Curable compositions comprising polymerizable reactive diluents for making orthodontic appliances

Abstract

The present disclosure provides a curable composition comprising one or more photopolymerizable monomers as reactive diluents, and a polymeric material formed from the curable composition. The present disclosure also provides methods of making the compositions, and methods of making medical devices (e.g., orthodontic appliances) using the compositions.

Description

Background Art

[0001] Orthodontic appliances have strict requirements for strength, flexibility, durability, size, weight, and appearance. Although generally a robust appliance is needed to achieve the desired treatment effect, such as tooth alignment, due to practical limitations in terms of comfort, appearance, and patient compliance, these appliances are typically required to be small in size, light in weight, and transparent or neutral in appearance. Additionally, for many dental applications, the material must be compatible with high-resolution printing methods. Curable compositions are commonly used for the additive manufacturing of polymeric materials, such as materials for manufacturing orthodontic appliances. Increasing the viscosity of the material and / or using components with a lower vapor pressure and / or high boiling point can enable a more simplified production method for many applications and provide superior thermomechanical properties by enhancing the physical interactions between chains, increasing the average weight of the monomers, and increasing the conformational freedom of the monomers (e.g., their potential to rotate around specific chemical bonds, etc.). Therefore, providing a curable resin with polymerizable components having a lower vapor pressure may be beneficial for achieving high-temperature printing processes. Summary of the Invention

[0002] The present invention provides a curable composition comprising one or more polymerizable monomers as reactive diluents, suitable for use in a lithography-based photopolymerization process for manufacturing orthodontic appliances, such as aligners, expanders, or spacers.

[0003] In various aspects, the present invention provides a curable composition for a photopolymerization process, the curable composition comprising: an initiator and a polymerizable monomer. The polymerizable monomer is a substituted phenyl (meth)acrylate having a vapor pressure of at most about 12 Pa at 60 °C. At least one ortho position of the benzene ring is substituted with a group containing at least one heteroatom selected from N, O, and S or a group containing a silicon atom. The content of the polymerizable monomer is such that the viscosity of the composition at the printing temperature is from 30 cP to 50,000 cP.

[0004] In some embodiments, the polymerizable monomer has the following structure according to formula (I):

[0005] Wherein:

[0006] X is O, S, NR 6 or SiR 7 R 8 ;

[0007] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or a halogen;

[0008] R 2 is substituted or unsubstituted C1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0009] R 3 、R 4 and R 5 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 ; or R 4 and R 5 together form a 4-, 5-, 6-, 7- or 8-membered ring selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8) )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0010] wherein Y is O, S, NH or C(O)O;

[0011] n is an integer from 0 to 6;

[0012] R 6 、R 7 and R 8 are independently H or substituted or unsubstituted C 1-6 alkyl; and

[0013] R 9 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0014] In some embodiments, X is O. In some embodiments, R 1 is H or methyl. In some embodiments, R 2 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6Heteroalkyl, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl. In some embodiments, R 2 is unsubstituted C 1-6 alkyl. In some embodiments, R 2 is methyl or ethyl. In some embodiments, R 3 is H. In some embodiments, R 3 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 . In some embodiments, R 3 is methyl or ethyl. In some embodiments, R 4 is H. In some embodiments, R 4 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 . In some embodiments, R 5 is H. In some embodiments, R 5 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 . In some embodiments, R 5 is methoxy.

[0015] In some embodiments, the polymerizable monomer has one of the following structures:

[0016]

[0017] In some embodiments, the curable composition comprises 10 - 80 wt% of a polymerizable monomer. In some embodiments, the polymerizable monomer reduces the viscosity of the curable composition by at least 5% compared to a composition without the polymerizable monomer. In some embodiments, the initiator comprises a photoinitiator. In some embodiments, the photoinitiator comprises a free radical photoinitiator. In some embodiments, the initiator further comprises a thermal initiator. In some embodiments, the thermal initiator comprises azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), or a combination thereof. In some embodiments, the curable composition comprises 0.01 - 10 wt% of the initiator. In some embodiments, the curable composition further comprises a telechelic oligomer, a telechelic polymer, or a combination thereof. In some embodiments, the number average molecular weight of the telechelic oligomer is greater than 500 Da but less than 3 kDa. In some embodiments, the number average molecular weight of the telechelic polymer is greater than 5 kDa but less than 50 kDa. In some embodiments, the telechelic oligomer or the telechelic polymer comprises photo-reactive moieties at both of its ends. In some embodiments, the photo-reactive moiety is an acrylate, methacrylate, acrylate vinyl ester, methacrylate vinyl ester, allyl ether, silene, alkyne, alkene, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some embodiments, the photo-reactive moiety is an acrylate or methacrylate moiety. In some embodiments, the curable composition comprises 0.5 - 99.5 wt%, 1 - 99 wt%, 10 - 95 wt%, 20 - 90 wt%, 25 - 60 wt%, or 35 - 50 wt% of a polymerizable monomer and a telechelic polymer and / or oligomer. In some embodiments, the polymerizable monomer according to formula (I) is a first polymerizable monomer, and the curable composition further comprises a second polymerizable monomer different from the polymerizable monomer shown in formula (I). In some embodiments, the second polymerizable monomer comprises an alkyl acrylate, an alkyl methacrylate, a homomenthyl acrylate, a homomenthyl methacrylate, or a combination thereof. In some embodiments, the second polymerizable monomer is a homomenthyl acrylate, a homomenthyl methacrylate, or a combination thereof. In some embodiments, the curable composition comprises 25 - 35 wt% of the first polymerizable monomer and 10 - 50% of the second polymerizable monomer. In some embodiments, the curable composition further comprises one or more of the following: a crosslinking modifier, a glass transition temperature modifier, a polymerization catalyst, a polymerization inhibitor, a photoresist, a plasticizer, a surface energy modifier, a pigment, a dye, a filler, a biologically significant chemical, and a solvent. In some embodiments, the curable composition is capable of 3D printing at a printing temperature higher than 25°C. In some embodiments, the printing temperature is at least 30°C, 40°C, 50°C, 60°C, 80°C, or 100°C.In some embodiments, the printing temperature is from 20°C to 150°C. In some embodiments, the curable composition comprises less than 20 wt% of hydrogen-bonding units. In some embodiments, the curable composition is liquid at a temperature of from about 40°C to about 100°C. In some embodiments, the curable composition is liquid at a temperature above about 40°C and has a viscosity of less than about 20 PaS. In some embodiments, the curable composition is in a liquid state at a temperature above about 40°C and has a viscosity of less than about 1 PaS. In some embodiments, at least a portion of the curable composition melts at a temperature between about 60°C and about 0°C.

[0018] The present invention also provides a polymeric material formed from the curable composition of the present invention. In some embodiments, the polymeric material has one or more of the following properties: (A) a storage modulus greater than or equal to 200 MPa; (B) a remaining flexural stress and / or flexural modulus greater than or equal to 1.5 MPa after being placed in a humid environment at 37 °C for 24 hours; (C) an elongation at break greater than or equal to 5% before and after being placed in a humid environment at 37 °C for 24 hours; (D) a water absorption rate less than 25 wt% when measured after being placed in a humid environment at 37 °C for 24 hours; (E) at least 30% of visible light passing through the polymeric material after being placed in a humid environment at 37 °C for 24 hours; and (F) comprising a plurality of polymer phases, wherein the Tg of at least one polymer phase in one or more polymer phases is at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C. The polymeric material is characterized in that 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% when measured after being placed in a humid environment at 37 °C for 24 hours. In some embodiments, compared with the curable composition, the polymeric material has a conversion rate of double bonds to single bonds greater than 60% as measured by FTIR. In some embodiments, after being placed in a humid environment at 37 °C for 24 hours, the ultimate tensile strength of the polymeric material 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 embodiments, the polymeric material is characterized in that the elongation at break is greater than 10%, greater than 20%, greater than 30%, the elongation at break is 5% to 250%, the elongation at break is 20% to 250% or the elongation at break value is 40% to 250% before and after being placed in a humid environment at 37 °C for 24 hours. In some embodiments, the polymeric material is characterized in that the storage modulus is 0.1 MPa to 4000 MPa, the storage modulus is 300 MPa to 3000 MPa, or the storage modulus is 750 MPa to 3000 MPa after being placed in a humid environment at 37 °C for 24 hours. In some embodiments, after being placed in a humid environment at 37 °C for 24 hours, the flexural stress and / or flexural modulus of the polymeric material 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, 60 MPa or higher.In some embodiments, after the polymeric material is placed in a moist environment at 37 °C for 24 hours, at least 40%, 50%, 60% or 70% of visible light can pass through the polymeric material. In some embodiments, the polymeric material is biocompatible, bio-inert or a combination thereof.

[0019] In various aspects, provided herein is a polymeric film comprising the polymeric material of the present disclosure. In some embodiments, the polymeric film has a thickness of at least 100 μm and no more than 3 mm.

[0020] In various aspects, provided herein is an orthodontic appliance comprising the polymeric material or polymeric film of the present disclosure. In some embodiments, the orthodontic appliance is an aligner, expander or spacer.

[0021] In various aspects, provided herein is a method of forming a polymeric material from the curable composition of the present disclosure. The method includes: providing the curable composition of the present disclosure; exposing the curable composition to a light source; and curing the curable composition to form a polymeric material. In some embodiments, the light source is an ultraviolet (UV) or visible light source. In some embodiments, the method further includes inducing phase separation during the photocuring process. In some embodiments, inducing phase separation includes generating one or more polymer phases in the polymeric material during the photocuring process. In some embodiments, at least one of the one or more polymer phases is an amorphous phase having a glass transition temperature (Tg) of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C. In some embodiments, at least 25%, 50% or 75% of the polymer phases generated during the photocuring process are amorphous phases having a glass transition temperature (Tg) of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C. In some embodiments, the at least one amorphous phase having a glass transition temperature (Tg) of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C comprises a polymerizable monomer incorporated in its polymer structure. In some embodiments, at least one of the one or more polymer phases is a crystalline phase comprising a crystalline polymeric material. In some embodiments, the crystalline polymeric material has a melting point of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C. In some embodiments, at least one of the one or more polymer phases is three-dimensional and has a length of at least one dimension less than 1000 μm, less than 500 μm, less than 250 μm or less than 200 μm. In some embodiments, the method further includes manufacturing an orthodontic appliance using the polymeric material.

[0022] The present disclosure provides, in various aspects, a method of fabricating an article by an additive manufacturing process. The method includes: providing a curable composition of the present disclosure; heating the curable composition to a processing temperature; exposing the curable composition to radiation; curing the curable composition layer by layer according to a predetermined design such that polymerizable monomers polymerize and crosslink to form a polymeric material; and fabricating an article using the polymeric material. 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.

[0023] The present disclosure provides, in various aspects, a method of repositioning a patient's teeth. The method includes: generating a treatment plan for the patient, the plan including a plurality of intermediate tooth alignments for moving teeth along a treatment path from an initial tooth alignment towards a final tooth alignment; fabricating an orthodontic appliance of the present disclosure, or an orthodontic appliance comprising the polymeric material of the present disclosure; and using the orthodontic appliance to move at least one tooth of the patient towards an intermediate tooth alignment or the final tooth alignment along an orbit. In some embodiments, fabricating the orthodontic appliance includes 3D printing the orthodontic appliance. In some embodiments, the method further includes tracking the progress of the patient's teeth along the treatment path after the orthodontic appliance is 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. In some embodiments, after 2 weeks of treatment, more than 60% of the patient's teeth are on the orbit of the treatment plan. In some embodiments, the repositioning force maintained by the orthodontic appliance on at least one tooth of the patient after 2 days 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.

[0024] Brief Description of the Drawings

[0025] Various aspects of the present disclosure will be best understood from the following detailed description in conjunction with the accompanying drawings. It should be noted that, in accordance with industry standard practice, the features in the drawings are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily enlarged or reduced for clarity of discussion.

[0026] Figure 1A An appliance for repositioning teeth according to some embodiments is shown.

[0027] Figure 1B A system for repositioning teeth according to some embodiments is shown.

[0028] Figure 1CIllustrated is a method of orthodontic treatment using multiple appliances according to an embodiment.

[0029] Figure 2 Illustrated is a method of designing an orthodontic appliance according to an embodiment.

[0030] Figure 3 Illustrated is a method of digitally planning orthodontic treatment according to an embodiment.

[0031] Figure 4 Illustrated is the generation and administration of treatment according to an embodiment of the present disclosure.

[0032] Figure 5 Illustrated is a graph of tensile stress versus tensile strain for three different photocurable polymer materials P1 - P3 (each material containing a different monomer) at two different strain rates (1.7 mm / min and 510 mm / min).

[0033] Figure 6 Illustrated is a graph of dynamic mechanical analysis (DMA) results obtained from polymer materials P1 - P3.

[0034] Figure 7 Illustrated is a stress relaxation graph of polymer materials P1 - P3.

[0035] Figure 8 Illustrated are the transverse dimension and the longitudinal dimension used herein.

[0036] Figure 9 Illustrated is a schematic configuration of a high - temperature additive manufacturing apparatus for curing a curable composition as described in the present disclosure by using a 3D printing process.

[0037] Detailed Invention

[0038] In the following description, certain specific details are set forth in order to provide a thorough understanding of various embodiments of the present disclosure. However, those skilled in the art will understand that the present disclosure may be practiced even without these details.

[0039] Unless the context requires otherwise, throughout the specification and claims, the word "comprising" and its variations, such as "comprises" and "comprising", are to be interpreted in an open, inclusive sense, i.e., "including but not limited to".

[0040] The phrase "in one embodiment" or "in an embodiment" as used in this specification refers to the fact that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of the phrase "in one embodiment" or "in an embodiment" throughout this specification are not necessarily all referring to the same embodiment. Moreover, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0041] A numerical range should be understood to include all values, i.e., including the indicated lower and upper limits. In addition, the term "about" as used herein, unless otherwise expressly stated, generally means and includes ±10% of the indicated value. For example, "about 10%" may represent a range from 9% to 11%, and "about 1" may include a range from 0.9 - 1.1.

[0042] Additive manufacturing (e.g., additive manufacturing based on lithography technology (L-AM)) techniques include a variety of techniques for manufacturing objects (e.g., three-dimensional objects) using photo-curable materials. Traditional practice has shown that there are many difficulties in manufacturing many medical devices by additive manufacturing techniques. One problem is that the existing materials used for additive manufacturing are not biocompatible and are even less suitable for the intraoral environment or other parts of the human body. Another problem is that the existing materials used for additive manufacturing generally do not have sufficient viscosity to form the precise and / or customizable features required for many devices. In addition, for safety and cost considerations, the curing or reaction temperatures of many current additive manufacturing techniques are relatively low, which is not conducive to the production of products that are stable at or above body temperature for many medical devices (including orthodontic devices). Another problem is that the existing materials used for additive manufacturing cannot provide the physical, chemical, and / or thermo-mechanical properties (elongation, time-stress relaxation, modulus, durability, toughness, etc.) required for orthodontic appliances, other dental appliances, hearing aids, and / or many medical devices. Therefore, the existing materials used for additive manufacturing lack many of the properties required for medical devices, such as the inability to precisely apply forces, torques, moments, and / or other movements consistent with the treatment plan.

[0043] Increasing the viscosity of the material and / or using components with a lower vapor pressure and / or a high boiling point can achieve a more simplified production method for many applications and provide more excellent thermo-mechanical properties by enhancing the physical interactions between chains, increasing the average weight of the monomers, and increasing the spatial freedom of the monomers (e.g., their potential to rotate around specific chemical bonds, etc.).

[0044] The present disclosure aims to provide a curable composition (e.g., a curable resin) that is suitable for, for example, a photopolymerization process based on high-temperature lithography. These curable compositions can be used in a variety of applications, including for manufacturing medical devices and / or articles for the intraoral environment, such as intraoral devices, such as aligners, expanders, or spacers. In particular, considering the challenges of using printable resins at high temperatures, the present disclosure provides a photocurable composition that comprises one or more polymerizable monomers having a low vapor pressure, which monomers are capable, in various circumstances, of acting as viscosity modifiers, glass transition temperature modifiers, and reactive diluents for other polymerizable components present in the curable compositions provided herein, for a photopolymerization process, such as a lithography-based process (e.g., a high-temperature lithography-based process that conducts electricity at a temperature above 90 °C). Such photocurable compositions can provide (e.g., after photocuring) a polymeric material having properties that are particularly suitable for medical devices (e.g., orthodontic appliances), thereby meeting the need for a photocurable composition that can produce materials having a variety of specific mechanical properties. In various embodiments, the present disclosure provides curable (e.g., photocurable) compositions that are capable of allowing polymerization-induced phase separation to occur during curing. This phase separation can result in one or more polymer phases. In some cases, at least one polymer phase in one or more of the phases is an amorphous polymer phase. In some cases, at least one polymer in one or more of the phases is a crystalline polymer phase. This phase separation can provide desirable physical and mechanical properties for the polymeric material that are suitable for medical devices (e.g., orthodontic appliances). Accordingly, in various embodiments, the present disclosure provides medical devices (e.g., orthodontic appliances) that can comprise one or more polymeric materials, which polymeric materials comprise, in polymeric form, one or more of the polymerizable monomers of the present disclosure.

[0045] As used herein, the term "polymer" generally refers to a molecule composed of repeating structural units connected by covalent chemical bonds, characterized by having a large number of repeating units (e.g., equal to or greater than 20 repeating units, typically equal to or greater than 100 repeating units, usually equal to or greater than 200 repeating units), and a molecular weight greater than or equal to 5,000 Daltons (Da) or 5 kDa, such as greater than or equal to 10 kDa, 15 kDa, 20 kDa, 30 kDa, 40 kDa, 50 kDa, or 100 kDa. A polymer is typically the polymerization product of one or more monomer precursors. The term "polymer" includes homopolymers, i.e., polymers consisting essentially of a single repeating monomer. The term "polymer" also includes copolymers, i.e., polymers formed by linking two or more different types of monomers in the same polymer. Copolymers can contain two or more monomer sub-units, including random copolymers, block copolymers, alternating copolymers, segmented copolymers, graft copolymers, tapered copolymers, and other copolymers. The term "cross-linked polymer" generally refers to a polymer having one or more connections between at least two polymer chains, which connections may be generated by polyvalent monomers during polymerization by forming cross-linking sites.

[0046] As used herein, the term "oligomer" generally refers to a molecule composed of repeating structural units connected by covalent chemical bonds, characterized by having a number of repeating units less than that of a polymer (e.g., equal to or less than 10 repeating units), and a molecular weight lower than that of a polymer (e.g., less than 5,000 Da or 2,000 Da). In some cases, an oligomer may be the polymerization product of one or more monomer precursors. In one embodiment, an oligomer or monomer by itself cannot be considered a polymer.

[0047] As used herein, the terms "telechelic polymer" and "telechelic oligomer" generally refer to polymers or oligomers whose molecules can participate in further polymerization through reactive groups.

[0048] As used herein, a "reactive diluent" generally refers to a substance that reduces the viscosity of other substances (such as monomers or curable resins). A reactive diluent can become part of other substances (such as a polymer obtained through a polymerization process). In some examples, a reactive diluent is a curable monomer that, when mixed with a curable resin, reduces the viscosity of the final formulation and is incorporated into the polymer formed after polymerization of the formulation.

[0049] By measuring the molecular weight and molecular weight distribution, oligomer and polymer mixtures can be characterized and distinguished from other oligomer and polymer mixtures.

[0050] The average molecular weight (M) is the average number n of repeating units multiplied by the molecular weight or molar mass of the repeating unit (Mi )。The number-average molecular weight (M n ) is the arithmetic mean, representing the total weight of the molecules present divided by the total number of molecules.

[0051] The photoinitiators described in the present disclosure may include those that can be activated by light and initiate the polymerization of polymerizable components in the formulation. As used herein, "photoinitiator" generally refers to a compound that is capable of generating free radical species and / or promoting free radical reactions upon exposure to radiation (such as ultraviolet or visible light).

[0052] The thermal initiators described in the present disclosure may include those that can be activated by heat and initiate the polymerization of polymerizable components in the formulation. As used herein, "thermal initiator" may generally refer to a compound that is capable of generating free radical species and / or promoting free radical reactions under heated conditions.

[0053] As used herein, the term "biocompatible" refers to a material that, when placed in a biological environment within the body, does not cause 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 contacts the biocompatible material, the change in biomarkers indicative of an immune response is less than 10%, less than 20%, less than 25%, less than 40%, or less than 50% relative to the baseline value. Alternatively, the immune response can be determined by histological methods, where the local immune response is evaluated by visually assessing markers (including immune cells or markers involved in the immune response pathway) inside and near the material. In one aspect, as determined histologically, the biocompatible material or device does not cause a significant change in the immune response. In some embodiments, the present disclosure provides biocompatible devices that can be used for an extended period (such as weeks to months) without causing adverse immune responses. The biological effects can be initially evaluated by measuring cytotoxicity, sensitization, irritation and intracutaneous reactivity, acute systemic toxicity, pyrogenicity, subacute / subchronic toxicity, and / or implantability. Supplementary biological tests for evaluation include chronic toxicity tests.

[0054] "Biologically inert" refers to a material that, when placed in a biological environment within the body, does not initiate an immune response in a human or animal. For example, when a human or animal is exposed to or contacts the biologically inert material, the biomarkers indicative of an immune response remain substantially constant (±5% of the baseline value). In some embodiments, the present disclosure provides biologically inert devices.

[0055] When a group of substituents is disclosed herein, it is to be understood that all individual members of the group and all subgroups thereof, including any isomers, enantiomers, and diastereomers of the members of the group, are individually disclosed. When a Markush group or other grouping is used herein, all individual members of the group and all possible combinations and subcombinations thereof are intended to be individually included in the disclosure. When a compound is described herein, if a particular isomer, enantiomer, or diastereomer of the compound is not explicitly specified (e.g., in a chemical formula or chemical name), the description is intended to cover each isomer and enantiomer of the compound, whether present individually or in any combination. In addition, unless otherwise stated, all isotopic variants of the compounds disclosed herein are intended to be included in the disclosure. Specific names of compounds are intended as examples, as it is known to those skilled in the art that different names may be used to refer to the same compound.

[0056] As used herein, the term "group" may refer to a functional group of a compound. A group of the compounds of the present invention refers to a single atom or collection of atoms that is part of the compound. The groups of the present invention may be connected to other atoms of the compound by one or more covalent bonds. Groups may also be characterized by their valence states. The present invention includes groups characterized by monovalent, divalent, trivalent, and other valence states.

[0057] As used herein, the term "substituted" means that a hydrogen in a compound (e.g., an alkyl chain) is replaced by another functional group or atom described herein.

[0058] The dashed lines in chemical structures used herein may be used to represent bonds connecting to the rest of the molecule. For example, in the representation of the attachment point of 1-methylcyclopentanoate to the rest of the molecule is at the 1-position. Alternatively, for example in may be used to represent the bond by which a given moiety (in this case, the cyclohexyl moiety) is attached to the molecule with a wavy line "capping".

