layer-by-layer manner to form the object. In yet another example, material jetting can be used to manufacture additively manufactured objects. This process involves jetting or extruding one or more materials onto a build surface to form continuous layers of the object's geometry.

[0407] In some embodiments, continuous liquid interface production (also known as “continuous liquid interface printing”) is used to manufacture additively manufactured objects, wherein the object is continuously constructed from a reservoir of photopolymerizable resin by forming a gradient of partially cured resin between the build surface of the object and a polymerization inhibition “dead zone.” In some embodiments, a semi-permeable membrane is used to control the transport of photopolymerization inhibitors (e.g., oxygen) into the dead zone to form a polymerization gradient. Representative examples of continuous liquid interface production processes that may be incorporated into the methods herein are described in U.S. Patent Publications 2015 / 0097315, 2015 / 0097316, and 2015 / 0102532, the disclosures of which are incorporated herein by reference in their entirety.

[0408] As another example, continuous additive manufacturing methods can achieve continuous construction of object geometry by continuously moving the build platform during the irradiation phase (e.g., along the longitudinal or Z-direction), such that the curing depth of the irradiated photopolymer is controlled by the movement speed. Therefore, continuous polymerization of the material can be achieved on the build surface. Such a method is described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety. In another example, continuous additive manufacturing methods can include extruding a composite material consisting of a curable liquid material surrounding a solid strand. The composite material can be extruded along a continuous three-dimensional path to form an object. This method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety. In yet another example, continuous additive manufacturing methods can utilize a "heliolithography" method, in which a liquid photopolymer is cured using focused radiation while the build platform is continuously rotated and raised. Therefore, object geometry can be continuously constructed along a helical build path. This method is described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety.

[0409] In another example, volumetric additive manufacturing (VAM) processes can be used to fabricate additively manufactured objects, where the entire object is produced from a 3D volume of resin in a single printing step, without layer-by-layer construction. During VAM, the entire build volume is irradiated with energy, but the projected pattern is configured such that only certain voxels accumulate a sufficient dose of energy for curing. Representative examples of VAM processes that can be incorporated into this technology include tomographic volumetric printing, holographic volumetric printing, multiphoton volumetric printing, and xolography. For example, tomographic VAM can be performed by projecting a 2D optical pattern at perpendicular and / or angular incidence onto a rotating volume of photosensitive material to produce a cured 3D structure. Holographic VAM can be performed by projecting overlapping light patterns onto a stationary reservoir of photosensitive material. Xolography processes can use photoinitiators to linearly excite the material by intersecting beams of different wavelengths, initiating localized polymerization within the photosensitive material volume. Further details of the VAM process applicable to this technology are described in U.S. Patent No. 11,370,173, U.S. Patent Publication No. 2021 / 0146619, U.S. Patent Publication No. 2022 / 0227051, International Publication No. WO 2017 / 115076, International Publication No. WO 2020 / 245456, International Publication No. WO 2022 / 011456 and U.S. Provisional Patent Application No. 63 / 181,645, the disclosures of which are incorporated herein by reference in their entirety.

[0410] Additively manufactured objects can be made from any suitable material or combination of materials. As discussed above, in some embodiments, additively manufactured objects are made partly or entirely of a polymeric material (e.g., a curable polymeric resin). The resin may consist of one or more monomeric components that are initially in a liquid state. The resin may be in a liquid state at room temperature (e.g., 20°C) or at elevated temperatures (e.g., temperatures in the range of 50°C to 120°C). When exposed to energy (e.g., light), the monomeric components may undergo a polymerization reaction, causing the resin to solidify into the desired object geometry. Representative examples of curable polymeric resins and other materials suitable for use with the additive manufacturing techniques described herein are described in International Publications WO 2019 / 006409, WO 2020 / 070639 and WO 2021 / 087061, the disclosures of which are incorporated herein by reference in their entirety.

[0411] Optionally, additively manufactured objects can be made from a variety of different materials (e.g., at least two, three, four, five, or more different materials). These materials may differ from one another in composition, curing conditions (e.g., curing energy wavelength), pre-curing material properties (e.g., viscosity), and post-curing material properties (e.g., stiffness, strength, transparency). In some embodiments, additively manufactured objects are formed from multiple materials in a single manufacturing step. For example, multiple types of materials can be selectively dispensed from different material supply sources using a multi-head extruder to manufacture objects from multiple different materials. Examples of this method are described in U.S. Patent Nos. 6,749,414 and 11,318,667, the disclosure of which is incorporated herein by reference in its entirety. Alternatively or in combination, additively manufactured objects can be formed from multiple materials in multiple successive manufacturing steps. For example, according to any method herein, a first portion of the object may be formed from a first material, then according to the method herein, a second portion of the object may be formed from a second material, and so on, until the entire object has been formed.

[0412] After an additively manufactured object is produced, it may undergo one or more additional process steps, referred to herein as “post-processing.” As described in detail below with respect to modules 704-712, post-processing may include removing excess material from the object, applying additional material to the object, performing additional curing, separating the object from any supports or other structures not intended to appear in the final product, and / or collecting the removed excess material for reuse.

[0413] For example, at module 704, method 700 continues, wherein excess material is removed from the additively manufactured object. Excess material may include uncured material (e.g., unpolymerized liquid resin) and / or other unwanted material (e.g., debris) remaining on the additively manufactured object after manufacturing. For example, certain materials used in additive manufacturing (e.g., high-viscosity polymer resins used in high-temperature lithography) may adhere to the surface of the additively manufactured object. Furthermore, excess material may accumulate in certain object features (e.g., cavities, cracks, dents, openings, etc.). Therefore, the additively manufactured object may require cleaning before further processing and use.

[0414] Excess material can be removed in a variety of ways. For example, in some embodiments, excess material is removed by centrifugally separating it from the surface of the additively manufactured object by rotating it. The rotation can be performed using suitable apparatus or systems (e.g., centrifuges) that include components for supporting the additively manufactured object and applying rotational forces thereto. Alternatively or in combination, excess material can be removed by spraying or otherwise applying fluids (e.g., water, solvents) to the object, partially or completely immersing the object in a fluid, blowing gas (e.g., air) onto the object, applying a vacuum to the object, applying other types of mechanical forces (e.g., vibration, agitation, tumbling, brushing) to the object, and / or other cleaning techniques known to those skilled in the art.

[0415] At module 706, method 700 may optionally include curing the additively manufactured object. This additional curing step (also referred to as “post-curing”) can be used when the additively manufactured object is still in a partially cured “green” state after manufacturing. For example, the curing energy used in module 702 to manufacture the additively manufactured object may only partially polymerize the resin forming the object. Therefore, a post-curing step may be needed to fully cure (e.g., fully polymerize) the additively manufactured object to its final usable state. Post-curing can provide various benefits, such as improved mechanical properties of the additively manufactured object (e.g., stiffness, strength) and / or temperature stability. Post-curing can be performed by heating the object, applying radiation to the object (e.g., ultraviolet (UV), visible light, microwaves), or a suitable combination thereof. Post-curing can be performed by a dedicated device (e.g., an oven or curing station) or by the same device used in module 604 to rotate the additively manufactured object. However, in other embodiments, the post-curing process of module 606 is optional and may be omitted.

[0416] At module 708, method 700 may optionally include applying additional material to the additively manufactured object. For example, the additional material may be a coating, such as a polymer coating. The coating may be applied to one or more surfaces of the object for a variety of purposes, including but not limited to: providing a smooth final surface, which may be aesthetically pleasing and / or enhance user comfort if the object is intended to come into contact with a user's body (e.g., an orthodontic appliance worn on teeth); coloring the object and / or applying other aesthetic features; improving scratch resistance and / or other mechanical properties; providing antibacterial properties; and incorporating therapeutic agents into the object for controlled release.

[0417] At module 710, method 700 may include separating the additively manufactured object from the substrate. In some embodiments, the substrate is a build platform that mechanically supports the object during the manufacturing and post-processing steps described herein. The additively manufactured object can be attached to the substrate via sacrificial regions of cured material. Therefore, the sacrificial regions can be broken by applying pressure, thereby separating the additively manufactured object from the substrate. Once separated, the additively manufactured object is ready for packaging, shipping, and use.

[0418] At module 712, method 700 may optionally include collecting excess material removed from the additively manufactured object in module 704. The excess material may include uncured material that is still suitable for reuse in subsequent additive manufacturing processes (e.g., the manufacturing process of module 702). Therefore, module 712 may include collecting the excess material (e.g., through a container, absorbent element, pipe, etc.) and optionally separating the reusable excess material from any other unwanted components (e.g., water, solvents, debris) that may be present, by means of filtration, distillation, centrifugation, and / or other suitable techniques.

[0419] Method 700 can be modified in various ways. For example, although the steps of method 700 described above are for a single additively manufactured object, method 700 can be used to simultaneously manufacture and post-process any suitable number of additively manufactured objects, such as dozens, hundreds, or thousands of additively manufactured objects. As another example, Figure 7 The order of the steps shown can be changed; for example, the material application process of module 708 can be performed before the curing process of module 706. Some steps of method 700, such as any of modules 706, 708, and / or 712, can be omitted. Method 700 may also include Figure 7 Additional steps not shown in the diagram.

[0420] Figure 8 A representative example of an additive manufacturing apparatus 800 (“Apparatus 800”) configured according to an embodiment of the present technology is shown. Apparatus 800 can be used to manufacture any embodiment of the additively manufactured objects described herein. For example, Apparatus 800 can be used according to… Figure 7 Method 700, module 702, produces additively manufactured objects.

[0421] like Figure 8As shown, apparatus 800 is used to manufacture an additively manufactured object 802 (“object 802”). Apparatus 800 includes a printer assembly 804 configured to deposit resin 806 onto a build platform 808 (e.g., a tray, plate, film, sheet, or other planar substrate) to form object 802. Printer assembly 804 includes a carrier film 810 configured to deliver resin 806 to build platform 808. Carrier film 810 may be a flexible material ring having an outer surface and an inner surface. The outer surface of carrier film 810 may adhere to and carry a thin layer of resin 806. The inner surface of carrier film 810 may contact one or more rollers 812, which rotate to move carrier film 810 along a continuous loop trajectory, for example, as indicated by arrow 814.

[0422] The printer assembly 804 may also include a resin source 816 (schematically shown) configured to apply resin 806 to the carrier film 810. In the illustrated embodiment, the resin source 816 is located in the upper part of the printer assembly 804, near the upper horizontal section of the carrier film 810. However, in other embodiments, the resin source 816 may be located at different locations within the printer assembly 804. The resin source 816 may include nozzles, ports, reservoirs, etc., which deposit resin 806 onto the outer surface of the carrier film 810. The resin source 816 may also include one or more blades (e.g., a doctor blade, a recoating blade) for smoothing the deposited resin 806 into a relatively thin, uniform layer. In some embodiments, the resin 806 is formed as a layer with a thickness in the range of 200 micrometers to 300 micrometers.