[0059] "Alkyl" refers to a straight-chain or branched-chain hydrocarbon group consisting only of carbon and hydrogen atoms, being saturated, and having, for example, from 1 to 30 carbon atoms, particularly from 1 to 6 carbon atoms, and being connected to the remainder of the molecule by a single bond. Alkyl can include short alkyl groups having 1 to 3 carbon atoms, medium-length alkyl groups having 4 to 10 carbon atoms, and long alkyl groups having more than 10 carbon atoms, particularly long alkyl groups having 10 to 30 carbon atoms. The term "cycloalkyl" specifically refers to an alkyl group having a cyclic structure, for example, a cyclic structure containing from 3 to 30 carbon atoms, optionally from 3 to 20 carbon atoms, and optionally from 3 to 10 carbon atoms, including alkyl groups having one or more rings. Cycloalkyl includes cycloalkyl groups having 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered carbon rings, particularly cycloalkyl groups having 3-, 4-, 5-, 6-, 7- or 8-membered carbon rings. The carbon rings in cycloalkyl can also bear alkyl groups. Cycloalkyl can include bicyclic and tricyclic alkyl groups. Alkyl can be optionally substituted as described herein. Substituted alkyl can include alkyl groups substituted by aryl groups, and the aryl groups can in turn be optionally substituted. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, branched pentyl, cyclopentyl, n-hexyl, branched hexyl, and cyclohexyl, all of which alkyl groups can be optionally substituted. Unless otherwise defined herein, substituted alkyl includes fully halogenated or semi-halogenated alkyl groups, for example, alkyl groups in which one or more hydrogen atoms are replaced by one or more fluorine, chlorine, bromine, and / or iodine atoms. Thus, substituted alkyl can include fully fluorinated or semi-fluorinated alkyl groups, for example, alkyl groups in which one or more hydrogen atoms are replaced by one or more fluorine atoms. An alkoxy group is an alkyl group modified by connection to oxygen and can be represented by the formula R-O and can also be referred to as an alkyl ether group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and heptyloxy. Alkoxy includes substituted alkoxy groups, where the alkyl portion of these groups is substituted as described herein for alkyl groups. MeO- as used herein refers to CH3O-. In addition, thioalkoxy groups as used herein are alkyl groups modified by connection to a sulfur atom (instead of oxygen) and can be represented by the formula R-S.

[0060] "Alkenyl" means an unsaturated alkyl group containing at least one carbon-carbon double bond. Alkenyl groups include straight-chain, branched-chain, and cyclic alkenyl groups. Alkenyl groups include alkenyl groups having 1, 2, or more double bonds, and alkenyl groups in which two or more double bonds are conjugated double bonds. Unless otherwise defined herein, alkenyl groups include alkenyl groups having 2 to 20 carbon atoms. Alkenyl groups include short alkenyl groups having 2 to 3 carbon atoms. Alkenyl groups include medium-length alkenyl groups having 4 to 10 carbon atoms. Alkenyl groups include long alkenyl groups having more than 10 carbon atoms, particularly long alkenyl groups having 10 to 20 carbon atoms. Cycloalkenyl groups include groups in which the double bond is within the ring or the double bond is in an alkenyl group attached to the ring. The term "cycloalkenyl" specifically refers to an alkenyl group having a cyclic structure, including alkenyl groups having 3-, 4-, 5-, 6-, 7-, 8-, 9-, or 10-membered carbon rings, particularly alkenyl groups having 3-, 4-, 5-, 6-, 7-, or 8-membered carbon rings. The carbon rings in cycloalkenyl groups may also bear alkyl groups. Cycloalkenyl groups may include bicyclic and tricyclic alkenyl groups. Alkenyl groups are optionally substituted. Unless otherwise defined herein, substituted alkenyl groups include, but are not limited to, alkenyl groups substituted with alkyl or aryl groups, and these groups may in turn be optionally substituted. Specific alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-cyclopropenyl, 1-butenyl, 2-butenyl, 1-cyclobutenyl, 2-cyclobutenyl, 1-pentenyl, 2-pentenyl, branched pentenyl, 1-cyclopentenyl, 1-hexenyl, branched hexenyl, and cyclohexenyl, all of which may be optionally substituted. Substituted alkenyl groups may include fully halogenated or semi-halogenated alkenyl groups, such as alkenyl groups in which one or more hydrogen atoms are replaced by one or more fluorine atoms, chlorine atoms, bromine atoms, and / or iodine atoms. Substituted alkenyl groups include fully fluorinated or semi-fluorinated alkenyl groups, such as alkenyl groups in which one or more hydrogen atoms are replaced by one or more fluorine atoms.

[0061] "Aryl" refers to a ring system containing at least one carbocyclic aromatic ring. In some embodiments, aryl contains 6 to 18 carbon atoms. Aryl includes groups having one or more 5-, 6-, 7- or 8-membered aromatic rings (including heteroaromatic rings). The term "heteroaryl" specifically refers to an aryl having at least one 5-, 6-, 7- or 8-membered heteroaromatic ring. Aryl may contain one or more fused aromatic rings (including one or more fused heteroaromatic rings), and / or a combination of one or more aromatic rings and one or more non-aromatic rings, and these rings may be fused or covalently linked. The ring of the heteroaromatic ring may contain one or more N, O or S atoms. Heteroaromatic rings may include heteroaromatic rings having one, two or three N atoms, heteroaromatic rings having one or two O atoms, and heteroaromatic rings having one or two S atoms, or heteroaromatic rings having a combination of one, two or three N, O or S atoms. Aryl may be optionally substituted. Substituted aryl includes, but is not limited to, aryl substituted with alkyl or alkenyl, and these groups may be optionally substituted. Specific aryls include phenyl, biphenyl, pyrrolidinyl, imidazolidinyl, tetrahydrofuryl, tetrahydrothienyl, furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl and naphthyl, all of which may be optionally substituted. Substituted aryl includes fully halogenated or semi-halogenated aryl, for example, one or more hydrogen atoms on the aryl are substituted with one or more fluorine atoms, chlorine atoms, bromine atoms and / or iodine atoms. Substituted aryl includes fully fluorinated or semi-fluorinated aryl, for example, aryl in which one or more hydrogens are substituted with one or more fluorine atoms. Aryl includes, but is not limited to, groups containing an aromatic group or a heterocyclic aromatic group corresponding to any of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, tetracene, tetracenedione, pyridine, quinoline, isoquinoline, indole, isoindole, pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furan, benzofuran, dibenzofuran, carbazole, acridine, acridone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthene, xanthone, flavone, coumarin, azulene or anthracycline. Groups corresponding to the above groups as used herein specifically include aromatic or heterocyclic aromatic groups in the aromatic and heterocyclic aromatic groups listed herein, including monovalent, divalent and polyvalent groups, and these groups exist in any suitable connection point of the compounds of the present disclosure in a covalently bonded configuration. In some embodiments, aryl contains 5 to 30 carbon atoms. In some embodiments, aryl contains an aromatic or heteroaromatic six-membered ring and one or more additional five- or six-membered aromatic or heteroaromatic rings. In some embodiments, the ring of aryl contains 5 to 18 carbon atoms.The aryl optionally has one or more aromatic rings or heteroaromatic rings, which aromatic rings or heteroaromatic rings have one or more electron-donating groups, electron-withdrawing groups, and / or targeting ligands as substituents.

[0062] Arylalkyl refers to an alkyl group substituted by one or more aryl groups, wherein the alkyl group optionally bears other substituents, and the aryl group is also optionally substituted. Specific arylalkyl refers to an alkyl group substituted by a phenyl group, such as benzyl. Alkylaryl can also be described as an aryl group substituted by one or more alkyl groups, wherein the alkyl group optionally bears other substituents, and the aryl group is also optionally substituted. Specific alkylaryl refers to a phenyl group substituted by an alkyl group, such as methylphenyl. Substituted alkylaryl includes fully halogenated or semi-halogenated arylalkyl, such as arylalkyl having one or more alkyl groups and / or aryl groups in which one or more hydrogens are substituted by one or more fluorine atoms, chlorine atoms, bromine atoms, and / or iodine atoms.

[0063] As used herein, the terms "alkylene" and "alkylene group" are synonymous and both refer to the divalent group "-CH2-" derived from the alkyl group as defined herein. The present disclosure includes compounds having one or more alkylene groups. The alkylene group in some compounds can be used as a linking group and / or a spacer group. The compounds of the present disclosure can have substituted and / or unsubstituted C1-C 20 alkylene, C1-C 10 alkylene and C1-C6 alkylene.

[0064] As used herein, the terms "cycloalkylene" and "cycloalkylene group" are synonymous and both refer to the divalent group derived from the cycloalkyl group as defined herein. The present disclosure includes compounds having one or more cycloalkylene groups. The cycloalkylene group in some compounds can be used as a linking group and / or a spacer group. The compounds of the present disclosure can have substituted and / or unsubstituted C3-C 20 cycloalkylene, C3-C 10 cycloalkylene and C3-C5 cycloalkylene.

[0065] As used herein, the terms "arylene" and "arylene group" are synonymous and both refer to the divalent group derived from the aryl group as defined herein. The present disclosure includes compounds having one or more arylene groups. In some embodiments, the arylene is a divalent group derived by removing hydrogen atoms from two intra-ring carbon atoms of the aromatic ring of the aryl group. The arylene group in some compounds is used as a linking group and / or a spacer group. The arylene group in some compounds is used as a chromophore, fluorophore, aromatic whisker, dye, and / or imaging group. The compounds of the present disclosure include substituted and / or unsubstituted C5-C 30 arylene, C5-C 20 arylene and C5-C 12 arylene.

[0066] As used herein, the terms "heteroarylene" and "heteroarylene group" are synonymous and each refers to a divalent group derived from a heteroaryl as defined herein. The present disclosure includes compounds having one or more heteroarylenes. In some embodiments, the heteroarylene is a divalent group derived by removing hydrogen atoms from two ring carbon atoms or ring nitrogen atoms within the heteroaryl ring or aryl ring of the heteroaryl. In some compounds, the heteroarylene group serves as a linking group and / or a spacer group. In some compounds, the heteroarylene group serves as a chromophore, an aromatic whisker, a fluorophore, a dye, and / or an imaging group. The compounds of the present disclosure include substituted and / or unsubstituted C5-C 30 heteroarylene, C5-C 20 heteroarylene and C5-C 12 heteroarylene.

[0067] As used herein, the terms "alkenylene" and "alkenylene group" are synonymous and each refers to a divalent group derived from an alkenyl as defined herein. The present invention includes compounds having one or more alkenylenes. The alkenylene in some compounds can serve as a linking group and / or a spacer group. The compounds of the present disclosure include substituted and / or unsubstituted C2-C 20 alkenylene, C2-C 10 alkenylene and C2-C5 alkenylene.

[0068] As used herein, the terms "cycloalkenylene" and "cycloalkenylene group" are synonymous and each refers to a divalent group derived from a cycloalkenyl as defined herein. The present disclosure includes compounds having one or more cycloalkenylenes. The cycloalkenylene in certain compounds can serve as a linking group and / or a spacer group. The compounds of the present disclosure include substituted and / or unsubstituted C3-C 20 cycloalkenylene, C3-C 10 cycloalkenylene and C3-C5 cycloalkenylene.

[0069] As used herein, the terms "alkynylene" and "alkynylene group" are synonymous and each refers to a divalent group derived from an alkynyl as defined herein. The present disclosure includes compounds having one or more alkynylenes. The alkynylene in some compounds can serve as a linking group and / or a spacer group. The compounds of the present disclosure include substituted and / or unsubstituted C2-C 20 alkynylene, C2-C 10 alkynylene and C2-C5 alkynylene.

[0070] As used herein, the terms "halo" and "halogen" are used interchangeably and refer to a halogen group such as fluoro (-F), chloro (-Cl), bromo (-Br), or iodo (-I).

[0071] The term "heterocycle" refers to a ring structure in which the ring contains at least one other atom in addition to carbon atoms. Examples of such heteroatoms include nitrogen, oxygen, and sulfur. Heterocycles include heterocyclic alicyclic rings and heterocyclic aromatic rings. Examples of heterocycles include, but are not limited to, pyrrolidinyl, piperidinyl, imidazolidinyl, tetrahydrofuryl, tetrahydrothienyl, furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl, and tetrazolyl. The atoms of the heterocycle can be bonded to a variety of other atoms and reactive functional groups, such as provided as substituents.

[0072] The term "carbocycle" refers to a cyclic structure that contains only carbon atoms in the ring. The carbon atoms of the carbocycle can be bonded to various other atoms and functional groups, such as provided as substituents.

[0073] The term "alicyclic ring" refers to one or more fused rings that are not aromatic rings. Alicyclic rings include carbocycles and heterocycles.

[0074] The term "aromatic ring" refers to one or more fused rings that contain at least one aromatic ring group. The term aromatic ring includes aromatic rings that contain carbon, hydrogen, and heteroatoms. Aromatic rings include carbocyclic and heterocyclic aromatic rings. Aromatic rings are a component of aryl groups.

[0075] The term "fused ring" or "fused ring structure" refers to multiple alicyclic rings and / or aromatic rings provided in a fused ring configuration, such as fused rings that share at least two ring carbon atoms and / or heteroatoms.

[0076] The term "alkoxyalkyl" as used herein refers to a substituent of the formula alkyl-O-alkyl.

[0077] The term "polyhydroxyalkyl" as used herein 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 groups.

[0078] The term "polyalkoxyalkyl" as used herein refers to a substituent of the formula alkyl-(alkoxy) n -alkoxy, where n is an integer from 1 to 10, such as from 1 to 4, and in some aspects from 1 to 3.

[0079] As used herein, the term "heteroalkyl" generally refers to an alkyl, alkenyl or alkynyl as defined herein, wherein at least one carbon atom of the alkyl is replaced by a heteroatom. In some cases, the chain of the heteroalkyl may contain 1 to 18 non-hydrogen atoms (carbon and heteroatoms), or 1 to 12 non-hydrogen atoms, or 1 to 6 non-hydrogen atoms, or 1 to 4 non-hydrogen atoms. The heteroalkyl can be straight-chain or branched-chain, and can also be saturated or unsaturated. The unsaturated heteroalkyl has one or more double bonds and / or one or more triple bonds. The heteroalkyl can be unsubstituted or substituted. Exemplary heteroalkyls include, but are not limited to, alkoxyalkyl (e.g., methoxymethyl) and aminoalkyl (e.g., alkylaminoalkyl and dialkylaminoalkyl). The heteroalkyl can be optionally substituted with one or more substituents.

[0080] As used herein, the term "carbonyl", e.g., in the context of a 1-6 carbonyl substituent, generally refers to a carbon chain of a given length (e.g., C 1-6 ), wherein each carbon atom of the given carbon chain can form a carbonyl bond, as long as it is chemically feasible in terms of the valence state of the carbon atom. Thus, in some cases, a "C 1-6 carbonyl" substituent refers to a carbon chain of 1 to 6 carbon atoms, and the terminal carbon contains a carbonyl functionality, or an internal carbon contains a carbonyl functionality (in this case, the substituent can be described as a ketone). As used herein, the term "carboxyl", e.g., in the context of a 1-6 carboxyl substituent, generally refers to a carbon chain of a given length (e.g., C 1-6 ), wherein the terminal carbon contains a carboxyl functionality, unless otherwise defined herein.

[0081] For any group described herein that contains one or more substituents, it should be understood that such groups do not contain any spatially unrealistic and / or synthetically infeasible substitutions or substitution patterns. In addition, the compounds of the present disclosure include all stereochemical isomers resulting from the substitution of these compounds.

[0082] Unless otherwise defined herein, the optional substituents of any alkyl, alkenyl and aryl include being substituted with one or more of the following substituents, including:

[0083] Halogen, including fluorine, chlorine, bromine or iodine;

[0084] Pseudohalides, including -CN, -OCN (cyanate), -NCO (isocyanate), -SCN (thiocyanate) and -NCS (isothiocyanate);

[0085] –COOR, wherein R is hydrogen or alkyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted;

[0086] –COR, where R is hydrogen or alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of these groups being optionally substituted;

[0087] –CON(R)2, where each R is independently of each other R hydrogen or alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of these groups being optionally substituted; and where R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms;

[0088] –OCON(R)2, where each R is independently of each other R hydrogen or alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of these groups being optionally substituted; and where R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms;

[0089] –N(R)2, where each R is independently of each other R hydrogen or alkyl or acyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl, phenyl or acetyl, all of these groups being optionally substituted; and where R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms;

[0090] –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;

[0091] –SO2R or –SOR, where R is alkyl or aryl, more specifically where R is methyl, ethyl, propyl, butyl or phenyl, all of these groups being optionally substituted;

[0092] –OCOOR, where R is alkyl or aryl;

[0093] –SO2N(R)2, where each R is independently of each other R hydrogen or alkyl or aryl, all of these groups being optionally substituted, and where R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms; and

[0094] –OR, where R is H, alkyl, aryl or acyl, all of these groups being optionally substituted. In a specific instance, R may be acyl, giving –OCOR”, where R” is hydrogen or alkyl or aryl, more specifically where R” is methyl, ethyl, propyl, butyl or phenyl, all of these groups being optionally substituted.

[0095] Specific substituted alkyl groups include haloalkyl groups, especially trihalomethyl groups and specifically trifluoromethyl groups. Specific substituted aryl groups include mono-, di-, tri-, tetra- and pentahalogeno-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa- and hepta-halogeno-substituted naphthyl groups; 3- or 4-halogeno-substituted phenyl groups, 3- or 4-alkyl-substituted phenyl groups, 3- or 4-alkoxy-substituted phenyl groups, 3- or 4-RCO-substituted phenyl groups, 5- or 6-halogeno-substituted naphthyl groups. More specifically, substituted aryl groups include acetylphenyl groups, especially 4-acetylphenyl groups; fluorophenyl groups, especially 3-fluorophenyl groups and 4-fluorophenyl groups; chlorophenyl groups, especially 3-chlorophenyl groups and 4-chlorophenyl groups; methylphenyl groups, especially 4-methylphenyl groups; and methoxyphenyl groups, especially 4-methoxyphenyl groups.

[0096] For any of the above groups containing one or more substituents, it should be understood that such groups do not contain any substituents or substitution patterns that are spatially impracticable and / or synthetically infeasible. In addition, the compounds of the present disclosure may include all stereochemical isomers resulting from the substitution of these compounds.

[0097] I. Polymerizable monomers

[0098] The present disclosure provides polymerizable monomers. The polymerizable monomers of the present disclosure can be used as part of a polymerizable composition (e.g., a photocurable resin). As described herein, the polymerizable monomers according to the present disclosure can be used as, for example, reactive diluents for highly viscous curable resins, and in some embodiments, can also provide a crosslinked polymer that can have thermomechanical properties useful for devices such as medical devices (e.g., orthodontic appliances).

[0099] In various embodiments, the polymerizable monomers herein can be compounds according to formula (I):

[0100]

[0101] Wherein:

[0102] X is O, S, NR 6 or SiR 7 R 8 ;

[0103] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0104] R 2 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, substituted or unsubstituted cyclic (C3-8 ) an alkyl group, a substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0105] R 3 、R 4 and R 5 are each independently H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group or -Y-(CH2) n -R 9 ; or R 4 and R 5 together form a 4-, 5-, 6-, 7- or 8-membered ring, and the ring is selected from a substituted or unsubstituted cyclo(C 4-8 ) alkyl group, a substituted or unsubstituted cyclo(C 4-8) ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0106] wherein Y is O, S, NH or C(O)O;

[0107] n is an integer from 0 to 6;

[0108] R 6 、R 7 and R 8 are independently H or a substituted or unsubstituted C 1-6 alkyl group; and

[0109] R 9 is a substituted or unsubstituted cyclo(C 3-8 ) alkyl group, a substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0110] In some cases, R 3 is H. In some cases, R 3 is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group or -Y-(CH2) n-R 9 。In some cases, R 3 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, or a substituted or unsubstituted C 1-6 alkoxy. In some cases, R 3 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, or a substituted or unsubstituted C 1-6 alkoxy. In some cases, R 3 is a substituted or unsubstituted C 3-6 alkyl, a substituted or unsubstituted C 3-6 heteroalkyl, or a substituted or unsubstituted C 3-6 alkoxy. In some cases, R 3 is a substituted or unsubstituted C 1-2 alkyl or a substituted or unsubstituted C 1-2 alkoxy. In some cases, R 3 is an unsubstituted C 1-2 alkyl or an unsubstituted C 1-2 alkoxy. In some cases, R 3 is methyl or ethyl.

[0111] In some cases, R 4 is H. In some cases, R 4 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl, or -Y-(CH2) n -R 9 。In some cases, R 4 is a substituted or unsubstituted C 1-2 alkyl, a substituted or unsubstituted C 1-2 heteroalkyl, a substituted or unsubstituted C 1-2 alkoxy, a substituted or unsubstituted C 1-2 thioalkoxy. In some cases, R 4 is a substituted or unsubstituted C 3-6 alkyl, a substituted or unsubstituted C 3-6 heteroalkyl, a substituted or unsubstituted C 3-6 alkoxy, a substituted or unsubstituted C 3-6 thioalkoxy. In some cases, R 4}is a substituted or unsubstituted C 3-6 alkyl or a substituted or unsubstituted C 3-6 alkoxy. In some cases, R 4 is a substituted or unsubstituted C 4-6 alkyl or a substituted or unsubstituted C 4-6 alkoxy.

[0112] In various cases, R 1 is H or methyl. In some cases, X is O. In some cases, R 3 , R 4 and R 5 are each independently H, a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 ). In some cases, R 3 , R 4 and R 5 are each independently H, a substituted or unsubstituted C 1-6 alkyl, or a substituted or unsubstituted C 1-6 alkoxy; in some cases, at least one of R 3 , R 4 and R 5 is a substituted or unsubstituted C 1-6 alkoxy.

[0113] In some cases, R 5 is H. In some cases, R 5 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 . In some cases, R 5 is a substituted or unsubstituted C 1-2 alkyl, a substituted or unsubstituted C 1-2 heteroalkyl, a substituted or unsubstituted C 1-2 alkoxy, a substituted or unsubstituted C 1-2Thioalkoxy. In some cases, R 5 is a substituted or unsubstituted C 3-6 alkyl, a substituted or unsubstituted C 3-6 heteroalkyl, a substituted or unsubstituted C 3-6 alkoxy, or a substituted or unsubstituted C 3-6 thioalkoxy. In some cases, R 5 is a substituted or unsubstituted C 3-6 alkyl, or a substituted or unsubstituted C 3-6 alkoxy. In some cases, R 5 is a substituted or unsubstituted C 4-6 alkyl, or a substituted or unsubstituted C 4-6 alkoxy.

[0114] In some embodiments, R 2 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. In some cases, R 2 is an unsubstituted cyclo(C 3-8 )alkyl, an unsubstituted cyclo(C 3-8 )heteroalkyl, an unsubstituted aryl, or an unsubstituted heteroaryl. In some cases, R 2 is a substituted or unsubstituted cyclo(C 3-8 )alkyl or a substituted or unsubstituted aryl. In some cases, R 2 is an unsubstituted cyclo(C 3-8 )alkyl or an unsubstituted aryl. In some cases, R 2 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 carbonyl, or a substituted or unsubstituted C 1-6 carboxyl. In some cases, R 2 is an unsubstituted C 1-6 alkyl, an unsubstituted C 1-6 heteroalkyl, an unsubstituted C 1-6 carbonyl, or an unsubstituted C 1-6 carboxyl. In some cases, R 2 is a substituted or unsubstituted C 1-6 alkyl or a substituted or unsubstituted C 1-6 heteroalkyl. In some cases, R 2 is an unsubstituted C 1-3 alkyl or an unsubstituted C 1-3 heteroalkyl. In some cases, R 2 is an unsubstituted C 4-6alkyl or unsubstituted C 4-6 heteroalkyl. In some cases, R 2 is a substituted or unsubstituted C 1-2 alkyl. In some cases, R 2 is methyl or ethyl.

[0115] In some embodiments, X is O, R 2 is unsubstituted cyclo(C 3-8 )alkyl, unsubstituted aryl or unsubstituted heteroaryl, and R 3 , R 4 and R 5 are independently H. In this case, the polymerizable monomer can be selected from the following group:

[0116]

[0117] In some embodiments, X is O, R 2 is unsubstituted C 1-6 alkyl, and R 3 , R 4 and R 5 are independently H. In this case, the polymerizable monomer can be selected from the following group:

[0118]

[0119] In some embodiments, X is O, R 2 is unsubstituted C 1-6 alkyl, R 3 and R 4 are independently H, R 5 is unsubstituted C 1-6 alkoxy. In this case, the polymerizable monomer can be selected from the following group:

[0120] Or

[0121] In some embodiments, X is O, R 2 and R 3 are independently unsubstituted C 1-6 alkyl, R 4 is H, R 5 is unsubstituted C 1-6 alkoxy. In this case, the polymerizable monomer can be selected from the following group:

[0122]

[0123] In some embodiments, X is S or SiR 7 R 8 , and R 5is substituted or unsubstituted C 1-6 In this case, the polymerizable monomer may be:

[0124] or

[0125] In various embodiments, the polymerizable monomer herein may be a compound according to formula (II):

[0126]

[0127] in:

[0128] R 1 is H, substituted or unsubstituted C 1-3 Alkyl, or halogen;

[0129] R 10 is substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, substituted or unsubstituted ring (C 3-8 )alkyl, substituted or unsubstituted ring (C 3-8 ) heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0130] R 11 and R 12 are each independently H, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, or -X-(CH2) n -R 13 , or R 11 and R 12 Together they form a 4-, 5-, 6-, 7- or 8-membered ring selected from substituted or unsubstituted rings (C 4-8 )alkyl, substituted or unsubstituted ring (C 4-8 ) heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0131] wherein X is O, S, NH or C(O)O;

[0132] n is an integer from 0 to 6; and

[0133] R 13 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0134] In some cases, R 11 is H. In some cases, R 12 is H. In various cases, R 1 is H or methyl. In some cases, R 11 and R 12 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -X-(CH2) n -R 13 . In some cases, R 11 and R 12 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 alkoxy or substituted or unsubstituted C 1-6 thioalkoxy. In some cases, R 11 and R 12 are each independently H, substituted or unsubstituted C 3-6 alkyl, substituted or unsubstituted C 3-6 alkoxy, or substituted or unsubstituted C 3-6 thioalkoxy. In some cases, R 11 and R 12 are each independently H, substituted or unsubstituted C 3-6 alkyl. In some cases, R 11 and R 12 are each independently H, substituted or unsubstituted C 3-6 alkoxy. In some cases, at least one of R 11 and R 12 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -X-(CH2) n -R 13 。

[0135] In certain cases, R 10 is substituted or unsubstituted C 1-6 alkoxy. In this case, the polymerizable monomer can be:

[0136]

[0137] In various embodiments, the polymerizable monomers herein can be compounds according to formula (III):

[0138]

[0139] wherein:

[0140] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0141] R 14 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0142] R 15 and R 16 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or -X-(CH2) n -R 17 , or R 15 and R 16 together form a 4, 5, 6, 7 or 8-membered ring, said ring being selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0143] wherein X is O, S, NH or C(O)O;

[0144] n is an integer from 0 to 6; and

[0145] R 17 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0146] In some cases, R 1 is H or methyl. In some cases, R 14 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. In these cases, R 14 can be a substituted or unsubstituted aryl.

[0147] In some cases, R 14 is a substituted or unsubstituted C 1-6 alkyl, or a substituted or unsubstituted C 1-6 heteroalkyl. In some cases, R 14 is a substituted or unsubstituted C 1-3 alkyl, or a substituted or unsubstituted C 1-3 heteroalkyl. In some cases, R 14 is a substituted or unsubstituted C 4-6 alkyl, a substituted or unsubstituted C 4-6 heteroalkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, or a substituted or unsubstituted heteroaryl. In some cases, R 14 is an unsubstituted C 1-3 alkyl. In some cases, R 14 is an unsubstituted C 4-6 alkyl. In some cases, R 14 is a substituted or unsubstituted C 1-2 alkyl. In some cases, R 14 is an unsubstituted C 1-2 alkyl.

[0148] In some cases, at most one of R 15 and R 16 is H. In some cases, R 15 and R 16 are each independently H, a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl or -X-(CH2) n -R 17 . In some cases, R 15 and R 16 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 alkoxy or substituted or unsubstituted C 1-6 thioalkoxy. In some cases, R 15 and R 16 are each independently H, substituted or unsubstituted C 3-6 alkyl, substituted or unsubstituted C 3-6 alkoxy, or substituted or unsubstituted C 3-6 thioalkoxy. In some cases, R 15 and R 16 are each independently H, substituted or unsubstituted C 3-6 alkyl. In some cases, R 15 and R 16 are each independently H, substituted or unsubstituted C 3-6 alkoxy. In some cases, R 15 and R 16 are each independently H, substituted or unsubstituted C 1-2 alkyl. In some cases, R 15 and R 16 are each independently H, substituted or unsubstituted C 1-2 alkoxy.

[0149] In some embodiments, R 15 and R 16 are independently H, and R 14 is unsubstituted C 1-6 alkyl. In this case, the polymerizable monomer can be:

[0150] Or

[0151] In some cases, R 15 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -X-(CH2)n -R 17 。In some cases, R 16 is a substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -X-(CH2) n -R 17 。In some cases, R 15 and R 16 at least one of which is a substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy or substituted or unsubstituted C 1-6 thioalkoxy. In some cases, R 15 and R 16 together form a 4-, 5-, 6-, 7- or 8-membered ring selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8 )heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.

[0152] In some embodiments, R 15 and R 16 are independently H, and R 14 is unsubstituted aryl. In this case, the polymerizable monomer can be:

[0153] In this case, the polymerizable monomer can be:

[0154]

[0155] In some cases, the compound according to formula (III) has the structure according to formula (IIIa):

[0156]

[0157] Wherein:

[0158] R 82 is hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, OR 83 、-NR 83 R 84 、SR 83 or halogen; and

[0159] R 83 and R 84 are each independently selected from hydrogen and C 1-3 alkyl, or wherein R 83 and R 84 together form a 4-, 5-, 6-, 7- or 8-membered substituted or unsubstituted heterocyclic ring. In some cases, one or more of R 82 -R 84 are substituted by halogen, OH, NH2, NH(C 1-6 alkyl), N(C 1-6 alkyl)(C 1-6 alkyl) or C 1-3 alkyl. In some cases, one or more of R 82 -R 84 are substituted by halogen, OH or NH2.

[0160] In various embodiments, the polymerizable monomers herein can be compounds according to formula (IV):

[0161]

[0162] Wherein:

[0163] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0164] R 18 is substituted or unsubstituted C 1-6 alkyl or substituted or unsubstituted C 1-6 heteroalkyl; and

[0165] R 19 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, or substituted or unsubstituted C 1-6 carboxyl.

[0166] In some cases, R 1 is H or methyl. In some cases, R 18 is substituted or unsubstituted C 1-6 alkyl. In some cases, R 18 is substituted or unsubstituted C 1-3 alkyl. In certain cases, R 18 is unsubstituted C 1-3 alkyl. In certain cases, R 18is a substituted or unsubstituted C 1-2 alkyl. In certain cases, R 18 is an unsubstituted C 1-2 alkyl. In certain cases, R 18 is a substituted or unsubstituted C 4-6 alkyl. In certain cases, R 18 is an unsubstituted C 4-6 alkyl. In certain cases, R 19 is a substituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, or a substituted or unsubstituted C 1-6 carboxyl. In certain cases, R 19 is a substituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, or a substituted or unsubstituted C 1-6 alkoxy. In certain cases, R 18 is a substituted or unsubstituted C 3-6 alkyl, R 19 is a substituted or unsubstituted C 1-6 alkoxy. In certain cases, R 18 is a substituted or unsubstituted C 3-6 alkyl, R 19 is a substituted or unsubstituted C 1-6 alkyl. In certain cases, R 18 is a substituted or unsubstituted C 3-6 alkyl, R 19 is a substituted or unsubstituted C 1-6 heteroalkyl. In certain cases, R 18 is a substituted or unsubstituted C 3-4 alkyl, R 19 is a substituted or unsubstituted C 1-3 alkoxy. In certain cases, R 18 is a substituted or unsubstituted C 3-4 alkyl, R 19 is a substituted or unsubstituted C 1-3 alkyl. In certain cases, R 18 is a substituted or unsubstituted C 3-4 alkyl, R 19 is a substituted or unsubstituted C 1-3 heteroalkyl. In certain cases, R 18 is a substituted C 2-6 alkyl, R 19 is an unsubstituted C1-6 Alkyl. In some cases, R 18 is a substituted or unsubstituted C 1-2 alkyl, and R 19 is a substituted or unsubstituted C 1-6 alkoxy. In some cases, R 18 is a substituted or unsubstituted C 1-2 alkyl, and R 19 is a substituted or unsubstituted C 1-6 alkyl. In some cases, R 18 is a substituted or unsubstituted C 1-2 alkyl, and R 19 is a substituted or unsubstituted C 1-6 heteroalkyl. In some cases, R 18 is a substituted or unsubstituted C 1-2 alkyl, and R 19 is a substituted or unsubstituted C 1-3 alkoxy. In some cases, R 18 is a substituted or unsubstituted C 1-2 alkyl, and R 19 is a substituted or unsubstituted C 1-3 alkyl. In some cases, R 18 is a substituted or unsubstituted C 1-2 alkyl, and R 19 is a substituted or unsubstituted C 1-3 heteroalkyl. In some cases, R 18 is a substituted C1 alkyl, and R 19 is an unsubstituted C 1-6 alkyl. In this case, the polymerizable monomer can be:

[0167] Or

[0168] In various embodiments, the polymerizable monomer herein can be a compound according to formula (V):

[0169]

[0170] Wherein:

[0171] R 1 is H, a substituted or unsubstituted C 1-3 alkyl, or a halogen;

[0172] R 20 and R 22 are each independently a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6alkoxy, substituted or unsubstituted C1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 1 -(CH2) a -R 28 ;

[0173] R 21 and R 23 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 2 -(CH2) b -R 29 ;

[0174] R 24 and R 26 are each independently substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 3 -(CH2) c -R 30 ;

[0175] R 25 and R 27 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 4 -(CH2) d -R 31 ;

[0176] X 1 、X 2 、X 3 and X 4Each is independently a key, O, or S;

[0177] a, b, c, and d are each independently an integer from 0 to 6; and

[0178] R 28 , R 29 , R 30 and R 31 are each independently a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0179] In various embodiments, the polymerizable monomers herein can be compounds according to formula (V):

[0180]

[0181] wherein:

[0182] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0183] R 20 and R 22 are each independently substituted or unsubstituted C 4-6 alkyl, substituted or unsubstituted C 3-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 1 -(CH2) a -R 28 ;

[0184] R 21 and R 23 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 2 -(CH2) b -R 29 ;

[0185] R 24 and R26 Each is independently a substituted or unsubstituted C 3-6 alkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 2-6 carboxyl, or –X 3 -(CH2) c -R 30 ;

[0186] R 25 and R 27 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 4 -(CH2) d -R 31 ;

[0187] X 1 、X 2 、X 3 and X 4 are each independently a bond, O or S;

[0188] a, b, c and d are each independently an integer from 0 to 6; and

[0189] R 28 、R 29 、R 30 and R 31 are each independently a substituted cyclo(C 3-8 )alkyl, substituted cyclo(C 3-8 )heteroalkyl, substituted aryl, or substituted or unsubstituted heteroaryl.

[0190] In some cases, at least one of R 20 and R 22 is –X 1 -(CH2) a -R 28 ; at least one of R 21 and R 23 is –X 2 -(CH2) b -R 29 ; at least one of R 24 and R 26 is –X3 -(CH2) c -R 30 ; R 25 and R 27 at least one of which is –X 4 -(CH2) d -R 31 ; or a combination thereof.

[0191] In some cases, Cy is In some cases, R 20 , R 21 , R 22 and R 23 at least one of which is a substituted or unsubstituted C 1-6 alkoxy.

[0192] In some cases, Cy is In some cases, R 24 , R 25 , R 26 and R 27 at least one of which is a substituted or unsubstituted C 1-6 alkoxy.

[0193] In certain cases, R 20 and R 22 are each independently a substituted or unsubstituted C 1-2 alkyl or a substituted or unsubstituted C 1-2 heteroalkyl. In certain cases, R 20 and R 22 are each independently a substituted or unsubstituted C 4-6 alkyl, a substituted or unsubstituted C 3-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy or –X 1 -(CH2) a -R 28 。In certain cases, R 20 and R 22 are each independently a substituted or unsubstituted C 4-6 alkyl, a substituted or unsubstituted C 1-6 alkoxy or –X 1 -(CH2) a -R 28 。In certain cases, R 20 and R 22 are each independently a substituted or unsubstituted C 4-6 alkyl or an unsubstituted C 1-6 alkoxy. In some cases, R 20 and R 22 are each independently an unsubstituted C1-2 alkyl or unsubstituted C 1-2 alkoxy group.

[0194] In certain cases, at least one of R 21 and R 23 is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group or –X 2 -(CH2) b -R 29 。 In certain cases, at least one of R 21 and R 23 is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group or –X 2 -(CH2) b -R 29 。 In certain cases, at least two of R 28 , R 29 , R 30 and R 31 are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. In certain cases, at least one of R 21 and R 23 is –X 2 -(CH2) b -R 29 , and each R 29 is independently a substituted or unsubstituted cyclo(C 3-8 )alkyl group, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. In certain cases, a is independently 2 - 6 in each instance. In certain cases, a is 0 in each instance.

[0195] In certain cases, R 24 and R 26 are each independently a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 alkoxy group or –X 3 -(CH2) c -R 30 。 In certain cases, R 24 and R 26Each independently is a substituted or unsubstituted C 1-2 alkyl, a substituted or unsubstituted C 3-6 alkyl, or an unsubstituted C 1-6 alkoxy.

[0196] In some cases, at least one of R 25 and R 27 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl or –X 4 -(CH2) d -R 31 . In some cases, at least one of R 25 and R 27 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy or –X 4 -(CH2) d -R 31 . In some cases, at least one of R 25 and R 27 is a substituted or unsubstituted C 1-3 alkyl or an unsubstituted C 1-3 alkoxy. In some cases, c is independently 2 - 6 in each instance. In some cases, c is 0 in each instance.

[0197] In this case, the polymerizable monomer may be selected from the following group:

[0198]

[0199]

[0200] In various embodiments, the polymerizable monomer herein may be a compound according to formula (VI):

[0201]

[0202] Wherein:

[0203] R 1 is H, a substituted or unsubstituted C 1-3 alkyl, or a halogen;

[0204] R 32 and R34 Each independently is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group, or –X 5 -(CH2) e -R 42 ;

[0205] R 33 and R 35 Each independently is H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group, or –X 6 -(CH2) f -R 43 ;

[0206] R 36 and R 38 Each independently is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group, or –X 7 -CH2) g -R 44 ;

[0207] R 37 and R 39 Each independently is H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group, or –X 8 -(CH2) h -R 45;

[0208] R 40 is substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, or –X 9 -(CH2) i -R 46 ;

[0209] R 41 is H, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, or –X 10 -(CH2) j -R 47 ;

[0210] X 5 、X 6 、X 7 、X 8 、X 9 and X 10 are each independently a bond, O or S;

[0211] e, f, g, h, i, and j are each independently an integer from 0 to 6; and

[0212] R 42 、R 43 、R 44 、R 45 、R 46 and R 47 Each independently is a substituted or unsubstituted ring (C 3-8 )alkyl, substituted or unsubstituted ring (C 3-8 ) heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0213] In some cases, Cy is or In some cases, Cy is In some cases, R 32 、R 33 、R 34and R 35 at least one of which is a substituted or unsubstituted C 1-6 alkoxy or a substituted or unsubstituted C 1-6 thioalkoxy. In some cases, Cy is In some cases, R 36 , R 37 , R 38 and R 39 at least one of which is a substituted or unsubstituted C 1-6 alkoxy or a substituted or unsubstituted C 1-6 thioalkoxy. In some cases, Cy is In some cases, R 41 is a substituted or unsubstituted C 1-6 alkoxy or a substituted or unsubstituted C 1-6 thioalkoxy. In some cases, R 40 is a substituted or unsubstituted C 3-6 alkoxy or a substituted or unsubstituted C 3-6 thioalkoxy. In some cases, R 40 is a substituted or unsubstituted C 1-2 alkoxy or a substituted or unsubstituted C 1-2 thioalkoxy.

[0214] In some cases, R 33 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl or –X 6 -(CH2) f -R 43 。In some cases, R 33 and R 35 are each independently a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl or –X 6 -(CH2) f -R 43 。In some cases, R 37 is a substituted or unsubstituted C 1-6Alkyl, substituted or unsubstituted C 1-6 Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl or –X 6 -(CH2) f -R 43 . In some cases, R 37 and R 39 are each independently a substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 6 -(CH2) f -R 43 .

[0215] In various embodiments, the polymerizable monomer can be a compound according to formula (VI):

[0216]

[0217] Wherein:

[0218] R 1 is H, a substituted or unsubstituted C 1-3 alkyl, or a halogen;

[0219] R 32 and R 34 are each independently a substituted or unsubstituted C 3-6 alkyl, substituted or unsubstituted C 3-6 heteroalkyl, substituted or unsubstituted C 1- 6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 5 -(CH2) e -R 42 ;

[0220] R 33 and R 35 are each independently H, a substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 6 -(CH2) f -R 43 ;

[0221] R 36 and R 38 are each independently substituted or unsubstituted C 3-6 alkyl, substituted or unsubstituted C 4-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 7 -CH2) g -R 44 ;

[0222] R 37 and R 39 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 8 -(CH2) h -R 45 ;

[0223] X 5 、X 6 、X 7 and X 8 are each independently a bond, O or S;

[0224] e, f, g and h are each independently an integer from 0 to 6;

[0225] R 42 and R 43 are each independently substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and

[0226] R 44 and R 45Each independently is a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted aryl, or substituted or unsubstituted heteroaryl.

[0227] In certain cases, R 1 is H or methyl. In such cases, the polymerizable monomer can be selected from the following group:

[0228]

[0229] In certain cases, the polymerizable monomer can be selected from the following group:

[0230]

[0231] In certain cases, any one or more of R 1 -R 84 can be substituted by halogen, OH, NH2, NH(C 1-6 alkyl), N(C 1-6 alkyl)(C 1-6 alkyl) or C 1-3 alkyl. In certain cases, R 1 -R 84 can be substituted by halogen, OH, NH2 or C 1-3 alkyl. In certain cases, R 1 -R 84 can be substituted by fluorine, chlorine, bromine, OH or C 1-3 alkyl. In certain cases, R 1 -R 84 can be substituted by halogen, OH or NH3.

[0232] In some embodiments, provided herein is a polymerizable monomer according to formula (IX):

[0233]

[0234] Wherein:

[0235] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0236] R 77 is nitrile, substituted or unsubstituted C 1-6 alkyl cyanide, or substituted or unsubstituted C 1-6 carbonyl;

[0237] R 78 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxy, substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0238] R 79 and R 80 are each independently H, C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxy, substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and

[0239] R 81 is substituted or unsubstituted C 1-6 alkoxy.

[0240] In some cases, R 77 is nitrile or substituted or unsubstituted C 1-6 alkyl cyanide. In some cases, R 79 and R 80 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxy, substituted or unsubstituted cyclo(C 3-8 )alkyl or substituted or unsubstituted cyclo(C 3-8 )heteroalkyl. In some cases, R 79 and R 80 are each independently H, unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted cyclo(C 3-8 )alkyl or substituted or unsubstituted cyclo(C 3-8)Heteroalkyl. In some cases, R 79 and R 80 are each independently H, unsubstituted C 1-4 alkyl, or unsubstituted C 1-4 alkoxy. In some cases, R 81 is unsubstituted C 1-6 alkoxy.