[0423] Resin 806 can be carried to build platform 808 by carrier film 810. In the illustrated embodiment, build platform 808 is located below printer assembly 804, near the lower horizontal segment of carrier film 810. However, in other embodiments, build platform 808 may be located at a different position relative to printer assembly 804. Printer assembly 804 includes light source 818 (e.g., projector or light engine) that outputs light 820 (e.g., UV light) having a wavelength configured to partially or completely cure resin 806. Carrier film 810 may be optically transparent, such that light 820 from light source 818 passes through carrier film 810 and irradiates a portion of resin 806 above build platform 808, thereby forming a layer of cured resin 806 on build platform 808 and / or a previously formed portion of object 802. Light 820 may be patterned or scanned according to a suitable pattern corresponding to the desired cross-sectional geometry of object 802. Optionally, a transparent plate 822 may be provided between the light source 818 and the carrier film 810 to guide the carrier film 810 to a specific position (e.g., height) relative to the construction platform 808.

[0424] Once the cross-section of the object is formed, the build platform 808 can be reduced by a predetermined amount to separate the cured resin from the carrier film 810. The remaining uncured resin 806 can be carried away from the build platform 808 by the carrier film 810 and returned to the resin source 816. The resin source 816 can deposit additional resin 806 onto the carrier film 810 and / or smooth the resin 806 to reform a uniform layer of resin 806 on the carrier film 810. The resin 806 can then be recycled back to the build platform 808 to create additional layers of the object 802. This process can be repeated to iteratively build individual object layers on the build platform 808 until the object 802 is complete. The object 802 and the build platform 808 can then be removed from the apparatus 800 for post-processing.

[0425] In some embodiments, apparatus 800 is used for high-temperature photolithography processes utilizing high-viscosity resins. Therefore, printer assembly 804 may include one or more heat sources (heating plates, infrared lamps, etc.) for heating resin 806 to reduce its viscosity to a range suitable for additive manufacturing. For example, printer assembly 804 may include a first heat source 824a positioned prior to build platform 808 and a second heat source 824b positioned prior to build platform 808 and the carrier film 810. Alternatively or in combination, printer assembly 804 may include heat sources located at other locations.

[0426] The apparatus 800 also includes a controller 826 (schematically shown) operatively coupled to the printer assembly 804 and the build platform 808 to control their operation. The controller 826 may be or include a computing device including one or more processors and a memory storing instructions for performing the additive manufacturing operations described herein. For example, the controller 826 may receive a digital 3D model of an object 802 to be manufactured, determine multiple object cross-sections to build the object 802 from resin 806, and may send instructions to a light source 818 to output light 820 to form the object cross-sections. As another example, the controller 826 may also determine and control other operating parameters, such as the positioning (e.g., height) of the build platform 808 relative to the carrier film 810, the speed and direction of movement of the carrier film 810, the amount of resin 806 deposited, the thickness of the resin layer on the carrier film 810, and / or the amount of heat applied to the resin 806.

[0427] although Figure 8 A representative example of an additive manufacturing apparatus is shown, but this is not intended to limit it, and the embodiments described herein can be used in combination with other types of additive manufacturing apparatus (e.g., urn-based systems) and / or other types of additive manufacturing processes (e.g., material jetting, binder jetting, FDM, powder bed melting, sheet lamination, directional energy deposition).

[0428] Figure 9 A method 900 for designing orthodontic appliances according to some embodiments of the present technology is illustrated. Method 900 can be applied to any embodiment of the orthodontic appliances described herein. Some or all of the steps of method 900 can be performed by any suitable data processing system or device (e.g., one or more processors configured with suitable instructions).

[0429] In module 910, a movement path is determined to move one or more teeth from an initial alignment to a target alignment. The initial alignment can be determined by a mold or scan of the patient's teeth or oral tissues, for example, using wax bite method, direct contact scanning, X-ray imaging, tomography, ultrasound imaging, and other techniques for acquiring information about the location and structure of teeth, jawbone, gingiva, and other orthodontic-related tissues. From the obtained data, a digital dataset representing the initial (e.g., pre-treatment) alignment of the patient's teeth and other tissues can be derived. Optionally, the initial digital dataset is processed to segment the tissue components to each other. For example, a data structure digitally representing a single tooth crown can be generated. Advantageously, a digital model of the entire tooth can be generated, including the measured or extrapolated hidden surfaces and root structures, as well as the surrounding bone and soft tissues.

[0430] The target alignment of teeth (e.g., the expected and anticipated outcome of orthodontic treatment) can be received from the clinician in the form of a prescription, calculated based on fundamental orthodontic principles, and / or inferred from the clinical prescription through calculation. By specifying the expected final position of the teeth and a digital representation of the teeth themselves, the final position and surface geometry of each tooth can be designated to form a complete model of the expected tooth alignment at the end of treatment.

[0431] After obtaining the initial and target positions for each tooth, a movement path can be defined for the movement of each tooth. In some implementations, the movement path is configured to move the tooth from its initial position to its desired target position in the fastest manner with the fewest round trips. Optionally, the tooth path can be segmented, and the segments can be calculated such that the movement of each tooth within a segment remains within threshold limits of linearity and rotational translation. In this way, the endpoints of each path segment can constitute a clinically feasible repositioning, and the set of segment endpoints can constitute a clinically feasible sequence of tooth positions such that moving from one point to the next in the sequence does not result in tooth collision.

[0432] In Module 920, the force system that produces movement of one or more teeth along the movement path is determined. The force system may include one or more forces and / or one or more torques. Different force systems result in different types of tooth movement, such as tilting, translation, rotation, squeezing, intrusion, root movement, etc. Biomechanical principles, modeling techniques, force calculation / measurement techniques, and other knowledge and methods commonly used in orthodontics can be used to determine the appropriate force system to be applied to the teeth to achieve tooth movement. Sources that may be considered when determining the force system to be applied include literature, force systems determined through experimental or virtual modeling, computer-based modeling, clinical experience, minimizing unwanted forces, etc.