[0241] In some embodiments, the polymerizable monomer of formula (IX) can be vanillin, such as o-vanillin, or a derivative thereof. In this case, R 77 is nitrile. In this case, R 77 is carbonyl or aldehyde. In any such case, R 81 can be methoxy, R 1 is hydrogen or methyl. In this case, the polymerizable monomer of formula (IX) can have the following structure:

[0242] Or

[0243] In some embodiments, provided herein is a polymeric material comprising a polymer that comprises the monomer of formula (VII) in polymerized form:

[0244]

[0245] Wherein:

[0246] X is N or CR 59 ;

[0247] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0248] R 48 , R 49 and R 50 are each independently H, nitrile, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –Y 1 -(CH2) a -R 60 , or R 48 and R 49 together form a 4-, 5-, 6-, 7- or 8-membered ring selected from substituted or unsubstituted cyclo(C4-8 ) an alkyl group, a substituted or unsubstituted cyclo(C 4-8 ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0249] R 51 、R 52 、R 53 and R 54 are each independently H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group or –Y 2 -(CH2) b -R 61 ;

[0250] R 55 、R 56 、R 57 and R 58 are each independently H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group or –Y 3 -(CH2) c -R 62 ;

[0251] R 59 is H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group, or –Y 4 -(CH2) d -R 63 ;

[0252] Y 1 、Y 2 、Y 3 and Y 4 are each independently a bond, O or S;

[0253] a, b, c, and d are each independently an integer from 0 to 6; and

[0254] R 60 , R 61 , R 62 and R 63 are each independently a substituted or unsubstituted cyclo(C 3-8 )alkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0255] In some cases, referring to formula (VII),

[0256]

[0257] wherein:

[0258] X is N or CR 59 ;

[0259] R 1 is H, a substituted or unsubstituted C 1-3 alkyl, or a halogen;

[0260] R 48 , R 49 and R 50 are each independently H, a nitrile, a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl, or –Y 1 -(CH2) a -R 60 , or R 48 and R 49 together form a 4-, 5-, 6-, 7-, or 8-membered ring selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0261] R 59 is H, a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –Y 4 -(CH2) d -R 63 ;

[0262] Y 1 and Y 4 each independently is a bond, O, or S;

[0263] a and d each independently are integers from 0 to 6; and

[0264] R 60 and R 63 each independently are substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0265] In some embodiments, provided herein is a polymeric material comprising a polymer that comprises a monomer in polymerized form as shown in formula (VII):

[0266]

[0267] wherein:

[0268] X is N or CH;

[0269] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0270] R 48 , R 49 and R 50 each independently are H, nitrile, substituted or unsubstituted C 1-6 alkyl cyanide, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –Y 1 -(CH2) a -R 60 ; or R 48 together with R 49 forms a 4-, 5-, 6-, 7-, or 8-membered ring selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8Heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, wherein R 48 , R 49 and R 50 at most one of which is H;

[0271] R 51 , R 52 , R 53 and R 54 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –Y 2 -(CH2) b -R 61 ;

[0272] R 55 , R 56 , R 57 and R 58 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –Y 3 -(CH2) c -R 62 ;

[0273] Y 1 , Y 2 , Y 3 and Y 4 are each independently a bond, O or S;

[0274] a, b, c and d are each independently an integer from 0 to 6;

[0275] R 60 and R 62 are each independently substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and

[0276] R 61 is a substituted cyclo(C3-8 ) an alkyl group, a substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0277] In some cases, R 1 is H or methyl. In this case, X is N or CR 59 , R 49 is H, R 48 and R 50 are each independently a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group or –Y 1 -(CH2) a -R 60 , where Y 1 is a bond, O or S, a is an integer from 0 to 6, and R 59 is H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, R 60 is a substituted or unsubstituted cyclo(C 3-8 ) alkyl group, a substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or, R 48 and R 49 together form a 4-, 5-, 6-, 7- or 8-membered ring selected from a substituted or unsubstituted cyclo(C 4-8 ) alkyl group, a substituted or unsubstituted cyclo(C 4-8 ) heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. In some cases, X is N or CH, R 49 is H, R 48 and R 50 are each independently a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group or –Y 1 -(CH2) a -R 60 , where Y 1 is a bond or O, a is 0, 1 or 2, and R 60 is a substituted or unsubstituted cyclo(C 3-8 ) alkyl group, a substituted or unsubstituted cyclo(C3-8 ) heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other cases, X is N or CH, and R 49 is H, and R 48 and R 50 are each independently substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 alkoxy, or –Y 1 -(CH2) a -R 60 , where Y 1 is a bond or O, a is 0, 1, or 2, and R 60 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0278] In some cases, referring to formula (VII),

[0279]

[0280] where:

[0281] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0282] R 51 , R 52 , R 53 and R 54 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –Y 2 -(CH2) b -R 61 ;

[0283] Y 2 is a bond, O, or S;

[0284] b is an integer from 0 to 6; and

[0285] R 61 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0286] In some cases, R 1 is H or methyl. In such cases, R 51 , R 52 , R 53 and R 54 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy or –Y 2 -(CH2) b -R 61 , where Y 2 is a bond, O or S, b is an integer from 0 to 6, and R 61 is substituted or unsubstituted cyclic(C 3-8 )alkyl, substituted or unsubstituted cyclic(C 3-8 )heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. In some cases, R 52 and R 54 are H, and R 51 and R 53 are each independently substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy or –Y 2 -(CH2) b -R 61 , where Y 2 is a bond, O or S, b is an integer from 0 to 6, and R 61 is substituted or unsubstituted cyclic(C 3-8 )alkyl, substituted or unsubstituted cyclic(C 3-8 )heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. In other cases, R 52 and R 54 are H, and R 51 and R 53 are each independently substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy or –Y 2 -(CH2) b -R 61 , where Y 2 is a bond or O, b is an integer from 0 to 3, and R 61 is substituted or unsubstituted cyclic(C3-8 ) an alkyl, a substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0287] In some cases, referring to formula (VII),

[0288]

[0289] wherein:

[0290] R 1 is H, a substituted or unsubstituted C 1-3 alkyl, or a halogen;

[0291] R 55 , R 56 , R 57 and R 58 are each independently H, a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl or –Y 3 -(CH2) c -R 62 ;

[0292] Y 3 is a bond, O or S;

[0293] c is an integer from 0 to 6; and

[0294] R 62 is a substituted or unsubstituted cyclo(C 3-8 ) alkyl, a substituted or unsubstituted cyclo(C 3-8) ) heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0295] In certain cases, R 1 is H or methyl. In this case, R 55 , R 56 , R 57 and R 58 are each independently H, a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C1-6 carboxyl or –Y 3 -(CH2) c -R 62 , wherein Y 3 is a bond, O or S, c is an integer from 0 to 6, and R 62 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In some aspects, in some cases, R 56 and R 58 are H, R 55 and R 57 are each independently a substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –Y 3 -(CH2) c -R 62 , wherein Y 3 is a bond, O or S, c is an integer from 0 to 6, and R 62 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other cases, R 56 and R 58 are H, R 55 and R 57 are each independently a substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy or –Y 3 -(CH2) c -R 62 , wherein Y 3 is a bond or O, c is an integer from 0 to 3, and R 62 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0296] In some embodiments, provided herein is a polymeric material comprising a polymer that comprises a monomer in polymerized form as shown in formula (VIII):

[0297]

[0298] Wherein:

[0299] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0300] R 64 、R 65 、R 66 and R 67 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 1 -(CH2) a -R 74 ;

[0301] R 68 、R 69 、R 70 and R 71 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 2 -(CH2) b -R 75 ;

[0302] R 72 and R 73 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 3 -(CH2) c -R 76 ;

[0303] X1 , X 2 and X 3 are each independently a bond, O, or S;

[0304] a, b, and c are each independently an integer from 0 to 6; and

[0305] R 74 , R 75 and R 76 are each independently a substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0306] In some embodiments, provided herein is a polymeric material comprising a polymer that comprises a monomer in polymerized form as shown in formula (VIII):

[0307]

[0308] wherein:

[0309] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0310] R 64 , R 65 , R 66 and R 67 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 1 -(CH2) a -R 74 , where R 64 , R 65 , R 66 and R 67 at most two of which are H;

[0311] R 68 , R 69 , R 70 and R 71 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl or –X 2 -(CH2) b -R 75 wherein R 68 、R 69 、R 70 and R 71 at most two of which are H;

[0312] R 72 and R 73 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 3 -(CH2) c -R 76 ;

[0313] X 1 、X 2 and X 3 are each independently a bond, O or S;

[0314] a, b and c are each independently integers from 0 to 6; and

[0315] R 74 、R 75 and R 76 are each independently substituted or unsubstituted cyclic(C 3-8 )alkyl, substituted or unsubstituted cyclic(C 3-8 )heteroalkyl, substituted aryl, or substituted or unsubstituted heteroaryl.

[0316] In some cases, referring to formula (VIII),

[0317]

[0318] wherein:

[0319] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0320] R 64 、R 65 、R 66 and R67 Each independently is H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 1 -(CH2) a -R 74 ;

[0321] X 1 is a bond, O or S;

[0322] a is an integer from 0 to 6; and

[0323] R 74 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0324] In some cases, R 1 is H or methyl. In this case, R 65 and R 67 are H, R 64 and R 66 each independently is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 1 -(CH2) a -R 74 where X 1 is a bond or O, a is an integer from 0 to 3, and R 74 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.

[0325] In some cases, referring to formula (VIII),

[0326]

[0327] where:

[0328] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0329] R 68 , R 69 , R 70 and R 71 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 2 -(CH2) b -R 75 ;

[0330] X 2 is a bond, O or S;

[0331] b is an integer from 0 to 6; and

[0332] R 75 is substituted or unsubstituted cyclic(C 3-8 )alkyl, substituted or unsubstituted cyclic(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0333] In some cases, R 1 is H or methyl. In such cases, R 69 and R 71 are H, R 68 and R 70 are each independently substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 2 -(CH2) b -R 75 , where X 2 is a bond or O, b is an integer from 0 to 3, and R 75 is substituted or unsubstituted cyclic(C 3-8 )alkyl, substituted or unsubstituted cyclic(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0334] In some cases, referring to formula (VIII),

[0335]

[0336] wherein:

[0337] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0338] R 72 and R 73 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or –X 3 -(CH2) c -R 76 ;

[0339] X 3 is a bond, O or S;

[0340] c is an integer from 0 to 6; and

[0341] R 76 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0342] In certain cases, R 1 is H or methyl. In such cases, R 72 and R 73 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy or –X 3 -(CH2) c -R 76 , wherein X 3 is a bond or O, c is an integer from 0 to 3, and R 75 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8) heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In other cases, R 72 is H, R 73 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy or –X 3 -(CH2) c -R 76 where X 3 is a bond or O, c is an integer from 0 to 3, and R 75 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0343] In some cases, referring to Formulas (VII) and (VIII), one or more of R 1 or R 48 -R 81 are substituted by halogen, OH, NH2, NH(C 1-6 alkyl), N(C 1-6 alkyl)(C 1-6 alkyl), or C 1-3 alkyl.

[0344] In some embodiments, the polymerizable monomers of the present disclosure have a low vapor pressure and a high boiling point at elevated temperatures. This low vapor pressure is particularly advantageous for using such monomers in curable (e.g., photocurable) compositions and additive manufacturing, as elevated temperatures (e.g., 60 °C, 80 °C, 90 °C or higher) may be used in these applications. In various cases, the vapor pressure of the polymerizable monomer at 60 °C is at most about 12 Pa. In various cases, the vapor pressure of the polymerizable monomer at 60 °C is at most about 2 Pa to 10 Pa. In various cases, the vapor pressure of the polymerizable monomer at 60 °C is at most about 2 Pa to 5 Pa. Thus, in some embodiments, the polymerizable monomers of the present disclosure may have a lower mass loss at elevated temperatures. The mass loss of a compound used herein when heated for a specific period of time (e.g., 2 hours) at a specific temperature (e.g., 90 °C) can be used as a measure of the volatility of such a compound. As used herein, "substantially non-volatile" may refer to a mass loss of less than 1 wt% at the corresponding temperature (e.g., when heated at 90 °C for 2 hours). In various cases, the polymerizable monomers of the present disclosure may have a mass loss of less than 1 wt% after being heated at 90 °C for 2 hours. In some embodiments, the polymerizable monomer may have a mass loss of less than about 0.5% after being heated at 90 °C for 2 hours. In some embodiments, the polymerizable monomer may have a mass loss of about 0.1% to about 0.45% after being heated at 90 °C for 2 hours. In some embodiments, the polymerizable monomer may have a mass loss of about 0.05% to about 0.25% after being heated at 90 °C for 2 hours.

[0345] In some embodiments, the molecular weight of the polymerizable monomers of the present disclosure can 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 from 190 to 320 daltons. In some cases, the molecular weight of the polymerizable monomer is from 200 to 280 daltons.

[0346] In some embodiments, the melting point of the polymerizable monomers of the present disclosure can be at least about 20°C, 30°C, 40°C, 50°C or higher. The polymerizable monomers of the present disclosure, for example, monomers according to any one of formulas (I)-(VI) and (IX), in terms of their possible use as reactive diluents in curable compositions, have a melting point lower than the processing temperature employed in current high-temperature lithography-based photopolymerization processes, which is typically in the range of 50 - 120°C, for example 90 - 120°C. Thus, the melting point of the polymerizable monomers that can be used as reactive diluents provided herein can be less than 120°C, less than 90°C, less than 70°C, or even less than 50°C or less than 30°C, which results in a lower melt viscosity. Therefore, when they are used as reactive diluents for high-temperature lithography-based polymerizable and curable resins, their viscosity-reducing effect is more significant. In certain cases, they are in a liquid state at room temperature and are easy to handle in addition to the above advantages.

[0347] In various embodiments, any of the polymerizable monomers described herein, for example, compounds according to any one of formulas (I)-(VI) and (IX), can be photo-polymerizable monomers. In various cases, the photo-polymerizable monomers of the present disclosure can be components of a photo-polymerizable composition (e.g., a photo-curable resin), and the composition can be 3D printed as described herein.

[0348] In some embodiments, the photo-polymerizable monomers of the present disclosure can be added to the photo-curable resins described herein to, for example, change (e.g., reduce) the viscosity of the resin, promote cross-linking between telechelic polymers during polymerization (e.g., during curing), extend the polymer chains during polymerization, initiate and / or enhance phase separation induced by polymerization during curing (e.g., photo-curing), control the size of the phases or domains formed during the phase separation process, increase the toughness of the polymeric material made from the resin, change the glass transition temperature (Tg) of the amorphous regions (e.g., amorphous polymer phase) of the polymeric material made from the resin, change the melting point temperature (Tm) of the crystalline regions (e.g., crystalline polymer phase) of the polymeric material made from the resin, or adjust the refractive index of the amorphous regions of the polymeric material made from the resin.

[0349] II. Photo-Curable Resins

[0350] The present disclosure provides curable resins that can comprise one or more of the polymerizable monomers described herein. In certain cases, the curable resins are photo-curable, chemically curable, thermally curable, or any combination thereof. In certain cases, the curable resins described herein are photo-curable resins that can comprise one or more photo-polymerizable monomers, such as one or more compounds according to any one of formulas (I)-(VI) and (IX).

[0351] Resin Composition

[0352] The photocurable resin of the present disclosure may include one or more components. One or more of these components may be a photopolymerizable component. In this case, the photocurable resin herein may include 1, 2, 3, 4, 5 or more different types of photopolymerizable monomers described herein. In certain cases, each monomer may be a compound conforming to any one of formulas (I)-(VI) and (IX).

[0353] In some cases, the photocurable resin comprises 10 - 80 wt% of a compound of any one of formulas (I)-(VI) and (IX). In some cases, the photocurable resin comprises 15 - 45 wt% of a compound of any one of formulas (I)-(VI) and (IX). In some cases, the photocurable resin comprises 25 - 35 wt% of a compound of any one of formulas (I)-(VI) and (IX). In some cases, the photocurable resin comprises 10 - 50 wt% of a second acrylate or methacrylate monomer that is copolymerizable with the polymerizable monomer of any one of formulas (I)-(VI) and (IX). In some cases, the second acrylate or methacrylate monomer is an alkyl acrylate, alkyl methacrylate, homomenthyl acrylate, homomenthyl methacrylate, or a combination thereof. In some cases, the second acrylate or methacrylate monomer is homomenthyl acrylate, homomenthyl methacrylate, or a combination thereof. The photocurable resin of the present disclosure may further comprise one or more photopolymerizable components in addition to one or more photopolymerizable monomers. These photopolymerizable components may include one or more telechelic oligomers, one or more telechelic polymers, or a combination thereof. In such cases, the number average molecular weight of the telechelic oligomer may be greater than 500 Da (0.5 kDa) and less than 5 kDa. The number average molecular weight of the telechelic polymer may be greater than 10 kDa and less than 50 kDa. The number average molecular weight of the telechelic polymer may be greater than 5 kDa and less than 50 kDa. The number average molecular weight of the telechelic polymer may be greater than 5 kDa and less than 300 kDa. The ends of the telechelic oligomer and / or polymer may comprise a photoreactive moiety. In some cases, the photoreactive moiety may be an acrylate, methacrylate, acrylate vinyl ester, methacrylate vinyl ester, allyl ether, silene, alkyne, alkene, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some cases, the photoreactive moiety may be an acrylate or methacrylate. The telechelic polymers herein may include polyurethanes, polyesters, block copolymers, or any other commercial polymers having reactive (e.g., photoreactive) end groups. Thus, in various cases, the telechelic block copolymers of the present disclosure are capable of photopolymerization with one or more other telechelic polymers, telechelic block copolymers, telechelic oligomers, or polymerizable monomers according to any one of formulas (I)-(VI) and (IX) through their terminal monomers. In various cases, the terminal monomers comprise a photoreactive moiety, thereby enabling further photopolymerization reactions. Such photopolymerization reactions of the telechelic block copolymers with other polymers, oligomers, and / or monomers may occur during the photocuring process, e.g., in cases where these components are part of the photocurable resin. In some cases, the telechelic polymer may have one or more glass transition temperatures, at least one of which is 0 °C or lower.

[0354] In some aspects, the photo-polymerizable monomers of the present disclosure are miscible with another, second photo-polymerizable component (e.g., a telechelic polymer). In some aspects, the polymerizable monomers herein may be partially or completely insoluble in the second polymerizable component.

[0355] The photo-curable resins disclosed herein may comprise from about 0.5 - 99.5 wt%, about 1 - 99 wt%, about 10 - 95 wt%, about 20 - 90 wt%, about 25 - 60 wt% or about 35 - 50 wt% of one or more polymerizable monomers, telechelic polymers and / or oligomers according to any one of formulas (I)-(VI) and (IX), or any combination thereof.

[0356] The photo-curable resins described herein may further comprise a photoinitiator. Such photoinitiators, when activated with light of an appropriate wavelength (e.g., ultraviolet / visible light), may initiate a polymerization reaction (e.g., during the photocuring process) between the telechelic polymers, monomers and other potentially polymerizable components that may be present in the photo-curable resin, thereby forming the polymeric materials further described herein. Generally, the photoinitiators described in the present disclosure may include those that can be activated by light and initiate the polymerization of the polymerizable components in the formulation.

[0357] In some embodiments, the photoinitiator is a free radical photoinitiator. In certain embodiments, the free radical photoinitiator comprises an α-hydroxy ketone moiety (such as 2-hydroxy-2-methylpropiophenone or 1-hydroxycyclohexyl phenyl ketone), an α-amino ketone (such as 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), 4-methyldibenzoyl, an azo compound (such as 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanenitrile), azobisisobutyronitrile, 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 photoinitiator that includes SpeedCure TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate). In some aspects, the photocurable resin comprises a photoinitiator selected from benzophenone, a mixture of benzophenone and a tertiary amine containing a carbonyl group directly bonded to at least one aromatic ring, and Irgacure (such as Irgacure 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) or Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one). In some embodiments, the photoinitiator includes an acetophenone photoinitiator (such as 4'-hydroxyacetophenone, 4'-phenoxyacetophenone, 4'-ethoxyacetophenone), benzoin, benzoin derivatives, benzil, benzil derivatives, benzophenone (such as 4-benzoyl biphenyl, 3,4-(dimethylamino)benzophenone, 2-methylbenzophenone), cationic photoinitiators (such as diphenyliodonium nitrate, (4-iodophenyl)diphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate), anthraquinone, quinones (such as camphorquinone), phosphine oxides, phosphinates, 9,10-phenanthrenequinone, thioxanthone, any combination thereof, or any derivative thereof.

[0358] In some embodiments, the maximum wavelength absorbance of the photoinitiator can be 200 to 300 nm, 300 to 400 nm, 400 to 500 nm, 500 to 600 nm, 600 to 700 nm, 700 to 800 nm, 800 to 900 nm, 150 to 200 nm, 200 to 250 nm, 250 to 300 nm, 300 to 350 nm, 350 to 400 nm, 400 to 450 nm, 450 to 500 nm, 500 to 550 nm, 550 to 600 nm, 600 to 650 nm, 650 to 700 nm or 700 to 750 nm. In some embodiments, the maximum wavelength absorbance of the photoinitiator is between 300 and 500 nm.

[0359] In some embodiments, the photocurable resin of the present disclosure comprises more than one initiator (e.g., 2, 3, 4, 5 or more than 5 initiators). In some embodiments, the photocurable resin comprises one thermal initiator as an initiator. In certain embodiments, the thermal initiator comprises an organic peroxide. In some embodiments, the thermal initiator comprises an azo compound, an inorganic peroxide, an organic peroxide, or any combination thereof. In some embodiments, the thermal initiator is selected from tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanenitrile), 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, potassium persulfate, derivatives thereof, and combinations thereof. In a preferred embodiment, the thermal initiator comprises azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), or a combination thereof.

[0360] In some embodiments, the photocurable resin comprises 0.01-10 wt%, 0.02-5 wt%, 0.05-4 wt%, 0.1-3 wt%, 0.1-2 wt% or 0.1-1 wt% of an initiator. In a preferred embodiment, the photocurable resin comprises 0.1-2 wt% of an initiator. In some embodiments, the photocurable resin 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. In a preferred embodiment, the photocurable resin comprises 0.1-2 wt% of a photoinitiator. In some embodiments, 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 thermal initiator. In a preferred embodiment, the photocurable resin comprises 0 to 0.5 wt% of a thermal initiator.

[0361] In some embodiments, the photocurable resin of the present disclosure may include a crosslinking modifier (e.g., in addition to polymerizable monomers that can act as crosslinking agents, or in cases where the polymerizable monomers do not act as crosslinking agents), a solvent, a glass transition temperature modifier, a toughness modifier, a polymerization catalyst, a polymerization inhibitor, a photoresist, a plasticizer, a surface energy modifier, a pigment, a dye, a filler, a biologically significant chemical substance, or a combination thereof.

[0362] In certain aspects, the photocurable resin includes a crosslinking modifier. As used herein, "crosslinking modifier" refers to a substance that bonds one oligomer or polymer chain to another oligomer or polymer chain, thereby forming a crosslink. The crosslinking modifier can become part of another substance, such as crosslinks in a polymer material obtained through a polymerization process. In some embodiments, the crosslinking modifier is a curable unit that, when mixed with the photocurable resin, is incorporated as a crosslink into the polymer material formed by polymerization of the formulation. In certain embodiments, the photocurable resin includes 0 - 25 wt% of the crosslinking modifier, and the number average molecular weight of the crosslinking modifier is less than or equal to 3 kDa, less than or equal to 2.5 kDa, less than or equal to 2 kDa, less than or equal to 1.5 kDa, less than or equal to 1.25 kDa, less than or equal to 1 kDa, less than or equal to 800 Da, less than or equal to 600 Da, or less than or equal to 400 Da. In some embodiments, the crosslinking modifier may have a relatively high glass transition temperature (Tg), resulting in a relatively high heat distortion temperature. In some embodiments, the glass transition temperature of the crosslinking modifier is greater than -10 °C, greater than -5 °C, greater than 0 °C, greater than 5 °C, greater than 10 °C, greater than 15 °C, greater than 20 °C, or greater than 25 °C. In some specific embodiments, the photocurable resin includes 0 - 25 wt% of the crosslinking modifier, and the number average molecular weight of the crosslinking modifier is equal to or less than 1.5 kDa. In some embodiments, the crosslinking modifier includes (meth)acrylate - terminated polyester, bis(triethylene glycol dimethacrylate), vinyl - ester - terminated polyester, vinyl ester of tricyclodecanediol, derivatives thereof, or combinations thereof.