[0433] Determining the force system can include constraints on permissible forces, such as permissible direction and magnitude, and the desired movement induced by the applied forces. For example, different movement strategies may be desired for different patients when fabricating a palatal expander. For instance, the amount of force required to separate the palate may depend on the patient's age, as the palatal sutures may not be fully formed in very young patients. Therefore, palatal expansion can be achieved with smaller forces in adolescent patients and other patients whose palatal sutures are not fully closed. Slower palatal movement also facilitates bone growth to fill the expanded palatal sutures. For other patients, faster expansion may be desired, which can be achieved by applying greater forces. These requirements can be combined as needed to select the structure and materials of the appliance; for example, by selecting a palatal expander capable of applying larger forces to disrupt the palatal sutures and / or cause rapid palatal expansion. Subsequent appliance stages can be designed to apply forces of varying magnitudes, such as initially applying larger forces to disrupt the palatal sutures, followed by smaller forces to maintain suture separation or gradually expand the palate and / or dental arch.

[0434] Determining the force system can also include modeling the patient's facial structures, such as the skeletal structure of the jaw and palate. For example, scan data of the palate and dental arch, such as X-ray data or 3D optical scan data, can be used to determine parameters of the patient's oral skeletal and muscular systems, thereby determining the force sufficient to provide the desired expansion of the palate and / or dental arch. In some implementations, the thickness and / or density of the palatal suture can be measured or input by a treatment professional. In other implementations, the treatment professional can select appropriate treatment based on the patient's physiological characteristics. For example, the nature of the palate can also be estimated based on factors such as the patient's age—for instance, younger adolescent patients typically require less force to expand the palatal suture than older patients because the suture has not yet fully formed.

[0435] In module 930, the design of an orthodontic appliance configured to generate a force system is determined. The design may include appliance geometry, material composition, and / or material properties, and may be determined in various ways, such as using a treatment or force application simulation environment. The simulation environment may include, for example, a computer modeling system, a biomechanical system, or a device. Optionally, a digital model of the appliance and / or teeth, such as a finite element model, may be generated. The finite element model can be created using computer program application software available from various vendors. To create a solid geometry model, computer-aided engineering (CAE) or computer-aided design (CAD) programs can be used, such as AutoCAD® software products offered by Autodesk, Inc., San Rafael, California. To create and analyze the finite element model, program products from multiple vendors can be used, including the finite element analysis software package from ANSYS, Inc., Fort Cannons, Pennsylvania, and the SIMULIA (Abaqus) software product from Dassault Systèmes, Waltham, Massachusetts.

[0436] Optionally, one or more designs can be selected for testing or force modeling. As described above, the desired tooth movement and the required or desired force system to induce the desired tooth movement can be identified. Using a simulation environment, candidate designs can be analyzed or modeled to determine the actual force system generated using the candidate apparatus. Optionally, one or more modifications can be made to the candidate apparatus, and force modeling can be further analyzed as described, for example, to iteratively determine the apparatus design that produces the desired force system.

[0437] In module 940, manufacturing instructions incorporating the designed orthodontic appliance are generated. These instructions can be configured to control a manufacturing system or apparatus to produce an orthodontic appliance with the specified design. In some embodiments, the instructions are configured to manufacture the orthodontic appliance using direct manufacturing methods (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct manufacturing, multimaterial direct manufacturing, etc.) according to the various methods presented herein. In alternative embodiments, the instructions can be configured to indirectly manufacture the appliance, for example, by thermoforming.

[0438] While the steps described above illustrate a method 900 for designing orthodontic appliances according to some embodiments, those skilled in the art will recognize variations based on the teachings herein. Some steps may include sub-steps. Some of these steps may be repeated as needed. One or more steps of method 900 may be performed using any suitable manufacturing system or apparatus (e.g., the embodiments described herein). Some steps may be optional, and the order of the steps may be changed as needed.

[0439] Figure 10Method 1000 for digitally planning orthodontic treatment and / or designing or manufacturing appliances is illustrated according to some embodiments. Method 1000 can be applied to any treatment procedure described herein and can be performed by any suitable data processing system.

[0440] In module 1010, a digital representation of the patient's teeth is received. The digital representation may include surface topographic data of the patient's oral cavity (including teeth, gingival tissue, etc.). The surface topographic data can be generated by directly scanning the oral cavity, a physical model (positive or negative) of the oral cavity, or an impression of the oral cavity using a suitable scanning device (e.g., a handheld scanner, a desktop scanner, etc.).

[0441] In module 1020, one or more treatment phases are generated based on the digital representation of the teeth. A treatment phase can be an incremental repositioning phase of an orthodontic treatment procedure designed to move one or more of a patient's teeth from an initial tooth alignment to a target alignment. For example, a treatment phase can be generated by determining the initial tooth alignment indicated by the digital representation, determining the target tooth alignment, and determining the movement path of one or more teeth in the initial alignment necessary to achieve the target tooth alignment. The movement path can be optimized based on minimizing the total distance of movement, preventing collisions between teeth, avoiding more difficult tooth movements, or any other suitable criteria.

[0442] In module 1030, at least one orthodontic appliance is manufactured based on the generated treatment phase. For example, a set of appliances can be manufactured, each shaped according to the tooth alignment specified in a treatment phase, allowing the patient to wear the appliances sequentially to incrementally reposition the teeth from the initial alignment to the target alignment. The appliance set may include one or more orthodontic appliances as described herein. Manufacturing the appliances may involve creating a digital model of the appliance for use as input to a computer-controlled manufacturing system. The appliances may be formed using direct manufacturing methods, indirect manufacturing methods, or a combination thereof, as needed.