[0363] In some embodiments, the photocurable resin comprises a solvent. In some embodiments, the solvent comprises a nonpolar solvent. In certain embodiments, the nonpolar solvent comprises pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, ether, dichloromethane, its derivatives, or a combination thereof. In some embodiments, the solvent comprises a polar aprotic solvent. In certain embodiments, the polar aprotic solvent comprises tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, DMSO, propylene carbonate, its derivatives, or a combination thereof. In some embodiments, the solvent comprises a polar protic solvent. In certain embodiments, the polar protic solvent comprises formic acid, n-butanol, isopropanol, n-propanol, tert-butanol, ethanol, methanol, acetic acid, water, its derivatives, or a combination thereof. In some embodiments, the photocurable resin comprises a solvent in a weight percentage of less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 15%, less than 10%, less than 5%, less than 3%, less than 2%, or less than 1%. In certain cases, the solvent is configured to evaporate after curing or separate from the curable resin.

[0364] In some embodiments, the photocurable resins described herein, in addition to containing the polymerizable monomers described herein, further contain a component that can alter the glass transition temperature of the cured polymeric material. In such cases, based on the total weight of the composition, about 0 to 50 wt% of a glass transition temperature modifier (also referred to herein as a Tg modifier) may be present in the photocurable resin. The Tg modifier can have a relatively high glass transition temperature, which can result in a relatively high heat distortion temperature, which may be necessary for using the material at high temperatures. In some embodiments, the photocurable resin contains 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 the Tg modifier. In certain embodiments, the photocurable resin contains 0 - 50 wt% of the glass transition temperature modifier. In certain cases, the number average molecular weight of the Tg modifier is 0.4 to 5 kDa. In some embodiments, the number average molecular weight of the Tg 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 monomers of the present disclosure (which can themselves be used as Tg modifiers) and the separate Tg modifier compounds are miscible and compatible in the methods described herein. When used in the compositions of the present invention, the Tg modifier can provide high Tg and strength values, sometimes at the expense of elongation at break.

[0365] In some embodiments, the photocurable resins herein comprise a toughness modifier that can alter the toughness of the cured polymeric material. In certain cases, the toughness modifier can provide high elongation at break and toughness through reinforcement, and the polymerizable monomers described herein can improve the processability of the formulation, such as by acting as a reactive diluent, especially for compositions containing a large amount of toughness modifier, and at the same time maintaining a relatively high strength and Tg value of the formulation. The average number-average molecular weight of the toughness modifier can be from 2 to 20 kDa. The toughness modifier can include polyolefins, polyesters, polyurethanes, polyethylene, polyamides, polyethers, polyacrylic acids, polycarbonates, polysulfones, polyarylates, cellulose-based resins, polyvinyl chloride resins, polyvinylidene fluoride, polyvinylidene chloride, cycloolefin-based resins, polybutadiene, glycidyl methacrylate or methacrylates. For example, the toughness modifier can contain urethane groups, carbonate groups, or both urethane groups and carbonate groups. In some embodiments, the toughness modifier comprises a telechelic polymer. In some embodiments, the telechelic polymer is a polyol with (meth)acrylate end groups. In some embodiments, the telechelic polyol includes polyether diol, polyester diol or polycarbonate diol. In some embodiments, the photocurable resin can comprise from 10 to 70 wt%, from 10 to 60 wt%, from 10 to 50 wt%, from 10 to 40 wt%, from 10 to 30 wt%, from 10 to 25 wt%, from 20 to 60 wt%, from 20 to 50 wt%, from 20 to 40 wt%, from 20 to 35 wt%, from 20 to 30 wt%, from 25 to 60 wt%, from 25 to 50 wt%, from 25 to 45 wt%, from 25 to 40 wt% or from 25 to 35 wt% of the toughness modifier.

[0366] In some embodiments, the photocurable resins herein contain a polymerization catalyst. In some embodiments, the polymerization catalyst includes a tin catalyst, a platinum catalyst, a rhodium catalyst, a titanium catalyst, a silicon catalyst, a palladium catalyst, a metal trifluoromethanesulfonate catalyst, a boron catalyst, a bismuth catalyst, or any combination thereof. Non-limiting examples of the titanium catalyst include dibutylbutoxychlorotin, dibutyldiacetoxytin, dibutyldilauryltin, dimethyldineodecanoatetin, dioctyldilauryltin, tetramethyltin, and dioctylbis(2-ethylhexyl maleate)tin. Non-limiting examples of the platinum catalyst include platinum-divinyltetramethyldisiloxane complex, platinum-cyclohexenylmethylsiloxane complex, platinum-octanal complex, and platinum-carbonylcyclohexenylmethylsiloxane complex. Non-limiting examples of the rhodium catalyst include tris(dibutyl sulfide)rhodium trichloride. Non-limiting examples of the titanium catalyst include titanium isopropoxide, titanium 2-ethylhexoxide, titanium trichloride triisopropoxide, titanium ethoxide, and titanium diisopropoxide bis(ethylacetoacetate). Non-limiting examples of the silicon catalyst include tetramethylammonium siloxanolate and tetramethylsilylmethyl-trifluoromethane sulfonate. Non-limiting examples of the palladium catalyst include tetrakis(triphenylphosphine)palladium(0). Non-limiting examples of the metal trifluoromethanesulfonate catalyst include scandium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, and ytterbium trifluoromethanesulfonate. Non-limiting examples of the boron catalyst include tris(pentafluorophenyl)boron. Non-limiting examples of the bismuth catalyst include bismuth zinc neodecanoate, bismuth 2-ethylhexanoate, metal carboxylates of bismuth and zinc, and metal carboxylates of bismuth and zirconium.

[0367] In some embodiments, the photocurable resins herein include a polymerization inhibitor to stabilize the composition and prevent premature polymerization. In some embodiments, the polymerization inhibitor is a photo-polymerization inhibitor (such as oxygen). In some embodiments, the polymerization inhibitor is a phenolic compound (such as BHT). In some embodiments, the polymerization inhibitor is a stable free radical (such as, 2,2,4,4-tetramethylpiperidin-1-oxyl radical, 2,2-diphenyl-1-picrylhydrazyl radical, galvinoxyl radical or triphenylmethyl radical). In some embodiments, multiple polymerization inhibitors are present in the resin. In some embodiments, the polymerization inhibitor is an antioxidant, a hindered amine light stabilizer (HAL), a hindered phenol or an inactivated free radical (such as, a peroxide). In some embodiments, the polymerization inhibitor is selected from 4-tert-butylcatechol, tert-butylhydroquinone, 1,4-benzoquinone, 6-tert-butyl-2,4-xylenol, 2-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 1,1-diphenyl-2-picrylhydrazyl radical, hydroquinone, 4-methoxyphenol, phenothiazine, their derivatives, and any combination thereof.

[0368] In some embodiments, the photocurable resins herein include a light blocker for dissipating UV radiation. In some embodiments, the light blocker absorbs UV energy at specific values and / or ranges. In some embodiments, the light blocker is a UV light absorber, a pigment, a masterbatch or an IR light absorber. In some embodiments, the light blocker includes benzotriazole (such as, 2-(2'-hydroxyphenyl)benzotriazole, 2,2-dihydroxy-4-methoxybenzophenone, 9,10-diethoxyanthracene, hydroxyphenyltriazine, oxanilide, benzophenone or a combination thereof). In some embodiments, the photocurable resin includes 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 the light blocker. In more specific embodiments, the photocurable resin includes 0 to 0.5 wt% of the light blocker.

[0369] In some embodiments, the photocurable resins herein contain fillers. In some embodiments, the fillers include calcium carbonate (i.e., chalk), kaolin, metakaolin, kaolinite derivatives, magnesium hydroxide (i.e., talc), calcium silicate (i.e., wollastonite), glass fillers (such as glass beads, short glass fibers or long glass fibers), nano-fillers (such as nanosheets, nanofibers or nanoparticles), silica fillers (such as mica, silica gel, fumed silica or precipitated silica), carbon black, dolomite, barium sulfate, aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), diatomaceous earth, magnetite, halloysite, zinc oxide, titanium dioxide, cellulose, lignin, carbon fillers (such as chopped carbon fibers or carbon fibers), their derivatives or combinations thereof. The filler can be a minor component of the photocurable resin, such as less than 5% by weight of the photocurable resin, or can constitute a major portion of the weight of the photocurable resin. In some embodiments, the content of the filler is at least 0.05 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 5 wt%, at least 8 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 75 wt% or at least 80 wt% of the photocurable resin. In some embodiments, the filler accounts for at most 80 wt%, at most 75 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 8 wt%, at most 5 wt%, at most 3 wt%, at most 2 wt%, at most 1 wt% or at most 0.5 wt% of the photocurable resin. In some embodiments, the content of the filler is 0.05 to 60 wt%, 1 to 5 wt%, 1 to 10 wt%, 1 to 20 wt%, 2 to 5 wt%, 2 to 10 wt%, 2 to 20 wt%, 3 to 6 wt%, 3 to 10 wt%, 3 to 20 wt%, 5 to 10 wt%, 5 to 25 wt%, 8 to 20 wt%, 10 to 60 wt%, 12 to 25 wt%, 15 to 30 wt%, 15 to 40 wt%, 20 to 35 wt%, 25 to 50 wt%, 30 to 50 wt%, 35 to 65 wt%, 40 to 65 wt%, 40 to 80 wt%, 50 to 75 wt%, or 60 to 80 wt% of the photocurable resin. In some embodiments, the filler accounts for 10 to 60 wt% of the photocurable resin. In some embodiments, the filler accounts for 20 to 60 wt% of the photocurable resin. In some embodiments, the filler accounts for 20 to 40 wt% of the photocurable resin. In some embodiments, the filler accounts for 30 to 50 wt% of the photocurable resin.

[0370] In some embodiments, the photocurable resins herein include pigments, dyes, or combinations thereof. Pigments are generally suspended solids and may be insoluble in the resin. Dyes are generally dissolved in the photocurable resin. In some embodiments, the pigments include inorganic pigments. In some embodiments, the inorganic pigments include iron oxide, barium sulfide, zinc oxide, antimony trioxide, iron oxide yellow, iron oxide red, ammonium ferrocyanide, chrome yellow, carbon black, or aluminum flakes. In some embodiments, the pigments include organic pigments. In some embodiments, the organic pigments include azo pigments, anthraquinone pigments, copper phthalocyanine (CPC) pigments (such as phthalocyanine blue or phthalocyanine green), or combinations thereof. In some embodiments, the dyes include azo dyes (such as diarylide or Sudan dyes), anthraquinones (such as Oil Blue A or Disperse Red 11), or combinations thereof. In some embodiments, the photocurable resin includes from about 0.001 to about 3 wt% of the pigment. In some embodiments, the photocurable resin includes from about 0.005 to about 2 wt% of the pigment. In some cases, the photocurable resin includes from about 0.005 to about 0.5 wt% of the pigment. In some embodiments, the photocurable resin includes from about 0.01 to about 0.3 wt% of the pigment. In some embodiments, the photocurable resin includes from about 0.005 to about 0.1 wt% of the pigment.

[0371] In some embodiments, the photocurable resins herein include surface energy modifiers. In some embodiments, the surface energy modifiers can assist the process of polymer demolding from the mold. In some embodiments, the surface energy modifiers can act as defoaming agents. In some embodiments, the surface energy modifiers include defoaming agents, degassing agents, hydrophobic agents, leveling agents, wetting agents, or reagents for adjusting the fluidity of the photocurable resin. In some embodiments, the surface energy modifiers include alkoxylated surfactants, silicone surfactants, sulfosuccinates, fluorinated polyacrylates, fluoropolymers, silicones, star polymers, organically modified silicones, or any combination thereof. In some embodiments, the photocurable resin includes from about 0.01 to about 3 wt% of the surface energy modifier. In some embodiments, the photocurable resin includes from about 0.05 to about 1.5 wt%, from about 0.1 to about 1.5 wt%, from about 0.3 to about 1.5 wt%, from about 0.1 to about 1 wt%, from about 0.1 to about 0.5 wt%, from about 0.2 to about 1 wt%, from about 0.3 to about 0.7 wt%, or from about 0.4 to about 1 wt% of the surface energy modifier.

[0372] In some embodiments, the photocurable resins herein contain a plasticizer. The plasticizer can be a non-volatile substance that can reduce the interactions between polymer chains, thereby lowering the glass transition temperature, melt viscosity, and elastic modulus. In some embodiments, the plasticizer includes a dicarboxylate plasticizer, a tricarboxylate plasticizer, trimellitate, adipate, sebacate, maleate, or a bio-based plasticizer. In some embodiments, the plasticizer includes a dicarboxylate or tricarboxylate, including a diester, phthalate, bis(2-ethylhexyl) phthalate (DEHP), bis(2-propylheptyl) phthalate (DPHP), diisononyl phthalate (DINP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBZP), diisodecyl phthalate (DIDP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), di-n-hexyl phthalate, their derivatives, or combinations thereof. In some embodiments, the plasticizer contains trimellitate, including trimethyl trimellitate (TMTM), tris(2-ethylhexyl) trimellitate (TEHTM), tris(n-octyl,n-decyl) trimellitate (ATM), tris(heptyl,nonyl) trimellitate (LTM), n-octyl trimellitate (OTM), trioctyl trimellitate, their derivatives, or combinations thereof. In some embodiments, the plasticizer contains adipate, including bis(2-ethylhexyl) adipate (DEHA), dimethyl adipate (DMAD), monomethyl adipate (MMAD), dioctyl adipate (DOA), bis[2-(2-butoxyethoxy)ethyl] adipate, dibutyl adipate, diisobutyl adipate, diisodecyl adipate, their derivatives, or combinations thereof. In some embodiments, the plasticizer contains sebacate, such as dibutyl sebacate (DBS), bis(2-ethylhexyl) sebacate, diethyl sebacate, dimethyl sebacate, their derivatives, or combinations thereof. In some embodiments, the plasticizer contains maleate, such as bis(2-ethylhexyl) maleate, dibutyl maleate, diisobutyl maleate, their derivatives, or combinations thereof. In some embodiments, the plasticizer contains a bio-based plasticizer, such as acetylated monoglyceride, alkyl citrate, methyl ricinoleate, or a green plasticizer. In some embodiments, the alkyl citrate is selected from triethyl citrate, acetyltriethyl citrate, tributyl citrate, acetyltributyl citrate, trioctyl citrate, acetyltrioctyl citrate, trihexyl citrate, acetyltrihexyl citrate, butyryl trihexyl citrate, trimethyl citrate, their derivatives, or combinations thereof. In some embodiments, the green plasticizer is selected from epoxy soybean oil, epoxy vegetable oil, epoxy soybean oil ester, their derivatives, or combinations thereof.In some embodiments, the plasticizer includes azelaates, benzoates (such as sucrose benzoate), terephthalates (such as dioctyl terephthalate), diisononyl 1,2 - cyclohexanedicarboxylate, phenyl alkylsulfonate, sulfonamides (such as N - ethyltoluenesulfonamide, N-(2 - hydroxypropyl)benzenesulfonamide, N-(n - butyl)benzenesulfonamide), organophosphates (such as tricresyl phosphate or tributyl phosphate), glycols (such as triethylene glycol dihexanoate or tetraethylene glycol diheptanoate), polyethers, polybutenes, their derivatives, or combinations thereof.

[0373] In some embodiments, the photocurable resin herein contains biologically significant chemicals. In some embodiments, the biologically significant chemicals include hormones, enzymes, active pharmaceutical ingredients, antibodies, proteins, drugs, or any combination thereof. In some embodiments, the biologically significant chemicals include pharmaceutical compositions, chemicals, genes, polypeptides, enzymes, biomarkers, dyes, compliance indicators, antibiotics, analgesics, medical - grade drugs, chemical agents, bioactive agents, antibacterial agents, antibiotics, anti - inflammatory agents, immunosuppressants, immunostimulants, dentin desensitizers, odor - masking agents, immunological reagents, anesthetics, nutrients, antioxidants, lipopolysaccharide complexing agents, or peroxides.

[0374] In some embodiments, the added components (e.g., cross - linking modifiers, glass transition temperature modifiers, toughness modifiers, polymerization catalysts, polymerization inhibitors, photoresists, plasticizers, solvents, surface energy modifiers, pigments, dyes, fillers, or biologically significant chemicals) are functionalized to enable them to incorporate into the polymeric material and thus are less likely to precipitate out from the final cured material. In certain embodiments, the polymerization catalysts, polymerization inhibitors, photoresists, plasticizers, surface energy modifiers, pigments, dyes, and / or fillers are functionalized to facilitate their incorporation into the cured polymeric material.

[0375] Resin Properties

[0376] The photocurable resin of the present disclosure is characterized by having one or more properties. In some embodiments, the photopolymerizable monomers of the present disclosure, such as the compounds according to any one of formulas (I)-(VI) and (IX), can be used as reactive diluents in the curable resins disclosed herein. Thus, in certain cases, the photopolymerizable monomer can reduce the viscosity of the curable resin (e.g., the photocurable resin). In such cases, the photopolymerizable monomer can reduce the viscosity of the curable resin by at least about 5% compared to a resin without the polymerizable monomer. In certain cases, the photopolymerizable monomer can reduce the viscosity of the photocurable resin by at least about 5%, 10%, 20%, 30%, 40%, or 50%. In certain cases, the viscosity of the photocurable resin of the present disclosure at the printing temperature can be from about 30 CP to about 50,000 CP. In some embodiments, at 25 °C, the viscosity of the photocurable resin is 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 embodiments, the viscosity of the photocurable resin at 25 °C is less than 15,000 CP. In some embodiments, the viscosity of the photocurable resin at the printing temperature is less than or equal to 100,000 CP, less than or equal to 90,000 CP, less than or equal to 80,000 CP, less than or equal to 70,000 CP, less than or equal to 60,000 CP, less than or equal to 50,000 CP, less than or equal to 40,000 CP, less than or equal to 35,000 CP, less than or equal to 30,000 CP, less than or equal to 25,000 CP, less than or equal to 20,000 CP, less than or equal to 15,000 CP, less than or equal to 10,000 CP, less than or equal to 5,000 CP, less than or equal to 4,000 CP, less than or equal to 3,000 CP, less than or equal to 2,000 CP, less than or equal to 1,000 CP, less than or equal to 750 CP, less than or equal to 500 CP, less than or equal to 250 CP, less than or equal to 100 CP, less than or equal to 90 CP, less than or equal to 80 CP, less than or equal to 70 CP, less than or equal to 60 CP, less than or equal to 50 CP, less than or equal to 40 CP, less than or equal to 30 CP, less than or equal to 20 CP, or less than or equal to 10 CP.In some embodiments, at the printing temperature, the viscosity of the photocurable resin is from 50,000 CP to 30 CP, from 40,000 CP to 30 CP, from 30,000 CP to 30 CP, from 20,000 CP to 30 CP, from 10,000 CP to 30 CP, or from 5,000 CP to 30 CP. In some embodiments, the printing temperature is from 0 °C to 25 °C, from 25 °C to 40 °C, from 40 °C to 100 °C, or from 20 °C to 150 °C. In some embodiments, at the printing temperature, the viscosity of the photocurable resin is from 30 CP to 50,000 CP, wherein the printing temperature is from 20 °C to 150 °C. In other embodiments, the viscosity of the photocurable resin at the printing temperature is less than 20,000 CP. In some embodiments, the printing temperature is from 10 °C to 200 °C, from 15 °C to 175 °C, from 20 °C to 150 °C, from 25 °C to 125 °C, or from 30 °C to 100 °C. In a preferred embodiment, the printing temperature is from 20 °C to 150 °C.

[0377] The photocurable resin of the present disclosure can be 3D printed at a temperature higher than 25 °C. In some embodiments, the printing temperature is at least about 30 °C, 40 °C, 50 °C, 60 °C, 80 °C, or 100 °C. As described herein, the photo-polymerizable monomers of the present disclosure can be part of the photocurable resin and have a lower vapor pressure and / or mass loss at the printing temperature, thus providing better printing conditions compared to conventional resins used in additive manufacturing.

[0378] In some embodiments, the melting temperature of the photocurable resin described herein is higher than room temperature. In some embodiments, the melting temperature of the photocurable resin is higher than 20 °C, higher than 25 °C, higher than 30 °C, higher than 35 °C, higher than 40 °C, higher than 45 °C, higher than 50 °C, higher than 55 °C, higher than 60 °C, higher than 65 °C, higher than 70 °C, higher than 75 °C, or higher than 80 °C. In some embodiments, the melting temperature of the photocurable resin is from 20 °C to 250 °C, from 30 °C to 180 °C, from 40 °C to 160 °C, or from 50 °C to 140 °C. In some embodiments, the melting point of the photocurable resin is higher than 60 °C. In other embodiments, the melting point of the photocurable resin is from 80 °C to 110 °C. In certain cases, the melting point of the photocurable resin before polymerization is about 80 °C, and the melting point of the resulting polymer material after polymerization is about 100 °C.

[0379] In some cases, it may be advantageous for a photocurable resin to be liquid at elevated temperatures. For example, conventional photocurable resins may contain polymerizable components that can be viscous at processing temperatures and thus difficult to use in object fabrication (e.g., using 3D printing). As a solution to this technical problem, the present disclosure provides photocurable resins that include photopolymerizable components (e.g., monomers as described herein) that can be melted at elevated temperatures (e.g., at fabrication temperatures, e.g., during 3D printing) and have a reduced viscosity at elevated temperatures, which makes such resins more suitable for uses such as 3D printing. Accordingly, in some embodiments, photocurable resins that are liquid at elevated temperatures are provided herein. In some embodiments, the elevated temperature is equal to or higher than the melting temperature (Tm) of the photocurable resin. In certain embodiments, the elevated temperature is a temperature in the range of from about 40°C to about 100°C, from about 60°C to about 100°C, from about 80°C to about 100°C, from about 40°C to about 150°C, or from about 150°C to about 350°C. In some embodiments, the elevated temperature is a temperature higher than about 40°C, higher than about 60°C, higher than about 80°C, or higher than about 100°C. In some embodiments, the photocurable resins herein are liquid at elevated temperatures and have a viscosity less than about 50 PaS, less than about 20 PaS, less than about 10 PaS, less than about 5 PaS, or less than about 1 PaS. In some embodiments, the photocurable resins described herein are liquid at a temperature higher than about 40°C and have a viscosity less than about 20 PaS. In other embodiments, the photocurable resins described herein are liquid at a temperature higher than about 40°C and have a viscosity less than about 1 PaS.

[0380] In some embodiments, at least a portion of the photocurable resins described herein have a melting temperature lower than about 100°C, lower than about 90°C, lower than about 80°C, lower than about 70°C, or lower than about 60°C. In some embodiments, at least a portion of the photocurable resins described herein have a melting temperature between about 100°C and about 20°C, between about 90°C and about 20°C, between about 80°C and about 20°C, between about 70°C and about 20°C, between about 60°C and about 20°C, between about 60°C and about 10°C, or between about 60°C and about 0°C.

[0381] In various embodiments, the photocurable resins and their photopolymerizable components described herein can be biocompatible, bioinert, or both. In various cases, the photopolymerizable monomers of the resins described herein can have biocompatible and / or bioinert metabolites (e.g., hydrolysis products).

[0382] The photocurable resin of the present disclosure may comprise less than about 20 wt% or less than about 10 wt% of hydrogen-bonding units. In some aspects, the photocurable resin herein comprises less than about 15 wt%, less than about 10 wt%, less than about 9 wt%, less than about 8 wt%, less than about 7 wt%, less than about 6 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt% or less than about 1 wt% of hydrogen-bonding units, where wt% refers to the weight percentage of a substance capable of forming at least one hydrogen bond, and the substance includes monomer units in polymeric, oligomeric, and monomeric states.