[0443] In some cases, the staging of various arrangements or treatment phases may not be necessary for the design and / or manufacture of the device. For example... Figure 10 As shown by the dashed lines, the design and / or manufacture of orthodontic appliances and possible specific orthodontic treatments may include using a representation of the patient's teeth (e.g., including receiving a digital representation of the patient's teeth (module 1010)), and then designing and / or manufacturing the orthodontic appliance based on the representation of the patient's teeth in the arrangement represented by the received representation.

[0444] As noted herein, the techniques described herein can be used to directly manufacture dental appliances, such as orthodontic appliances and / or a series of appliances having tooth receiving cavities, configured to move a person's teeth from an initial alignment to a target alignment according to a treatment plan. The orthodontic appliance may include mandibular repositioning elements, such as those described in the following documents: U.S. Patent No. 10,912,629, filed November 30, 2015, entitled "Dental Appliance with Repositioning Mandibular Elements"; U.S. Patent No. 10,537,406, filed September 19, 2014, entitled "Dental Appliance with Repositioning Mandibular Elements"; and U.S. Patent No. 9,844,424, filed February 21, 2014, entitled "Dental Appliance with Repositioning Mandibular Elements"; all of which are incorporated herein by reference in their entirety.

[0445] The techniques used in this paper can also be used to manufacture attachment manufacturing templates, such as appliances for positioning prefabricated attachments on a person's teeth according to one or more aspects of a treatment plan. Examples of attachment manufacturing templates can be found in at least the following documents: U.S. Application Serial No. 17 / 249,218, entitled "Flexible 3D Printed Orthodontic Appliance," filed February 24, 2021; U.S. Application Serial No. 16 / 366,686, entitled "Dental Attachment Placement Structure," filed March 27, 2019; U.S. Application Serial No. 15 / 674,662, entitled "Apparatus and System for Creating Attachments," filed August 11, 2017; and U.S. Patent No. 11,10, entitled "Dental Attachment Placement Structure," filed June 14, 2017. U.S. Patent Application Serial No. 14 / 963,527, filed December 9, 2015, entitled “Dental Attachment Placement Structure”; U.S. Patent Application Serial No. 14 / 939,246, filed November 12, 2015, entitled “Dental Attachment Forming Structure”; U.S. Patent Application Serial No. 14 / 939,252, filed November 12, 2015, entitled “Dental Attachment Forming Structure”; and U.S. Patent No. 9,700,385, filed August 22, 2014, entitled “Attachment Structure”; all of these documents are incorporated herein by reference in their entirety.

[0446] The techniques described herein can be used to manufacture incremental palatal expanders and / or a series of incremental palatal expanders for expanding a person's palate from an initial position to a target position according to one or more aspects of a treatment plan. Examples of incremental palatal expanders can be found in at least the following documents: U.S. Application Serial No. 16 / 380,801, entitled "Releasable Palatal Expander," filed April 10, 2019; U.S. Application Serial No. 16 / 022,552, entitled "Apparatus, System, and Method for Dental Arch Expansion," filed June 28, 2018; and U.S. Patent No. 11,045,2018, entitled "Patard Expander with Bone Anchoring Device," filed June 8, 2018. 83; U.S. Patent Application Serial No. 15 / 831,159, filed December 4, 2017, entitled “Painful expander and method of expanding the palate”; U.S. Patent No. 10,993,783, filed December 4, 2017, entitled “Method and apparatus for custom rapid palatal expander”; and U.S. Patent No. 7,192,273, filed August 7, 2003, entitled “System and method for palatal expansion”; all of these documents are incorporated herein by reference in their entirety.

[0447] In some embodiments, the polymers, polymer compositions or other materials disclosed herein can be used to produce many different types of additively manufactured objects, such as orthodontic appliances (e.g., braces, palatal expanders, attachments, attachment templates, retainers), restorative objects (e.g., crowns, veneers, implants) and / or other dental appliances (e.g., oral sleep apnea appliances, oral protectors).

[0448] In some implementations, orthodontic appliances are orthodontic appliances or a series of orthodontic appliances, dental expanders, incremental palatal expanders, a series of incremental palatal expanders, dental spacers, retainers, oral protectors, and sports protectors.

[0449] One embodiment provides a 3D-printed article of article (e.g., an orthodontic appliance) comprising the polymer compositions or polymer films disclosed herein. In some embodiments, the orthodontic appliance comprises a plurality of additively formed layers, wherein one or more of the additively formed layers comprise the polymer compositions or polymer films disclosed herein.

Claims

1. A block copolymer having at least a first block and a second block, wherein: i) The first block is a poly(aryl acrylate) or poly(aryl methacrylate) block having 10-300 repeating units, or a poly(aryl methacrylate) block having 10-300 repeating units. ii) The second block is a poly(alkyl acrylate) block having 10-300 repeating units.

2. The block copolymer of claim 1, wherein: i) The first block is a poly(aryl acrylate) block or a poly(aryl methacrylate) block comprising the following substructures: in: R 1 Each time it appears, it is independently either hydrogen or CH3; n1 is an integer in the range of 10-300; and ii) The second block is a poly(alkyl acrylate) block comprising the following substructure: in: R 2 Each occurrence is independently a C1-C6 alkyl group; and n2 is an integer in the range of 10-300.

3. The block copolymer of any one of claims 1-2, wherein the block copolymer is a diblock copolymer comprising the following substructure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1 and n2 are each independent integers in the range of 10-300.

4. The block copolymer of any one of claims 1-3, wherein the block copolymer is a triblock copolymer comprising the following substructure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1, n2, and n3 are each independent integers in the range of 10-300.

5. The block copolymer of claim 4, wherein n3 is an integer in the range of 10-100.

6. The block copolymer according to any one of claims 1-5, wherein the block copolymer has the following structure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 It is a C1-C6 alkyl, a C1-C6 hydroxyalkyl, or R 3 It has the following structure: ； R 4 It is a halogenated product; n1 and n2 are both integers in the range of 10-300.

7. The block copolymer of claim 6, wherein R 3 It is either ethyl or -CH2CH2OH.

8. The block copolymer of any one of claims 6-7, wherein R 3 It has the following structure: 。 9. The block copolymer according to any one of claims 6-8, wherein R 4 It is bromine.

10. The block copolymer according to any one of claims 1-9, wherein the block copolymer has the following structure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 and R 4 Each is an independent halogenation; L 1 and L 3 Each of them independently has the following structure: ； L 2 It has the following structure: ;and n1, n2, n3, and n4 are each independent integers in the range of 10-300.

11. The block copolymer according to any one of claims 1-10, wherein R 1 Each time it appears, it is either hydrogen or methyl.

12. The block copolymer according to any one of claims 1-11, wherein R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl.

13. The block copolymer according to any one of claims 1-12, wherein R 2 Each time it appears, it is n-butyl.

14. The block copolymer according to any one of claims 1-13, wherein n1 is an integer in the range of 10-100.

15. The block copolymer according to any one of claims 1-14, wherein n2 is an integer in the range of 10-100.

16. The block copolymer according to any one of claims 6-15, wherein R 3 and R 4 All are bromine.

17. A micelle comprising a plurality of block copolymers, the micelle comprising: i) a core comprising at least a portion of a poly(alkyl acrylate) block of one or more block copolymers; and ii) an outer layer comprising at least a portion of a poly(aryl acrylate) block or a poly(aryl methacrylate) block of one or more block copolymers.

18. The micelles of claim 17, wherein the poly(aryl acrylate) block or the poly(aryl methacrylate) block comprises the following substructure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; and n1 is an integer in the range of 10-300.

19. The micelles of any one of claims 17-18, wherein n1 is an integer in the range of 10-100.

20. The micelles of any one of claims 17-19, wherein the poly(alkyl acrylate) block comprises the following substructure: in: R 2 Each occurrence is independently a C1-C6 alkyl group; and n2 is an integer in the range of 10-300.

21. The micelles of claim 20, wherein R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl.

22. The micelles according to any one of claims 20-21, wherein R 2 Each time it appears, it is n-butyl.

23. The micelles of any one of claims 20-22, wherein n2 is an integer in the range of 10-100.

24. The micelles of any one of claims 17-23, wherein one or more block copolymers are diblock copolymers comprising the following substructures: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1 and n2 are each independent integers in the range of 10-300.

25. The micelles of any one of claims 17-24, wherein each block copolymer is a diblock copolymer comprising the following substructures: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1 and n2 are each independent integers in the range of 10-300.

26. The micelles according to any one of claims 20-25, wherein R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl.

27. The micelles according to any one of claims 20-26, wherein R 2 Each time it appears, it is n-butyl.

28. The micelles of any one of claims 18-27, wherein n1 is an integer in the range of 10-100.

29. The micelles of any one of claims 20-28, wherein n2 is an integer in the range of 10-100.

30. The micelles of any one of claims 17-29, wherein at least one block copolymer is a triblock copolymer comprising the following substructures: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1, n2, and n3 are each independent integers in the range of 10-300.

31. The micelles of any one of claims 17-29, wherein each block copolymer is a triblock copolymer comprising the following substructures: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each occurrence is independently a C1-C6 alkyl group; and n1, n2, and n3 are each independent integers in the range of 10-300.

32. The micelles according to any one of claims 20-31, wherein R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl.

33. The micelles according to any one of claims 20-32, wherein R 2 Each time it appears, it is n-butyl.

34. The micelles according to any one of claims 20-33, wherein n1 is an integer in the range of 10-100.

35. The micelles according to any one of claims 20-34, wherein n2 is an integer in the range of 10-100.

36. The micelles of any one of claims 20-35, wherein n3 is an integer in the range of 10-100.

37. The micelles of any one of claims 17-36, wherein at least one block copolymer has the following structure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 It is a C1-C6 alkyl, a C1-C6 hydroxyalkyl, or R 3 It has the following structure: ； R 4 It is a halogenated product; and n1 and n2 are both integers in the range of 10-300.

38. The micelles of any one of claims 17-37, wherein each block copolymer has the following structure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 It is a C1-C6 alkyl, a C1-C6 hydroxyalkyl, or R 3 It has the following structure: ； R 4 It is a halogenated product; and n1 and n2 are both integers in the range of 10-300.

39. The micelles according to any one of claims 20-38, wherein R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl.

40. The micelles according to any one of claims 20-39, wherein R 2 Each time it appears, it is n-butyl.

41. The micelles according to any one of claims 38-40, wherein R 3 It is either ethyl or -CH2CH2OH.

42. The micelles according to any one of claims 38-41, wherein R 3 It has the following structure: 。 43. The micelles according to any one of claims 18-42, wherein n1 is an integer in the range of 10-100.

44. The micelles according to any one of claims 20-43, wherein n2 is an integer in the range of 10-100.

45. The micelles according to any one of claims 38-44, wherein R 4 It is bromine.

46. ​​The micelles according to any one of claims 17-45, wherein at least one of the block copolymers has the following structure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 and R 4 Each is an independent halogenation; L 1 and L 3 Each of them independently has the following structure: ； L 2 It has the following structure: ;and n1, n2, n3, and n4 are each independent integers in the range of 10-300.