[0383] III. Polymeric Materials

[0384] The present disclosure provides polymeric materials. Such polymeric materials can be produced by curing the curable compositions or resins described herein. The polymeric materials provided herein can be biocompatible, bio-inert, or a combination of both. In various cases, the polymeric materials described herein are produced by photocuring the photocurable compositions described herein. Such photocurable compositions can comprise one or more of the photopolymerizable monomers of the present disclosure.

[0385] Phase Separation of Polymeric Materials

[0386] In some aspects herein, the photocurable composition or resin herein can be cured by exposing such composition or resin to electromagnetic radiation of an appropriate wavelength. This curing or polymerization can initiate phase separation in the photocurable composition and / or the polymeric material being formed. This polymerization-induced phase separation can occur along one or more lateral and longitudinal directions (see, for example Figure 8 ). The polymerization-induced phase separation can produce one or more polymer phases in the resulting polymeric material. The photocurable composition undergoing polymerization and polymerization-induced phase separation can comprise one or more of the photopolymerizable monomers of the present disclosure. Thus, in certain cases, at least one of the one or more polymer phases produced during the curing process and present in the resulting polymeric material can comprise at least one of the one or more photopolymerizable monomers in a polymerized state. In one example, a photocurable composition comprising one photopolymerizable monomer species (e.g., a compound according to any one of formulas (I)-(VI) and (IX)) is cured by exposure to electromagnetic radiation of an appropriate wavelength. The cured polymeric material comprises 2 polymer phases: phase A and phase B. In certain cases, at least one of phase A or phase B can comprise the photopolymerizable monomer as a component in its polymer structure. In certain cases, both phase A and phase B can comprise the photopolymerizable monomer as a component in its polymer structure. Phase A and phase B can comprise different amounts or concentrations of the photopolymerizable monomer. Thus, in some cases herein, two or more phases comprising the photopolymerizable monomer can be separated by this concentration gradient of the monomer.

[0387] The polymer phase of the polymer material of the present disclosure may have a certain size or volume. In some embodiments, the polymer phase is three-dimensional, and at least one dimension may be less than 1000 μm, less than 500 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In certain embodiments, the polymer phase may have at least two dimensions that are less than 1000 μm, less than 500 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In certain embodiments, the polymer phase may have three dimensions with sizes less than 1000 μm, less than 500 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In some aspects, the size of the average polymer phase of the polymer material in at least one spatial dimension is less than about 5 μm.

[0388] In various aspects, the present disclosure provides a polymer material that may comprise one or more polymer phases, wherein at least one of the one or more polymer phases is a crystalline phase. In various aspects, the present disclosure provides a polymer material that may comprise one or more polymer phases, wherein at least one of the one or more polymer phases is an amorphous phase. In certain cases, the present disclosure provides a polymer material that may comprise two or more polymer phases, wherein at least one of the one or more polymer phases is a crystalline phase and at least one of the one or more polymer phases is an amorphous phase.

[0389] Thus, in some cases, the present disclosure provides a polymeric material comprising: (i) at least one crystalline phase comprising at least one polymer crystal having a melting temperature above 20 °C; and (ii) at least one amorphous phase comprising at least one amorphous polymer having a glass transition temperature above 40 °C. In some cases, the at least one crystalline phase may comprise a polymerized form of a photo-polymerizable monomer represented by any one of formulas (I)-(VI) and (IX). In some cases, the at least one amorphous phase may comprise a polymerized form of a photo-polymerizable monomer represented by any one of formulas (I)-(VI) and (IX). In some aspects, the glass transition temperature of such an amorphous phase is above 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C or above 110 °C. In some cases, such an amorphous phase may comprise a polymerized form of a photo-polymerizable monomer represented by any one of formulas (I)-(VI) and (IX). In some aspects, the melting temperature of the at least one polymer crystal is above 30 °C, 40 °C, 50 °C, 60 °C or above 70 °C. In some cases, such a crystalline phase may comprise a polymerized form of a photo-polymerizable monomer represented by any one of formulas (I)-(VI) and (IX).

[0390] Amorphous polymer phase

[0391] The present disclosure provides polymer materials that include one or more amorphous phases (e.g., amorphous phases resulting from polymerization-induced phase separation). Such polymer materials or regions of such materials that contain a polymer phase can provide a rapid response time to external stimuli, which can impart advantageous properties to polymer materials that include a crystalline phase and / or an amorphous phase, such as using the polymer materials in medical devices (e.g., orthodontic appliances). In some cases, polymer materials that include one or more amorphous phases can, for example, provide flexibility to a cured polymer material, thereby enhancing its durability (e.g., the material can be stretched or bent while maintaining its structure, whereas a similar material without an amorphous phase may break). In some embodiments, the amorphous phase is characterized by randomly oriented polymer chains (e.g., not parallelly stacked or not forming a crystal structure). In some embodiments, the glass transition temperature of such an amorphous polymer phase of the polymer material can be higher than about 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, or higher than about 110 °C. In some embodiments, the glass transition temperature of the amorphous polymer phase can be from about 40 °C to about 60 °C, from about 50 °C to about 70 °C, from about 60 °C to about 80 °C, or from about 80 °C to about 110 °C. In some embodiments, the glass transition temperature of the amorphous phase is lower than 10 °C, 0 °C, -10 °C, -30 °C, -50 °C. In some preferred aspects, the glass transition temperature of one or more phases is lower than 0 °C. In some embodiments, the glass transition temperature of two or more phases is higher than 60 °C and lower than 10 °C.

[0392] In some embodiments, the amorphous phases herein (also referred to herein as amorphous domains) can include at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or at least about 90% of amorphous polymer material in an amorphous state. The percentage of amorphous polymer material in the amorphous phase generally refers to the total volume percentage.

[0393] In some embodiments, the amorphous polymer phase can comprise one or more polymer types that may be formed during curing from polymerizable monomers, telechelic polymers, and / or oligomers, and any other polymerizable components that may be present in the curable composition used to produce the polymeric material comprising the amorphous polymer phase. In certain cases, the one or more polymer types can include one or more of the following: homopolymers, linear copolymers, block copolymers, alternating copolymers, periodic copolymers, statistical copolymers, random copolymers, gradient copolymers, branched copolymers, brush copolymers, comb copolymers, dendrimers, or any combination thereof. In certain cases, the amorphous polymeric material comprises a random copolymer. In some embodiments, the amorphous polymeric material can include poly(ethylene glycol) (PEG), poly(ethylene glycol) diacrylate, PEG-THF, polytetrahydrofuran, poly(tert-butyl acrylate), poly(ethylene-maleic anhydride copolymer), any derivatives thereof, or any combination thereof.

[0394] In certain cases, the polymerizable components in the resin can form a crystalline material, but instead form an amorphous phase when exposed to conditions that prevent its crystallization. Thus, in certain cases, a material that is typically considered a crystalline material can be used as an amorphous material. For example, polycaprolactone can be a crystalline polymer, but when mixed with other polymerizable monomers and telechelic polymers, it may prevent crystal formation and form an amorphous phase.

[0395] The amorphous phase may contain one or more polymerizable monomers according to any one of formulas (I)-(VI) and (IX) in polymeric form, and in addition thereto, may contain one or more of the following moieties: acrylic monomers, acrylamide, methacrylamide, acrylonitrile, bisphenol acrylate, carbohydrates, fluorinated acrylates, maleimides, 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[(butylamino)carbonyl]oxy]ethyl acrylate, tert-butyl 2-bromoacrylate, 2-carboxyethyl acrylate, 2-chloroethyl acrylate, 2-(diethylamino)ethyl acrylate, di(ethylene glycol)ethyl ether acrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl acrylate, dipentaerythritol penta- / hexa-acrylate, ethyl acrylate, 2-ethylacryloyl chloride, ethyl 2-(bromomethyl)acrylate, cis-(β-cyano)ethyl acrylate, ethylene glycol dicyclopentenyl 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, 2-acetamidomethyl acrylate, methyl acrylate, methylene malonate esters (e.g., dibutyl methylene malonate, dihexyl methylene malonate or dicyclohexyl methylene malonate), methylene malonate macromonomers (e.g., polyesters of 2-methylene malonate, e.g., Forza B3000 XP), α-bromomethyl acrylate, methyl 2-(bromomethyl)acrylate, methyl 2-(chloromethyl)acrylate, methyl 3-hydroxy-2-methylenebutyrate, 2-(trifluoromethyl)methyl 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-tetrahydropyranyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3,5,5-trimethylhexyl acrylate, 10-undecenyl acrylate, polyurethane acrylate, polyurethane methacrylate, tricyclodecane diacrylate, isobornyl acrylate, methacrylate, allyl methacrylate, benzyl methacrylate, (2-boc-amino)ethyl methacrylate, tert-butyl methacrylate, 9H-carbazol-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, glycopyranosyloxyethyl methacrylate, hexyl methacrylate, hydroxybutyl methacrylate, 2-hydroxy-5-N-methacryloylaminobenzoic acid, isobutyl methacrylate, methacryloyl chloride, methyl methacrylate, succinic acid mono-(2-methacryloyloxy)ethyl ester, 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'-hydroxy)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 acrylate, N,N’-methylenebisacrylamide, 3-(acryloyloxy)-2-hydroxypropyl) methacrylate, bis[2-(methacryloyloxy)ethyl] phosphate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diurethane dimethacrylate, N,N’-ethylenebis(acrylamide), glycerol 1,3-glycerolate diacrylate, 1,6-hexanediol diacrylate, hydroxyneopentyl hydroxyneopentanoate bis[6-(acryloyloxy)hexanoate], neopentyl glycol diacrylate, pentaerythritol diacrylate, 1,3,6-triacryloylhexahydro-1,3,5-triazine, trimethylolpropane ethoxylate, tris[2-(acryloyloxy)ethyl] isocyanurate, any derivative thereof or a combination thereof.,

[0396] The phases (e.g., amorphous or crystalline phases) of the polymeric materials of the present disclosure can include one or more reactive functional groups, which can allow for further modification of the polymeric materials, such as additional polymerization (e.g., post-curing). In some embodiments, the amorphous polymeric material contains a plurality of reactive functional groups, and the reactive functional groups can be located at one or both ends of the amorphous material, in the chain, in side chains (e.g., side groups attached to the polymer backbone), or any combination thereof. Non-limiting examples of reactive functional groups include free-radical polymerizable functionality, photoactive groups, groups that facilitate step-growth polymerization, thermally reactive groups, and / or groups that facilitate bond formation (e.g., covalent bond formation). In some embodiments, the functional groups include acrylate, methacrylate, acrylamide, vinyl, vinyl ether, thiol, allyl ether, norbornene, vinyl acetate, maleate, fumarate, maleimide, epoxide, ring-strained cyclic ether, ring-strained cyclic thioether, cyclic ester, cyclic carbonate, cyclic silane, cyclic siloxane, hydroxyl, amine, isocyanate, blocked isocyanate, acid chloride, activated ester, oxetane, Diels-Alder reactive groups, furan, cyclopentadiene, anhydride, groups that are favorable for photodimerization (e.g., anthracene, acenaphthylene, or coumarin), groups that photodegrade into reactive species (e.g., Norrish type 1 and 2 materials), azide, derivatives thereof, or combinations thereof.

[0397] Crystalline polymer phase

[0398] As further described herein, the polymeric materials of the present disclosure can include one or more crystalline phases, e.g., generated by phase separation initiated by polymerization during curing. As described herein, a crystalline phase is a polymeric phase in a cured polymeric material that contains at least one polymer crystal. As described herein, a crystalline phase can consist of a single polymer crystal or multiple polymer crystals.

[0399] In some embodiments, the melting temperature of the crystalline polymer phase can 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 certain cases, at least two of the multiple crystalline phases may have different melting temperatures due to differences in, for example, crystalline phase size, impurities, degree of crosslinking, chain length, thermal history, polymerization rate, degree of phase separation, or any combination thereof. In some aspects, the respective polymer crystal melting temperatures of at least two crystalline phases of the polymeric material can differ from each other by within about 5°C. In certain cases, such a melting temperature difference can be less than about 5°C. In other cases, such a melting temperature difference may be greater than about 5°C. In certain aspects, the melting temperature of each polymer crystal of the polymeric material can be from about 40°C to about 100°C. In certain aspects, at least about 80% of the crystalline domains of the polymeric material can comprise polymer crystals having a melting temperature between about 40°C and about 100°C.

[0400] In some embodiments, the crystal melting point of at least 80% of the crystalline phase is between 0°C and 100°C. In some embodiments, the crystal melting point of at least 80% of the crystalline phase is between 40°C and 60°C, between 40°C and 80°C, between 40°C and 100°C, between 60°C and 80°C, between 60°C and 100°C, between 80°C and 100°C, or above 100°C. In some embodiments, the crystal melting point of at least 90% of the crystalline phase is between 0°C and 100°C. In some embodiments, the crystal melting point of at least 90% of the crystalline phase is between 40°C and 60°C, between 40°C and 80°C, between 40°C and 100°C, between 60°C and 80°C, between 60°C and 100°C, between 80°C and 100°C, or above 100°C. In some embodiments, the crystal melting point of at least 95% of the crystalline phase is between 0°C and 100°C. In some embodiments, at least 95% of the crystalline phase has a crystal melting point at a temperature between 40°C and 60°C, between 40°C and 80°C, between 40°C and 100°C, between 60°C and 80°C, between 60°C and 100°C, between 80°C and 100°C, or above 100°C.

[0401] In certain embodiments, the temperature at which the crystalline phase of the cured polymeric material melts can be controlled, for example, by using different amounts and types of polymerizable components in the curable resin, such as, different amounts and types of polymerizable monomers (e.g., compounds according to any one of formulas (I)-(VI) and (IX) described herein), different amounts and types of telechelic polymers and / or oligomers, and / or by using polymer blocks (i.e., copolymers) having different crystal melting points.

[0402] In some embodiments, the curing of the resin can be carried out at a high temperature (e.g., about 90 °C), and when the cured polymeric material cools to room temperature (e.g., 25 °C), the cooling process can trigger the formation and / or growth of polymer crystals in the polymeric material. In some cases, the polymeric material can be solid at room temperature and may not contain crystals, but can form a crystalline phase over time. In such cases, the crystalline phase can form within 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 18 hours, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, or 7 days after cooling. In some embodiments, when the cured polymeric material is in a cooling environment, a crystalline phase can form, for example, a cooling environment with a temperature range of about 40 °C to about 30 °C, about 30 °C to about 20 °C, about 20 °C to about 10 °C, about 10 °C to about 0 °C, about 0 °C to about -10 °C, about -10 °C to about -20 °C, about -20 °C to about -30 °C, or below about -30 °C. In some cases, the polymeric material can be heated to a high temperature to initiate crystallization or form a crystalline phase. As a non-limiting example, a polymeric material near its glass transition temperature may contain polymer chains with insufficient mobility to organize into crystals, so further heating of the material can increase the mobility of the chains and initiate crystal formation.

[0403] In some embodiments, the generation, formation, and / or growth of the polymer phase is spontaneous. In some embodiments, the generation, formation, and / or growth of polymer crystals is facilitated by a triggering factor. In some embodiments, the triggering factor includes the addition of seed particles (also referred to herein as "seeds"), which can initiate crystallization. Such seeds can include, for example, finely ground solid materials having at least some properties similar to those of the crystal being formed. In some embodiments, the triggering factor includes lowering the temperature. In certain embodiments, lowering the temperature can include cooling the cured material to a temperature of 40°C to 30°C, 30°C to 20°C, 20°C to 10°C, 10°C to 0°C, 0°C to -10°C, -10°C to -20°C, -20°C to -30°C, or below -30°C. In certain embodiments, the triggering factor can include raising the temperature. In certain embodiments, raising the temperature can include heating the polymer cured material to a temperature of 20°C to 40°C, 40°C to 60°C, 60°C to 80°C, 80°C to 100°C, or above 100°C. In some embodiments, the triggering factor includes a force applied to the cured polymer material. In certain embodiments, the force includes squeezing, compaction, stretching, torsion, or any other physical force applied to the material. In some embodiments, the triggering factor includes a charge and / or an electric field applied to the material. In some embodiments, the formation of one or more crystalline phases can be initiated by multiple triggering factors (i.e., multiple types of triggering factors can facilitate the generation, formation, and / or growth of crystals). In some embodiments, the polymer material comprises multiple crystalline phases, and at least two crystalline phases can be initiated by different triggering factors.

[0404] In some embodiments, the polymer materials described herein comprise crystalline phases having a discontinuous phase transition (e.g., a first-order phase transition). In certain cases, the polymer material has a discontinuous phase transition, which is at least partially due to the presence of one or more crystalline domains. As a non-limiting example, a cured polymer material containing one or more crystalline domains may have one or more portions that melt at a high temperature and one or more portions that remain solid at this high temperature.

[0405] In some embodiments, the cured polymeric material comprises continuous and / or discontinuous crystalline phases. The continuous phase can be a phase that can be traced from one side of the polymeric material to the other side, or is connected to both sides of the polymeric material; for example, in a closed-cell foam, the material forming the foam can be traced from one side of the sample to the other side, while the closed cells (bubbles) represent the discontinuous phase formed by air cavities. In some embodiments, at least one crystalline phase forms the continuous phase, and at least one amorphous phase is discontinuous throughout the material. In another embodiment, at least one crystalline phase is discontinuous, and at least one amorphous phase is continuous throughout the material. In another embodiment, at least one crystalline phase and at least one amorphous phase are continuous throughout the material. In some embodiments, the polymeric material comprises multiple crystalline phases, wherein one or more of the multiple crystalline phases have a high melting point (e.g., at least about 50 °C, 70 °C, or 90 °C) and are in the discontinuous phase, while another or more of the multiple crystalline phases have a low melting point (e.g., below about 50 °C, 70 °C, or 90 °C) and are in the continuous phase. In some embodiments, there are two continuous amorphous phases. In other embodiments, there is one continuous amorphous phase and one discontinuous amorphous phase.

[0406] In some aspects, the polymeric material includes an average crystalline phase size of less than about 100 μm, 50 μm, 20 μm, 10 μm, or less than about 5 μm in at least one spatial dimension.

[0407] In some aspects, the polymer crystals of the crystalline phase can comprise greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, or greater than about 90 wt% of linear polymers and / or linear oligomers.

[0408] In some aspects, the crystalline phase content of the polymeric materials described herein can be about 10% to about 90%, about 20% to about 80%, about 30% to about 70%, about 40% to about 95%, or about 50% to about 95%, as measured by X-ray diffraction. In some aspects, the weight ratio of the crystalline phase to the amorphous phase of the polymeric materials described herein can be about 1:99 to about 99:1.

[0409] In various aspects, the present disclosure provides a polymeric material comprising: an amorphous phase; and a crystalline phase comprising a polymer having tacticity. In some aspects, the tacticity includes isotacticity, syndiotacticity, having a plurality of meso diads, having a plurality of racemic diads, having a plurality of isotactic triads, having a plurality of syndiotactic triads, or having a plurality of heterotactic triads. In some aspects, compared to a like polymeric material comprising a polymer having comparable atacticity, the polymeric material comprising a crystalline phase of a polymer having tacticity has a higher degree of crystallinity. In some aspects, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% of the crystalline phase has tacticity. In some aspects, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% of the polymeric material has tacticity. In some aspects, the polymeric material comprising a polymer having tacticity is characterized by at least one of the following: an elongation at break greater than or equal to 5%; a storage modulus greater than or equal to 500 MPa; a tensile modulus greater than or equal to 500 MPa; and a flexural stress retention greater than or equal to 0.01 MPa. In some aspects, a like polymeric material (which comprises an atactic polymer comparable to the polymer having tacticity) is characterized by at least one of the following: an elongation at break less than 5%; a storage modulus less than 500 MPa; a tensile modulus less than 500 MPa; and a flexural stress retention less than 0.01 MPa. In some aspects, the polymeric material is at least partially crosslinked. In some aspects, the polymeric material is a thermosetting material or a thermoplastic material. In some aspects, the polymeric material comprises semi-crystalline segments.

[0410] In some embodiments, a cured polymer (e.g., a crosslinked polymer) is characterized by its tensile stress-strain curve, which shows a yield point after which the specimen continues to elongate but the stress does not increase (detectably) or only increases very slightly. This yield point behavior can occur "near" the glass transition temperature where the material is between the glassy and rubbery states and may be characterized as having viscoelastic behavior. In some embodiments, viscoelastic behavior is observed in the 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 the tangent 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 stress maximum, the ultimate tensile strength is less than the yield strength. For a tensile test specimen, the strain is defined as ln(l / l0) and can be approximated as (l - l0) / l0 at small strains (e.g., less than about 10%), and the elongation is l / l0, where l is the gauge length after a certain deformation and l0 is the initial gauge length. The mechanical properties may depend on the temperature at which the measurement is made. The test temperature may be lower than the expected use temperature of the orthodontic appliance, e.g., 35 °C to 40 °C. In some embodiments, the test temperature is 23 ± 2 °C.

[0411] As further described herein, a polymer material comprising a crystalline phase (also referred to herein as crystalline domains) and an amorphous phase (also referred to herein as amorphous domains) can have improved properties such as the ability to react quickly (e.g., due to the elastic properties of the amorphous domains, vibrating and reacting quickly when a strain is applied), and providing a high modulus (e.g., due to the crystalline domains, being rigid and providing strength). The polymer crystals disclosed herein can comprise closely stacked and / or closely packed polymer chains. In some embodiments, the polymer crystals comprise long oligomers or long polymer chains that are stacked in an ordered manner and overlap parallel to each other. In certain cases, the polymer crystals can be pulled out from the crystalline phase, causing the polymer chains of the polymer crystals to be elongated (e.g., applying a force can pull the long polymer chains of the polymer crystals, introducing disorder in the stacked chains and pulling at least a portion out of its crystalline state without breaking the polymer chains). This is in stark contrast to the fillers conventionally used to form resins for high flexural modulus materials. When a polymer material is stressed or the filler is covalently bonded to the polymer, the filler easily slides past the amorphous phase, resulting in a reduced elongation at break of the material. Thus, using polymer crystals in the resulting polymer material can reduce the brittleness of the product, enabling it to retain more of its original physical properties (i.e., be more durable) after use and maintain elastic properties through the combination of the amorphous and crystalline phases.

[0412] In some embodiments, the polymer materials herein comprise a ratio (wt / wt) of the crystalline polymer phase to the amorphous polymer phase that is greater than about 1:10, greater than about 1:9, greater than about 1:8, greater than about 1:7, greater than about 1:6, greater than about 1:5, greater than about 1:4, greater than about 1:3, greater than about 1:2, greater than about 1:1, greater than about 2:1, greater than about 3:1, greater than about 4:1, greater than about 5:1, greater than about 6:1, greater than about 7:1, greater than about 8:1, greater than about 9:1, greater than about 10:1, greater than about 20:1, greater than about 30:1, greater than about 40:1, greater than about 50:1, or greater than about 99:1. In some embodiments, the polymer materials comprise a ratio (wt / wt) of the crystallizable polymer material to the amorphous polymer material that is at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In certain embodiments, the polymer materials include a ratio (wt / wt) of the crystalline polymer phase to the amorphous polymer phase that is from 1:9 to 99:1, from 1:9 to 9:1, from 1:4 to 4:1, from 1:4 to 1:1, from 3:5 to 1:1, from 1:1 to 5:3, or from 1:1 to 4:1.

[0413] In some embodiments, the polymer material of the present disclosure has a ratio (volume / volume) of the crystalline polymer phase to the amorphous polymer phase greater than about 1:10, greater than about 1:9, greater than about 1:8, greater than about 1:7, greater than about 1:6, greater than about 1:5, greater than about 1:4, greater than about 1:3, greater than about 1:2, greater than about 1:1, greater than about 2:1, greater than about 3:1, greater than about 4:1, greater than about 5:1, greater than about 6:1, greater than about 7:1, greater than about 8:1, greater than about 9:1, greater than about 10:1, greater than about 20:1, greater than about 30:1, greater than about 40:1, greater than about 50:1, or greater than about 99:1. In some embodiments, the ratio (volume / volume) of the crystalline polymer phase to the amorphous polymer phase contained in the polymer material is at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In certain embodiments, the ratio (volume / volume) of the crystalline polymer phase to the amorphous polymer phase included in the polymer material is between 1:9 and 99:1, 1:9 to 9:1, 1:4 to 4:1, 1:4 to 1:1, 3:5 to 1:1, 1:1 to 5:3, or 1:1 to 4:1.

[0414] Properties of the polymer material

[0415] The polymer material polymerized from the curable resin disclosed herein according to the present invention can provide more excellent properties compared with traditional polymer materials. In certain cases, as described herein, the polymer material may contain a certain proportion of crystallinity, which can endow the polymer material with higher toughness and higher modulus. At the same time, in certain cases, this material can also be used as a 3D printing material. In addition, the polymer materials described herein may also contain one or more amorphous phases, which can provide higher durability, prevent crack formation, and prevent crack propagation. In certain cases, the polymer material may also have a lower water absorption rate and solvent resistance. In certain cases, the polymer material can be characterized by one or more of the following properties: elongation at break, storage modulus, tensile modulus, residual bending stress, glass transition temperature, water absorption rate, hardness, color, transparency, hydrophobicity, lubricity, surface texture, percentage of crystallinity, phase composition ratio, phase domain size, and phase domain size and morphology. In addition, as described herein, the polymer materials provided herein can be used in a variety of applications, including 3D printing, to form materials with good properties of both elasticity and stiffness.

[0416] In some embodiments, the polymeric materials of the present disclosure may have one or more of the following characteristics: (A) a storage modulus greater than or equal to 200 MPa; (B) a remaining flexural stress and / or flexural modulus greater than or equal to 1.5 MPa after being placed in a humid environment at 37 °C for 24 hours; (C) an elongation at break greater than or equal to 5% before and after being placed in a humid environment at 37 °C for 24 hours; (D) a water absorption rate lower than 25 wt% when measured after being placed in a humid environment at 37 °C for 24 hours; (E) at least 30% of visible light passing through the polymeric material after being placed in a humid environment at 37 °C for 24 hours; and (F) comprising a plurality of polymer phases, wherein the Tg of at least one polymer phase in one or more polymer phases is at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C. In some cases, the polymeric materials described herein have at least two, three, four, five or all of the characteristics of (A), (B), (C), (D), (E) and (F).

[0417] In some cases, the polymeric material is characterized in that after being placed in a humid environment at 37 °C for 24 hours, its storage modulus is from 0.1 MPa to 4000 MPa, the storage modulus is from 300 MPa to 3000 MPa, or the storage modulus is from 750 MPa to 3000 MPa. In some cases, the polymeric material is characterized in that after being placed in a humid environment at 37 °C for 24 hours, its flexural stress and / or flexural modulus is greater than or equal to 5 MPa, greater than or equal to 10 MPa, greater than or equal to 20 MPa, greater than or equal to 30 MPa, greater than or equal to 40 MPa, greater than or equal to 50 MPa, greater than or equal to 60 MPa, greater than or equal to 80 MPa or greater than or equal to 100 MPa.

[0418] In some cases, for the polymeric materials herein, after being placed in a humid environment at 37 °C for 24 hours, its flexural stress and / or flexural modulus may be 400 MPa or greater, 300 MPa or greater, 200 MPa or greater, 180 MPa or greater, 160 MPa or greater, 120 MPa or greater, 100 MPa or greater, 80 MPa or greater, 70 MPa or greater, 60 MPa or greater.

[0419] In some cases, the polymeric material is characterized in that the elongation at break is greater than 10%, greater than 20%, greater than 30%, the elongation at break is from 5% to 250%, the elongation at break is from 20% to 250% or the elongation at break value is between 40% and 250% before and after being placed in a humid environment at 37 °C for 24 hours.

[0420] The polymer material is characterized in that when measured after being placed in a humid environment at 37 °C for 24 hours, its water absorption rate is lower than 20 wt%, lower than 15 wt%, lower than 10 wt%, lower than 5 wt%, lower than 4 wt%, lower than 3 wt%, lower than 2 wt%, lower than 1 wt%, lower than 0.5 wt%, lower than 0.25 wt% or lower than 0.1 wt%. In some cases, compared with a photocurable resin, the conversion rate of double bonds to single bonds of the polymer material can be higher than 50%, 60% or 70% (measured by FTIR).

[0421] In some cases, after being placed in a humid environment at 37 °C for 24 hours, the ultimate tensile strength of the polymer material 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.

[0422] In some cases, the polymer material may have a low hydrogen bonding content, which is beneficial to reducing the water absorption rate compared with traditional polymer materials with a high hydrogen bonding content. Therefore, in some cases, when the polymer material described herein is completely saturated at the use temperature (for example, about 20 °C, 25 °C, 30 °C or 35 °C), its water content can be lower than about 10 wt%, lower than about 9 wt%, lower than about 8 wt%, lower than about 7 wt%, lower than about 6 wt%, lower than about 5 wt%, lower than about 4 wt%, lower than about 3 wt%, lower than about 2 wt%, lower than about 1 wt% or lower than about 0.5 wt%. In some cases, the use temperature can include the temperature of the human oral cavity (for example, about 35 - 40 °C). The use temperature can be a temperature selected from the following: -100 to 250 °C, 0 to 90 °C, 0 to 80 °C, 0 to 70 °C, 0 to 60 °C, 0 to 50 °C, 0 to 40 °C, 0 to 30 °C, 0 to 20 °C, 0 to 10 °C, 20 to 90 °C, 20 to 80 °C, 20 to 70 °C, 20 to 60 °C, 20 to 50 °C, 20 to 40 °C, 20 to 30 °C, or below 0 °C.

[0423] In some embodiments, the polymer material described herein comprises at least one crystalline phase and at least one amorphous phase, wherein at least one crystalline phase, at least one amorphous phase or both comprise the polymerizable monomers of the present disclosure, and the monomer can be a compound conforming to any one of formulas (I)-(VI) and (IX). In some cases, the combination of these two phases or domains can form a polymer material having a high modulus phase (for example, a crystalline polymer material can provide a high modulus) and a low modulus phase (for example, provided by an amorphous polymer material). By having these two phases, the polymer material can have a high modulus and a high elongation rate, as well as a high residual bending stress after stress relaxation.

[0424] In various cases, the glass transition temperature of one or more amorphous phases of the polymeric material 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. In such cases, in one or more amorphous phases, at least one amorphous phase having a glass transition temperature of at least about 50 °C contains the polymerizable monomers described in the present disclosure incorporated into its polymer structure, such as the compounds described in any one of formulas (I)-(VI) and (IX).

[0425] In some cases, the polymeric material can include polymer crystals attached to the amorphous polymer. As a non-limiting example, the polymer crystals can be covalently bonded, entangled, crosslinked, and / or otherwise associated (e.g., by hydrophobic interactions, π-stacking, or hydrogen bonding interactions) with the amorphous polymeric material.

[0426] In some embodiments, the polymeric materials described herein can include crystalline and / or amorphous phases that are smaller in size (e.g., less than about 5 μm). The smaller polymeric phases in the polymeric material can facilitate the passage of light, making the polymeric material appear transparent. In contrast, larger polymeric phases (e.g., polymeric phases greater than about 1 μm) can scatter light, e.g., when the refractive index of the polymer crystals is different from the refractive index of its adjacent amorphous phase (e.g., amorphous material). In some cases, after being placed in a humid environment at 37 °C for 24 hours, at least 40%, 50%, 60%, or 70% of visible light will pass through the polymeric material.

[0427] Thus, in some cases, it may be advantageous to employ a polymeric material that includes a smaller polymeric phase (e.g., a crystalline or amorphous phase, e.g., measured by the longest dimension of the phase). In some embodiments, the average polymeric phase size of such a polymeric material is less than 5 μm. In some embodiments, the maximum polymeric phase size of the polymeric material can be about 5 μm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymeric phase sizes in the polymeric material are less than about 5 μm. In other embodiments, the average polymeric phase size of the polymeric material is less than about 1 μm. In some embodiments, the maximum polymeric phase size of the cured polymeric material is 1 μm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymeric phases in the polymeric material have a size less than about 1 μm. In yet other embodiments, the average polymeric phase size of the polymeric material is less than about 500 nm. In some embodiments, the maximum polymeric phase size of the cured polymeric material is about 500 nm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymeric phases in the polymeric material have a size less than 500 nm.

[0428] In some embodiments, the size of at least one or more polymeric phases (e.g., crystalline and amorphous phases) in the polymeric material can be controlled. Methods for controlling the polymeric phase size include, but are not limited to: rapidly cooling the cured polymeric material, annealing the cured polymeric material at an elevated temperature (i.e., above room temperature), annealing the cured polymeric material at a temperature below room temperature, controlling the polymerization rate, controlling the light intensity during a curing step using light, controlling and / or regulating the polymerization temperature, exposing the cured polymeric material to acoustic vibrations, and / or controlling the presence and amount of impurities (especially for crystalline phases), adding chemicals or particles that initiate crystallization (e.g., crystallization seeds).

[0429] In some embodiments, the refractive index of one or more crystalline phases and / or one or more amorphous phases of the polymeric materials described herein can be controlled. Reducing the refractive index difference between different phases (e.g., reducing the refractive index difference between a crystalline polymer and an amorphous polymer) can improve the transparency of the cured polymeric material, thereby providing a transparent or nearly transparent material. Light scattering can be reduced by minimizing the polymer crystal size and by reducing the refractive index difference at the interface between the amorphous polymer phase and the crystalline phase. In some embodiments, the refractive index difference between a given polymeric phase and an adjacent phase (e.g., a crystalline phase and an adjacent amorphous phase) can be less than about 0.1, less than about 0.01, or less than about 0.001.

[0430] The present disclosure further provides a polymer film comprising the polymer material of the present disclosure. In some cases, the thickness of such a polymer film can be at least about 50 μm, 100 μm, 250 μm, 500 μm, 1 mm, 2 mm and not more than 3 mm.

[0431] Polymer Materials in Medical Devices

[0432] The present disclosure provides a device comprising the polymer material described herein. As described herein, such polymer materials can include one or more polymerizable monomers described herein in their polymer structure, such as the compounds represented by formulas (I)-(VI) and (IX). In various cases, the device can be a medical device. The medical device can be an orthodontic appliance. The orthodontic appliance can be a dental aligner, a tooth expander, or a tooth spacer.

[0433] IV. Methods of Use

[0434] The present disclosure provides methods for synthesizing the polymerizable monomers described herein, methods for using compositions (e.g., resins and polymer materials) containing such monomers, and methods for using them in devices such as medical devices. The photo-polymerizable monomers of the present disclosure, such as the monomers according to any one of formulas (I)-(VIII), can be used as material components and are applicable to many industries such as transportation (e.g., airplanes, trains, ships, automobiles, etc.), makers, prototyping, medical, art and design, microfluidics, and molds. In various embodiments herein, such medical devices include orthodontic appliances.

[0435] Synthesis Methods

[0436] The present invention provides a synthesis method for preparing the polymerizable monomers described herein. In some embodiments, the polymerizable monomer represented by formula (I) of the present invention can be prepared according to the following exemplary Scheme 1:

[0437]

[0438] Wherein:

[0439] X is O, S, NR 6 or SiR 7 R 8 ;

[0440] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0441] R 2 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6Heteroalkyl, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0442] R 3 、R 4 and R 5 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or -Y-(CH2) n -R 9 , or R 4 and R 5 together form a 4-, 5-, 6-, 7- or 8-membered ring, the ring being selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0443] wherein Y is O, S, NH or C(O)O;

[0444] n is an integer from 0 to 6;

[0445] R 6 、R 7 and R 8 are independently H or substituted or unsubstituted C 1-6 alkyl; and

[0446] R 9 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0447] In some embodiments, the polymerizable monomer of formula (II) according to the present disclosure can be prepared as shown in the following exemplary Scheme 2:

[0448]

[0449] Wherein:

[0450] R 1is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0451] R 10 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0452] R 11 and R 12 each independently is H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or -X-(CH2) n -R 13 or R 11 and R 12 together form a 4-, 5-, 6-, 7- or 8-membered ring, the ring being selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0453] wherein X is O, S, NH or C(O)O;

[0454] n is an integer from 0 to 6; and

[0455] R 13 is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0456] In some embodiments, the polymerizable monomer of formula (III) according to the present disclosure can be prepared as shown in the following exemplary Scheme 3:

[0457]

[0458] Wherein:

[0459] PG is a suitable phenolic alcohol protecting group;

[0460] LG is a suitable leaving group, such as hydroxyl, chlorine, bromine, etc.

[0461] R 1 is H, a substituted or unsubstituted C 1-3 alkyl group, or a halogen;

[0462] R 14 is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted cyclo(C 3-8 )alkyl group, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0463] R 15 and R 16 are each independently H, a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 heteroalkyl group, a substituted or unsubstituted C 1-6 alkoxy group, a substituted or unsubstituted C 1-6 thioalkoxy group, a substituted or unsubstituted C 1-6 carbonyl group, a substituted or unsubstituted C 1-6 carboxyl group, or -X-(CH2) n -R 17 ; or R 15 and R 16 together form a 4-, 5-, 6-, 7- or 8-membered ring, and the ring is selected from a substituted or unsubstituted cyclo(C 4-8 )alkyl group, a substituted or unsubstituted cyclo(C 4-8 )heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

[0464] wherein X is O, S, NH or C(O)O;

[0465] n is an integer from 0 to 6; and

[0466] R 17 is a substituted or unsubstituted cyclo(C 3-8 )alkyl group, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0467] In some embodiments, the polymerizable monomer of formula (IV) according to the present invention can be prepared as shown in the following exemplary Scheme 4:

[0468]

[0469] Wherein:

[0470] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0471] R 18 is substituted C 2-6 alkyl, substituted or unsubstituted C 1-6 alkyl, or substituted or unsubstituted C 1-6 heteroalkyl; and

[0472] R 19 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, or substituted or unsubstituted C 1-6 carboxyl.

[0473] In some embodiments, the polymerizable monomer of formula (V) according to the present disclosure can be prepared as shown in the following exemplary Scheme 5:

[0474]

[0475] Wherein:

[0476] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0477] R 20 and R 22 are each independently substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 1 -(CH2) a -R 28 ;

[0478] R 21 and R 23 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C1-6 Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, or –X 2 -(CH2) b -R 29 ;

[0479] X 1 and X 2 each independently is a bond, O or S;

[0480] a and b each independently is an integer from 0 to 6; and

[0481] R 28 and R 29 each independently is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0482] In some embodiments, the polymerizable monomer of formula (VI) according to the present disclosure can be prepared as shown in the following exemplary Scheme 6:

[0483]

[0484] Wherein:

[0485] R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;

[0486] R 32 and R 34 each independently is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl, or –X 5 -(CH2) e -R 42 ;

[0487] R 33 and R 35 each independently is H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6Heteroalkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted C 1-6 Thioalkoxy, substituted or unsubstituted C 1-6 Carbonyl, substituted or unsubstituted C 1-6 Carboxyl, or –X 6 -(CH2) f -R 43 ;

[0488] X 5 and X 6 each independently is a bond, O, or S;

[0489] e and f each independently is an integer from 0 to 6; and

[0490] R 42 and R 43 each independently is substituted or unsubstituted cyclo(C 3-8 )alkyl, substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0491] In some embodiments, any such method can include separating a polymerizable monomer having a chemical purity of at least about 90%, 95%, or 99% in a chemical yield of at least about 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or at least about 95%.

[0492] Those skilled in the art will understand that substituents (e.g., R 1 -R 23 , R 28 -R 29 , R 32 -R 35 , and R 42 -R 43 ) can be changed before, during, or after the preparation of the phenyl acrylate backbone, and appropriate adjustments can be made to exemplary conditions (e.g., temperature, solvent, etc.). In addition, those skilled in the art should recognize that protecting groups may be necessary for the preparation of certain compounds and should be aware of the conditions compatible with the selected protecting groups.

[0493] Method for forming a polymeric material

[0494] The present disclosure also provides a method of polymerizing (e.g., photocuring) a curable composition (e.g., a photocurable resin), the curable composition comprising at least one polymerizable monomer described herein (e.g., monomers according to formulas (I)-(VI) and (IX)), and optionally one or more other components selected from the group consisting of telechelic polymers, telechelic oligomers, polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, colorants, surface modifiers, and mixtures thereof, to obtain an optionally crosslinked polymer, the method comprising the steps of: optionally after heating, mixing the curable composition with a reactive diluent, and then initiating polymerization by heating and / or irradiating the composition; wherein the reactive diluent is selected from polymerizable monomers, e.g., monomers according to any one of formulas (I)-(VI) and (IX) of the first aspect of the present disclosure, and mixtures thereof.

[0495] The present disclosure provides methods of producing polymeric materials using the curable resins described herein. In various embodiments, methods of photocuring a photocurable resin are provided herein. Thus, in various instances, a method of forming a polymeric material is provided, the method comprising: (i) providing a photocurable resin of the present disclosure; (ii) exposing the photocurable resin to a light source; and curing the photocurable resin to form the polymeric material.

[0496] In some embodiments, photocuring comprises a single curing step. In some embodiments, photocuring comprises multiple curing steps. In other embodiments, photocuring comprises at least one curing step of exposing the curable resin to light. Exposing the curable resin to light can initiate and / or facilitate 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, at least one step comprising exposure to a light source is used to form a cured polymeric material from the photocurable resin, wherein the light source comprises UV light, visible light, and / or IR light. In some embodiments, the light source comprises a wavelength from 10 nm to 200 nm, from 200 nm to 350 nm, from 350 nm to 450 nm, from 450 nm to 550 nm, from 550 nm to 650 nm, from 650 nm to 750 nm, from 750 nm to 850 nm, from 850 nm to 1000 nm, or from 1000 nm to 1500 nm.

[0497] In some embodiments, the method of forming a polymeric material from a photopolymerizable resin as described herein may further include initiating phase separation in the polymeric material being formed (i.e., during the photocuring process), wherein such phase separation may be polymerization-initiated. Polymerization-initiated phase separation may include generating one or more polymer phases in the polymeric material during the photocuring process. In certain cases, at least one of the one or more polymer phases is an amorphous polymer phase. The glass transition temperature (Tg) of such at least one amorphous polymer phase may be at least about 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 110 °C, or at least about 120 °C. In certain cases, the glass transition temperature (Tg) of at least 25%, 50%, or 75% of the polymer phases generated during the photocuring process is at least about 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 110 °C, or at least about 120 °C. In certain cases, at least one polymer phase having a glass transition temperature (Tg) of at least about 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 110 °C, or at least about 120 °C comprises a polymerizable monomer as shown in any one of formulas (I)-(VI) and (IX) incorporated into the polymer structure (i.e., in polymerized form). In various cases, at least one of the one or more polymer phases generated during the photocuring process comprises a crystalline polymeric material. Thus, in certain cases, at least one of the one or more polymer phases is a crystalline polymer phase. The melting point of such crystalline polymeric material (e.g., as part of the crystalline phase) may be at least about 40 °C, 50 °C, 60 °C, 80 °C, 90 °C, 100 °C, 110 °C, or at least about 120 °C.

[0498] In some embodiments, the method of forming a polymeric material from a photo-polymerizable resin as described herein may further include initiating and / or enhancing the formation of a crystalline phase in the polymeric material being formed. In certain embodiments, the initiating includes cooling the cured material, adding seed particles to the resin, applying a force to the cured material, applying an electric charge to the resin, or any combination thereof. In certain cases, polymer crystals yield after the application of strain (e.g., physical strain, such as twisting or stretching the material). Yield may include unraveling, unwinding, disentangling, dislocation, gross slip, and / or fine slip in the crystalline polymer. In some embodiments, the methods disclosed herein further include the step of growing polymer crystals. As further described herein, the polymer crystals comprise a crystallizable polymeric material.

[0499] Accordingly, in various embodiments, a method of forming a polymeric material from a photo-polymerizable resin described herein can include initiating phase separation in the polymeric material being formed (i.e., during photo-curing), where such phase separation can result in a polymeric material that includes one or more amorphous phases, one or more crystalline phases, or both one or more amorphous phases and one or more crystalline phases.

[0500] As described herein, a polymeric material prepared by the methods provided herein can have one or more of the following properties: (i) a storage modulus greater than or equal to 200 MPa; (ii) a remaining flexural stress and / or flexural modulus greater than or equal to 1.5 MPa after being placed in a moist environment at 37 °C for 24 hours; (iii) an elongation at break greater than or equal to 5% before and after being placed in a moist environment at 37 °C for 24 hours; (iv) a water absorption less than 25 wt% when measured after being placed in a moist environment at 37 °C for 24 hours; and (v) at least 30% of visible light passing through the polymeric material after being placed in a moist environment at 37 °C for 24 hours. In various cases, such polymeric materials can have at least 2, 3, 4, or all of the above properties.

[0501] Manufacture and use of orthodontic appliances

[0502] Provided herein are methods of manufacturing medical devices (such as dental aligners, tooth expanders, or tooth spacers) using polymerizable monomers, curable resins, and compositions containing such monomers, and polymeric materials prepared from such resins and compositions.

[0503] Accordingly, in some embodiments, the methods described herein further include the step of manufacturing a device or object using an additive manufacturing device, where the additive manufacturing device facilitates curing. In some embodiments, curing of the polymerizable resin results in a cured polymeric material. In certain embodiments, the polymerizable resin is cured using an additive manufacturing device to produce a cured polymeric material. In some embodiments, the method further includes the step of cleaning the cured polymeric material. In certain embodiments, cleaning the cured polymeric material includes washing and / or rinsing the cured polymeric material with a solvent that can remove uncured resin and unwanted impurities from the cured polymeric material.