47. The micelles of any one of claims 17-45, wherein each block copolymer has the following structure: in: R 1 Each time it appears, it is independently either hydrogen or CH3; R 2 Each time it appears, it is independently a C1-C6 alkyl group; R 3 and R 4 Each is an independent halogenation; L 1 and L 3 Each of them independently has the following structure: ； L 2 It has the following structure: ;and n1, n2, n3, and n4 are each independent integers in the range of 10-300.

48. The micelles according to any one of claims 20-47, wherein R 2 Each time it appears, it is independently methyl, ethyl, propyl, isopropyl, 2-methylpropyl, n-butyl, sec-butyl, or tert-butyl.

49. The micelles according to any one of claims 20-48, wherein R 2 Each time it appears, it is n-butyl.

50. The micelles of any one of claims 18-49, wherein n1 is an integer in the range of 10-100.

51. The micelles according to any one of claims 20-50, wherein n2 is an integer in the range of 10-100.

52. A photocurable resin comprising: i) aryl acrylate monomers, aryl methacrylate monomers, or combinations thereof; and ii) Macromolecular initiator compounds having the following structures: in: n2 is an integer in the range of 10-500.

53. A photocurable resin comprising: i) Aryl acrylate monomers, aryl methacrylate monomers, or combinations thereof; ii) Alkyl acrylate monomers; and iii) Initiator.

54. The photocurable resin of claim 53, wherein the initiator comprises a photoinitiator.

55. The photocurable resin of claim 54, wherein the photoinitiator comprises a free radical photoinitiator.

56. The photocurable resin according to any one of claims 53-55, wherein the initiator comprises a thermal initiator.

57. The photocurable resin of claim 56, wherein the thermal initiator comprises azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), or a combination thereof.

58. The photocurable resin according to any one of claims 52-57, wherein the photocurable resin is a photocurable composition.

59. The photocurable resin according to any one of claims 53-58, wherein the photocurable resin comprises 0.01-10 wt% of an initiator.

60. The photocurable resin according to any one of claims 52-59, further comprising one or more agents selected from the group consisting of: crosslinking modifiers, glass transition temperature modifiers, toughness modifiers, polymerization catalysts, polymerization inhibitors, light blocking agents, plasticizers, surface energy modifiers, pigments, dyes, fillers, biologically significant chemical substances, solvents, and combinations thereof.

61. The photocurable resin according to any one of claims 52-60, wherein the photocurable resin can be 3D printed at a printing temperature greater than 25°C.

62. The photocurable resin according to claims 52-61, wherein the printing temperature is at least 30°C, 40°C, 50°C, 60°C, 80°C, or 100°C, or is between 25°C and 150°C.

63. The photocurable resin according to any one of claims 52-62, wherein the photocurable resin has a viscosity of 30 cP to 50,000 cP at the printing temperature.

64. The photocurable resin according to any one of claims 52-63, wherein the photocurable resin comprises less than 20 wt% hydrogen-bonding units.

65. The photocurable resin according to any one of claims 52-64, wherein the photocurable resin is in a liquid state at a temperature of about 40°C to about 100°C.

66. The photocurable resin according to any one of claims 52-65, wherein the photocurable resin is liquid at a temperature above about 40°C and has a viscosity of less than about 20 PaS.

67. The photocurable resin according to any one of claims 52-66, wherein the photocurable resin is liquid at a temperature above about 40°C and has a viscosity of less than about 1 PaS.

68. The photocurable resin according to any one of claims 52-67, wherein at least a portion of the photocurable resin melts at a temperature between about 60°C and about 0°C.

69. A polymer composition formed from any one of the photocurable resins of claims 52-68.

70. The polymer composition of claim 69, wherein, as measured by FTIR, the polymer composition has a double-to-single bond conversion rate of greater than 60% compared to the photocurable resin.

71. A polymer composition comprising micelles dispersed in and in physical contact with a photopolymer network according to any one of claims 17-51.

72. A polymer composition comprising micelles dispersed in and covalently bonded to a photopolymer network according to any one of claims 17-51.

73. The polymer composition of any one of claims 71-72, wherein the photopolymer network comprises a poly(acrylate) polymer, a poly(methacrylate) polymer, a block copolymer comprising at least one poly(acrylate) block and at least one poly(methacrylate) block, or a combination thereof.

74. The polymer composition of any one of claims 71-73, wherein the photopolymer network comprises more than 50 wt% poly(acrylate) polymer based on the total weight of the polymer composition.

75. The composition of any one of claims 71-74, wherein the photopolymer network comprises more than 90 wt% poly(acrylate) polymer based on the total weight of the polymer composition.

76. The polymer composition of any one of claims 73-75, wherein the poly(acrylate) polymer comprises poly(2,6-dimethoxyphenyl acrylate).

77. The polymer composition according to any one of claims 73-76, wherein the poly(acrylate) polymer is greater than 20 wt% poly(2,6-dimethoxyphenyl acrylate) based on the total weight of the poly(acrylate) polymer.

78. The polymer composition of any one of claims 73-77, wherein the poly(acrylate) polymer is greater than 40 wt% poly(2,6-dimethoxyphenyl acrylate) based on the total weight of the poly(acrylate) polymer.

79. The polymer composition of any one of claims 71-78, wherein the photopolymer network comprises more than 50 wt% poly(methacrylate) polymer based on the total weight of the polymer composition.

80. The polymer composition of any one of claims 71-79, wherein the photopolymer network comprises more than 90 wt% poly(methacrylate) polymer based on the total weight of the polymer composition.

81. The polymer composition of any one of claims 73-80, wherein the poly(methacrylate) polymer comprises poly(2,6-dimethoxyphenyl methacrylate).

82. The polymer composition according to any one of claims 73-81, wherein the poly(methacrylate) polymer is greater than 20 wt% poly(2,6-dimethoxyphenyl methacrylate) based on the total weight of the poly(methacrylate) polymer.

83. The polymer composition according to any one of claims 73-82, wherein the poly(methacrylate) polymer is greater than 40 wt% poly(2,6-dimethoxyphenyl methacrylate) based on the total weight of the poly(methacrylate) polymer.

84. The polymer composition according to any one of claims 71-83, wherein the concentration of the micelles is less than 10 wt% relative to the total weight of the polymer composition.

85. The polymer composition according to any one of claims 69-84, wherein the polymer composition is characterized in that, when measured after 24 hours in a humid environment at 37°C, the water absorption rate is 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%.

86. The polymer composition according to any one of claims 69-85, wherein after 24 hours in a humid environment at 37°C, the ultimate tensile strength of the polymer composition is 10 MPa to 100 MPa, 15 MPa to 80 MPa, 20 MPa to 60 MPa, 10 MPa to 50 MPa, 10 MPa to 45 MPa, 25 MPa to 40 MPa, 30 MPa to 45 MPa, or 30 MPa to 40 MPa.

87. The polymer composition according to any one of claims 69-86, wherein the polymer composition is characterized in that, before and after 24 hours in a humid environment at 37°C, the elongation at break is greater than 10%, greater than 20%, greater than 30%, 5% to 250%, 20% to 250%, or the elongation at break is between 40% and 250%.

88. The polymer composition according to any one of claims 69-87, wherein the polymer composition is characterized in that, after 24 hours in a humid environment at 37°C, it has 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.

89. The polymer composition according to any one of claims 69-88, wherein after 24 hours in a humid environment at 37°C, the flexural stress, flexural modulus, or flexural stress and flexural modulus of the polymer composition is 400 MPa or higher, 300 MPa or higher, 200 MPa or higher, 180 MPa or higher, 160 MPa or higher, 120 MPa or higher, 100 MPa or higher, 80 MPa or higher, 70 MPa or higher, or 60 MPa or higher.

90. The polymer composition according to any one of claims 69-89, wherein after 24 hours in a humid environment at 37°C, at least 40%, 50%, 60%, or 70% of visible light passes through the polymer composition.

91. The polymer composition of any one of claims 69-90, wherein the polymer composition is biocompatible, bioinert, or a combination thereof.

92. A polymer film comprising the polymer composition according to any one of claims 69-91.

93. The polymer membrane of claim 92, wherein the thickness of the polymer membrane is at least 100 μm and not more than 3 mm.

94. A method for forming a polymer composition, the method comprising: Provides a photocurable resin according to any one of claims 52-68; Expose the photocurable resin to a light source; as well as The photocurable resin is polymerized to form the polymer.

95. The method of claim 94, wherein the light source is an ultraviolet (UV) or visible light source.

96. The method of any one of claims 94-95, further comprising manufacturing orthodontic appliances using the light-curable resin.

97. A method for preparing an article by additive manufacturing process, comprising: Provides a photocurable resin according to any one of claims 52-68; The photocurable resin is heated to the processing temperature; Expose the photocurable resin to radiation; Based on a predetermined design, the photocurable resin is polymerized layer by layer, thereby polymerizing the monomers to form a polymer composition; as well as The article is manufactured using the polymer composition.

98. The method of claim 97, wherein the processing temperature is from about 50°C to about 120°C.

99. The method of claim 97, wherein the processing temperature is about 90°C to about 110°C, about 100°C to about 120°C, about 105°C to about 115°C, or about 108°C to about 110°C.

100. The method of any one of claims 97-99, wherein the additive manufacturing process is a 3D printing process.

101. The method of any one of claims 97-100, wherein the article of manufacture is a medical device.

102. The method of claim 101, wherein the medical device is an orthodontic appliance.

103. An orthodontic appliance comprising the polymer composition of any one of claims 69-91 or the polymer film of any one of claims 92-93.

104. The orthodontic appliance of claim 103, wherein the orthodontic appliance is a dental appliance.

105. The orthodontic appliance of claim 104, wherein the orthodontic appliance is a dental appliance or a series of dental appliances, dental expanders, incremental palatal expanders or a series of incremental palatal expanders, dental spacers, retainers, oral protectors and motor protectors.

106. A method for repositioning a patient's teeth, comprising: A treatment plan is generated for the patient, the plan including multiple intermediate tooth arrangements for moving teeth along a treatment path from the initial tooth arrangement toward the final tooth arrangement; Producing orthodontic appliances comprising the polymer composition according to any one of claims 69-91; as well as The orthodontic appliance is used to move at least one of the patient's teeth along a track toward the intermediate or final tooth alignment.

107. The method of claim 106, wherein manufacturing orthodontic appliances includes 3D printing orthodontic appliances.

108. The method of any one of claims 106-107, further comprising tracking the progress of the patient's teeth along the treatment path after the orthodontic appliance is applied to the patient, the tracking comprising comparing the current alignment of the patient's teeth with the planned alignment of the patient's teeth.

109. The method of any one of claims 106-108, wherein after two weeks of treatment, more than 60% of the patient's teeth conform to the treatment plan.

110. The method of any one of claims 106-109, wherein after 2 days, the repositioning force retained by the orthodontic appliance for at least one tooth of the patient is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the repositioning force initially provided to at least one tooth of the patient.

111. A three-dimensional printed article comprising the polymer composition of any one of claims 69-91 or the polymer film of any one of claims 92-93.

112. An orthodontic appliance comprising a plurality of additively formed layers, wherein one or more of the plurality of additively formed layers comprise a polymer composition according to any one of claims 69-91 or a polymer film according to any one of claims 92-93.

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