[0504] In some embodiments, the polymerizable resins described herein can be curable and have a melting point below 100 °C, such that they remain liquid and processable at the temperatures typically employed in current additive manufacturing techniques. As described herein, the polymerizable monomers used as curable resin components in the present disclosure can have a lower vapor pressure at elevated temperatures compared to conventional reactive diluents or other polymerizable components for curable resins. This low vapor pressure of the monomers described herein is particularly advantageous for the use of such monomers in curable (e.g., photocurable) compositions and additive manufacturing that may use elevated temperatures (e.g., 60 °C, 80 °C, 90 °C or higher). In various cases, the vapor pressure of the polymerizable monomer at 60 °C can be at most about 12 Pa, or lower, as further described herein.

[0505] In some embodiments, the curable resin described herein can comprise at least one photoinitiator (i.e., a photoinitiator), and can be heated to a predetermined elevated temperature (in the range of about 50 °C to about 120 °C, such as about 90 °C to about 120 °C), and then irradiated with light having a wavelength suitable for absorption by the photoinitiator, thereby activating the photoinitiator to initiate polymerization of the curable resin to obtain a cured polymeric material, which can optionally be crosslinked. In some embodiments, the curable resin can comprise at least one polyvalent polymerizable monomer capable of providing a crosslinked polymer.

[0506] In some embodiments, the method of forming a polymeric material disclosed herein is part of a photopolymerization process based on high-temperature lithography, wherein a curable composition (e.g., a photocurable resin) that can comprise at least one photoinitiator is heated to an elevated process temperature (e.g., about 50 °C to about 120 °C, such as about 90 °C to about 120 °C). Thus, the method of forming a polymeric material according to the present disclosure can be used to rapidly and conveniently produce devices such as orthodontic appliances by additive manufacturing (e.g., 3D printing) using the curable resins disclosed herein. In various embodiments, such curable resins are photocurable resins comprising one or more of the photopolymerizable monomers described in any one of Formulas (I)-(VI) and (IX).

[0507] Photopolymerization can occur when the photocurable resin of the present disclosure is exposed to radiation (e.g., UV or visible light) at a wavelength sufficient to initiate polymerization. The radiation wavelength that can be used to initiate polymerization may depend on the photoinitiator used. "Light" as used herein includes any wavelength and power capable of initiating polymerization. Some wavelengths of light include ultraviolet (UV) or visible light. UV light sources include UVA (wavelength from about 400 nanometers (nm) to about 320 nm), UVB (about 320 nm to about 290 nm), or UVC (about 290 nm to about 100 nm). Any suitable light source can be used, including laser light sources. The light source can be broadband or narrowband, or a combination of both. The light source can provide continuous light or pulsed light during the process. The length of time the system is exposed to UV light and the intensity of the UV light can be varied to determine the ideal reaction conditions.

[0508] In some embodiments, the methods disclosed herein include using additive manufacturing techniques to produce devices comprising cured polymeric materials. Such devices can be orthodontic appliances. The orthodontic appliance can be a dental aligner, a tooth expander, or a tooth spacer. In certain embodiments, the methods disclosed herein use additive manufacturing techniques to produce devices comprising, consisting essentially of, or consisting of cured polymeric materials. Additive manufacturing includes a variety of techniques that directly fabricate three-dimensional objects from digital models by additive processes. In some aspects, materials are deposited layer by layer and "cured in situ". A variety of 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 layers of powder material according to a desired cross-sectional shape in order to build the object geometry. In many embodiments, fused deposition modeling involves melting and selectively depositing filaments of thermoplastic polymer in a layer-by-layer manner to form an object. In yet another example, 3D printing can be used to fabricate the orthodontic appliances herein. In many embodiments, 3D printing involves jetting or extruding one or more materials (e.g., the crystalline resins disclosed herein) onto a build surface to form successive layers of the object geometry. In some embodiments, the photocurable resins described herein can be used in inkjet or coating applications. Cured polymeric materials can also be fabricated by a "vat" process that utilizes light to selectively cure the curable resin within a vat or reservoir. Each layer of the curable resin can be selectively exposed to light in a single exposure or by scanning a light beam across the layer. Specific techniques that can be used herein can include stereolithography (SLA), digital light processing (DLP), and two-photon induced photopolymerization (TPIP).

[0509] In some embodiments, the methods disclosed herein use continuous direct manufacturing to produce devices that include cured polymeric materials. Such devices can be orthodontic appliances as described herein. In certain embodiments, the methods disclosed herein can include using continuous direct manufacturing to produce a device (e.g., an orthodontic appliance) that comprises, consists essentially of, or consists of a cured polymeric material. Non-limiting exemplary direct manufacturing processes can achieve the continuous construction of an object geometry by the continuous movement (e.g., along a longitudinal or Z direction) of a build platform during a radiation stage such that the depth of hardening of the irradiated photopolymer (e.g., the irradiated photocurable resin that hardens during the formation of the cured polymeric material) is controlled by the movement speed. Thus, continuous polymerization of the material (e.g., polymerization of a photocurable resin into a cured polymeric material) can be achieved on the build surface. Such methods are described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety. In another example, a continuous direct manufacturing method utilizes a "heliolithography" method in which a liquid resin (e.g., a photocurable resin) is cured by focused radiation while the build platform continuously rotates and ascends. Thus, the object geometry can be continuously constructed along a helical build path. Such methods are described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety. The continuous liquid interface production of 3D objects has also been reported (J. Tumbleston et al., Science, 2015, 347(6228), pp 1349-1352), which is incorporated herein by reference to describe the process. Another example of a continuous direct manufacturing method can include extruding a material that comprises a curable liquid material or resin around a solid strand. The material can be extruded along a continuous three-dimensional path to form an object. Such methods are described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0510] In some embodiments, the methods disclosed herein may include using high-temperature lithography to produce an instrument comprising a cured polymeric material. Such an instrument may be an orthodontic appliance as described herein. In certain embodiments, the methods disclosed herein use high-temperature lithography to produce an instrument comprising, consisting essentially of, or consisting of a cured polymeric material. As used herein, "high-temperature lithography" may refer to any lithography-based photopolymerization process that involves heating a photo-polymerizable material (e.g., the photo-curable resins disclosed herein). The heating may reduce the viscosity of the photo-curable resin before and / or during curing. Non-limiting examples of high-temperature lithography processes include those described in WO 2015 / 075094, WO 2016 / 078838, and WO 2018 / 032022. In some embodiments, high-temperature lithography may involve applying heat to the material to about 50 °C to about 120 °C, e.g., about 90 °C to about 120 °C, about 100 °C to about 120 °C, about 105 °C to about 115 °C, about 108 °C to about 110 °C, etc. The material may be heated to a temperature higher than about 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.

[0511] Since, in certain cases, the polymerizable monomers of the present disclosure may copolymerize during the polymerization process of the present disclosure method as part of a photo-curable resin, the resulting product may be an optionally cross-linked polymer that contains portions of one or more polymerizable monomers as repeating units. In certain cases, such polymers are cross-linked polymers and are generally suitable for orthodontic appliance applications.

[0512] In a further embodiment, the methods herein may include polymerizing a curable composition that comprises at least one polyvalent monomer that, upon polymerization, can form a cross-linked polymer that may contain portions derived from the polymerizable monomers of the present disclosure as repeating units. To obtain a cross-linked polymer that is particularly suitable for use as an orthodontic appliance, at least one polymerizable substance for the methods of the present disclosure may be selected based on various thermo-mechanical properties of the resulting polymer. In certain cases, the curable resins of the present disclosure may comprise one or more polyvalent polymerizable monomers. In certain cases, the polymerizable monomers of the present disclosure may also have cross-linking functional groups and thus can be used not only as reactive diluents with low vapor pressure but also as cross-linking agents during the polymerization of the curable resins described herein. In other embodiments, the resin comprises the polymerizable monomers and cross-linking monomers described herein, where the two monomers are different substances (i.e., chemical entities).

[0513] V. Orthodontic Appliances and Their Uses

[0514] The polymerizable monomers according to the present invention, such as the monomers according to any one of formulas (I)-(VI) and (IX), can be used as components of a viscous or highly viscous photocurable resin and can produce a polymeric material having advantageous thermomechanical properties (e.g., rigidity, residual bending stress, etc.) as described herein for use in orthodontic appliances, such as for moving one or more teeth of a patient.

[0515] As described herein, the present 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 alignments for moving the teeth along a treatment path from an initial tooth alignment to a final tooth alignment; (ii) producing an orthodontic appliance comprising a polymeric material as described herein (e.g., a polymeric material comprising monomers of formulas (I)-(VI) and (IX)); and (iii) using the orthodontic appliance to move at least one tooth of the patient along an orbit towards an intermediate tooth alignment or a final tooth alignment. Such orthodontic appliances can be produced 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 the orthodontic appliance is 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. In such a case, after 2 weeks of treatment, more than 60% of the patient's teeth are on the orbit of the treatment plan. In some cases, the orthodontic appliance has a retained repositioning force on at least one tooth of the patient after 2 days, the retained repositioning force being 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.

[0516] As used herein, the terms "rigidity" and "stiffness" may but need not be used interchangeably, as with the corresponding terms "rigid" and "stiff". As used herein, "multiple teeth" includes two or more teeth.

[0517] 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, cuspids, first bicuspids or second bicuspids.

[0518] In some embodiments, the compositions and methods described herein can be used to couple one or more groups of teeth to each other. One or more groups of teeth can 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 by a polymeric shell appliance as disclosed herein.

[0519] The embodiments disclosed herein are well suited for moving one or more teeth in a first set of one or more teeth, or moving one or more teeth in a second set of one or more teeth, and combinations thereof.

[0520] The embodiments disclosed herein are well suited for combination with one or more known commercially available tooth moving components (e.g., attachments and polymeric shell appliances). In many embodiments, the appliance and one or more attachments are configured to move one or more teeth along a tooth movement vector that includes six degrees of freedom, where three degrees of freedom are rotational and three degrees of freedom are translational.

[0521] The present disclosure provides orthodontic systems and related methods for designing and providing improved or more efficient tooth movement systems for effecting desired tooth movement and / or repositioning teeth into a desired alignment.

[0522] Although reference is made to appliances including polymeric shell appliances, the embodiments disclosed herein are well suited for use with many appliances that receive teeth, e.g., appliances that do not have one or more of a polymer or a shell. The appliance can be fabricated from one or more of many filling materials, e.g., metals, glass, reinforcing fibers, carbon fibers, composite materials, reinforced composite materials, aluminum, biomaterials, and combinations thereof. In some cases, the reinforced composite material can include a polymer matrix reinforced with, e.g., ceramic or metal particles. The appliance can be formed in many ways, e.g., thermoformed or directly fabricated as described herein. Alternatively or in combination, the appliance can be fabricated by machining, e.g., an appliance fabricated from a block of material by computer numerical control machining. In some cases, a polymerizable monomer according to the present disclosure is used, e.g., using the monomer as a reactive diluent for a curable resin, to fabricate the appliance.

[0523] Turning now to the drawings, in which like numerals represent like elements throughout the several views, Figure 1AAn exemplary tooth repositioning appliance or aligner 100 is shown that a patient may wear to effect progressive repositioning of a single tooth 102 within the jaw. The appliance may include a housing (e.g., a continuous polymeric housing or a segmented housing) having tooth receiving cavities for receiving and effecting tooth repositioning by elastic repositioning forces. The appliance or portions thereof may be indirectly fabricated using a physical model of the teeth. For example, a physical model of the teeth and a layer of a suitable polymeric material may be used to form the appliance (e.g., a polymeric appliance). In some embodiments, the physical appliance may be directly fabricated based on a digital model of the appliance, such as using rapid prototyping fabrication techniques. The appliance may cover all of the teeth of the upper jaw or the lower jaw, or less than all of the teeth. The appliance may be specifically designed based on the patient's tooth morphology (e.g., the topography of the tooth receiving cavities matches the topography of the patient's teeth), and may be fabricated based on a positive or negative mold of the patient's teeth, where the positive or negative mold is generated by impression, scanning, etc. Alternatively, the appliance may be a general appliance configured to receive teeth, but it is not necessarily shaped to match the topography of the patient's teeth. In some cases, only the particular teeth received by the appliance will be repositioned by the appliance, while other teeth may act as a base or an anchor region for securing the appliance in place when the appliance applies forces to one or more teeth to be repositioned. In some cases, some, most, or even all of the teeth will be repositioned at some point during treatment. The teeth being moved may also act as a base or an anchor point for securing the appliance in place when the patient wears the appliance. Generally, no wires or other devices are provided to hold the appliance in place on the teeth. However, in some cases, it may be desirable or necessary to provide separate attachments or other anchoring elements 104 on the tooth 102 and corresponding receptacles or apertures 106 in the appliance 100 so that the appliance can apply selected forces on the teeth. Exemplary appliances including those used in the system are described in a number of patents and patent applications assigned to Align Technology, Inc. (including, for example, U.S. Patent Nos. 6,450,807 and 5,975,893) and on the company's website (which is accessible on the World Wide Web (e.g., see the URL "invisalign.com")). Examples of tooth-mounted attachments suitable for use with orthodontic appliances are also described in patents and patent applications assigned to Align Technology, Inc. (including, for example, U.S. Patent Nos. 6,309,215 and 6,830,450). Exemplary appliances such as those used in the system. Examples of tooth-mounted attachments suitable for use with orthodontic appliances are also described in patents and patent applications assigned to Align Technology, Inc. (including, for example, U.S. Patent Nos. 6,309,215 and 6,830,450).

[0524] Figure 1B A tooth repositioning system 110 is shown that includes multiple appliances 112, 114, 116. Any of the appliances described herein can be designed as and / or provided as part of a multiple appliance kit in a tooth repositioning system. Each appliance can be configured such that the geometry of its tooth receiving cavity corresponds to the intended intermediate or final tooth alignment of the appliance. By placing a series of incremental position adjustment appliances over a patient's teeth, the patient's teeth can be gradually repositioned from an initial tooth alignment to a target tooth alignment. For example, the tooth repositioning system 110 can include a first appliance 112 corresponding to an initial tooth alignment, one or more intermediate appliances 114 corresponding to one or more intermediate alignments, and a final appliance 116 corresponding to a target alignment. The target tooth alignment can 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 some intermediate alignments of the patient's teeth during orthodontic treatment, which may include a variety of different treatment scenarios, including but not limited to the following: cases where surgery is recommended, cases suitable for interproximal reduction (IPR), cases where progress checks are planned, cases where the anchorage position is optimal, cases where palatal expansion is needed, cases involving restorative dentistry (e.g., inlays, onlays, crowns, bridges, implants, veneers, etc.). Thus, it can be understood that the target tooth alignment can be any planned final alignment of the patient's teeth after undergoing one or more incremental repositioning phases. Similarly, the initial tooth alignment can be any initial alignment of the patient's teeth before undergoing one or more incremental repositioning phases.

[0525] Figure 1CA method 150 for orthodontic treatment using multiple appliances according to various embodiments is shown. Method 150 can be practiced using any of the appliances or appliance sets described herein. In step 160, a first orthodontic appliance is applied to a patient's teeth to reposition the teeth from a first tooth alignment to a second tooth alignment. In step 170, a second orthodontic appliance is applied to the patient's teeth to reposition the teeth from the second tooth alignment to a third tooth alignment. If necessary, method 150 can be repeated using any suitable number and combination of successive appliances to progressively reposition the patient's teeth from an initial alignment to a target alignment. The appliances can be produced all at once in the same phase, or in sets or batches (e.g., at the start of a phase of treatment), or the appliances can be produced one at a time and the patient can wear each appliance until no further pressure on the teeth is felt from each appliance, or until a maximum amount of tooth movement expressed for a given phase is reached. Multiple different appliances (e.g., a set) can be designed and even manufactured before the patient wears any one of the multiple appliances. After wearing an appliance for an appropriate period of time, the patient can replace the current appliance with the next appliance in the series until no appliances remain. The appliances are generally not fixed to the teeth and the patient can place and replace the appliances at any time during the procedure (e.g., appliances that the patient can remove and replace themselves). The last appliance or several appliances in the series can have one or more selected geometries to overcorrect the tooth alignment. For example, the geometry of one or more appliances may, if fully realized, move individual teeth beyond a selected "final" tooth alignment. Such overcorrection may be desirable to counteract potential relapse after the repositioning method has ended (e.g., allowing individual teeth to move back to their pre-correction positions). Overcorrection may also help to speed up the correction (e.g., an appliance with a geometry that extends beyond the desired intermediate or final position may move individual teeth towards that position at a greater rate). In such cases, the use of the appliance can be terminated before the teeth reach the position defined by the appliance. Additionally, overcorrection may be deliberately performed to compensate for any inaccuracies or limitations of the appliance.

[0526] 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) herein can be produced using direct manufacturing, such as additive manufacturing techniques (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 a physical template (e.g., a mold, a mask, etc.) to define the geometry of the object. Additive manufacturing techniques can be classified into the following categories: (1) Vat photopolymerization (e.g., stereolithography), in which an object is constructed layer by layer from a vat of liquid photopolymer resin; (2) Material jetting, in which materials are jetted onto a build platform using a continuous or drop-on-demand (DOD) method; (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 print head; (4) Fused deposition modeling (FDM), in which material is extruded, heated, and deposited layer by layer through a nozzle; (5) Powder bed fusion, including but not limited to direct metal laser sintering (DMLS), electron beam melting (EBM), selective heat sintering (SHS), selective laser melting (SLM), and selective laser sintering (SLS); (6) Sheet lamination, including but not limited to laminated object manufacturing (LOM) and ultrasonic additive manufacturing (UAM); and (7) Directed energy deposition, including but not limited to laser engineered net shaping, directed light fabrication, direct metal deposition, and 3D laser cladding. For example, stereolithography can be used to directly manufacture one or more appliances herein. In some embodiments, stereolithography involves selectively polymerizing a photosensitive resin (e.g., a photopolymer) using light (e.g., ultraviolet light) according to a desired cross-sectional shape. By sequentially polymerizing multiple cross-sections of the object, the object geometry can be built layer by layer. As another example, selective laser sintering can be used to directly manufacture the appliances herein. In some embodiments, selective laser sintering involves selectively melting and fusing layers of powder material using a laser beam according to a desired cross-sectional shape to build the object geometry. As another example, the appliances herein can be directly manufactured by 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, material jetting can be used to directly manufacture the appliances herein. In some embodiments, material jetting involves jetting or extruding one or more materials onto a build surface to form successive layers of the object geometry.

[0527] Alternatively or in combination, some embodiments of the appliances (or portions thereof) herein can be produced using indirect manufacturing techniques, such as thermoforming over a male or female mold. Indirect manufacturing of orthodontic appliances can involve producing a male or female mold of a patient's dentition with a target alignment (e.g., by rapid prototyping, milling, etc.) and thermoforming one or more sheets of material over the mold to generate the appliance shell.

[0528] In some embodiments, the direct manufacturing methods provided herein build the object geometry in a layer-by-layer manner, where layers are successively formed in discrete build steps. Alternatively or in combination, direct manufacturing methods that allow for the continuous build of the object geometry, referred to herein as "continuous direct manufacturing," can be used. A variety of types of continuous direct manufacturing methods can be used. As an example, in some embodiments, "continuous liquid interface printing" is used to fabricate the apparatuses herein, where an object is continuously built from a photo-curable resin reservoir by forming a gradient of partially cured resin between the build surface of the object and a polymerization-inhibiting "dead zone." In some embodiments, a semi-permeable membrane is used to control the transport of a photo-polymerization inhibitor (e.g., oxygen) into the dead zone to form a polymerization gradient. Continuous liquid interface printing can achieve a manufacturing speed that is approximately 25 to approximately 100 times faster than other direct manufacturing methods, and by incorporating a cooling system, a speed that is approximately 1000 times faster can be achieved. Continuous liquid interface printing is described in U.S. Patent Publication Nos. 2015 / 0097315, 2015 / 0097316, and 2015 / 0102532, the respective disclosures of which are incorporated herein by reference in their entireties.

[0529] As another example, a continuous direct manufacturing method can achieve the continuous build of the object geometry by the build platform continuously moving (e.g., along a longitudinal or Z direction) during the irradiation phase, such that the depth of hardening of the irradiated photo-polymer is controlled by the speed of movement. Thus, 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.

[0530] In another example, a continuous direct manufacturing method can involve extruding a composite material composed of a curable liquid material surrounding a solid strand. The composite material can be extruded along a continuous three-dimensional path to form 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.

[0531] In yet another example, a continuous direct manufacturing method employs a "heliolithography" method, where a liquid photo-polymer is cured using focused radiation while the build platform is continuously rotated and raised. Thus, the 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.

[0532] The direct manufacturing method provided herein is compatible with a variety of materials, including but not limited to one or more of the following: polyester, copolyester, polycarbonate, thermoplastic polyurethane, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic, cyclic block copolymer, polyetheretherketone, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polysulfone, polytrimethylene terephthalate, styrene block copolymer (SBC), silicone rubber, elastomer alloy, thermoplastic elastomer (TPE), thermoplastic vulcanizate (TPV) elastomer, polyurethane elastomer, block copolymer elastomer, polyolefin blend elastomer, thermoplastic copolyester elastomer, thermoplastic polyamide elastomer, thermosetting material, or combinations thereof. The materials for direct manufacturing can be provided in an uncured form (e.g., liquid, resin, powder, etc.) and can be cured (e.g., by photopolymerization, photocuring, gas curing, laser curing, crosslinking, etc.) to form an orthodontic appliance or a part thereof. The properties of the material before curing may be different from the properties of the material after curing. Once cured, the materials herein can exhibit sufficient strength, stiffness, durability, biocompatibility, etc. to be used for orthodontic appliances. The post-curing characteristics of the materials used can be selected according to the desired characteristics of the corresponding parts of the appliance.

[0533] In some embodiments, the relatively rigid portions 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 copolymers, acrylic, cyclic block copolymer, polyetheretherketone, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polysulfone, and / or polytrimethylene terephthalate.

[0534] In some embodiments, the relatively elastic portions 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 vulcanizate (TPV) elastomer, polyurethane elastomer, block copolymer elastomer, polyolefin blend elastomer, thermoplastic copolyester elastomer, and / or thermoplastic polyamide elastomer.

[0535] Machine parameters can include curing parameters. For a digital light processing (DLP)-based curing system, the curing parameters can include power, curing time, and / or the gray scale of the complete image. For a laser-based curing system, the curing parameters can include power, speed, beam size, beam shape, and / or the power distribution of the beam. For a printing system, the 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 the process control on the manufacturing machine. The 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 through a feedback loop. For a DLP machine, depending on the stability of the system, the gray scale can be measured and calibrated before, during, and / or at the end of each build and / or at predetermined time intervals (e.g., every n builds, once an hour, once a day, once a week, etc.). Additionally, material properties and / or optical properties 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, gray scale, etc.) to compensate for changes in material properties. By implementing process control on the manufacturing machine, variations in appliance accuracy and residual stress can be reduced.

[0536] Optionally, the direct manufacturing methods described herein allow for the manufacture of appliances comprising multiple materials, herein referred to as "multi-material direct manufacturing". In some embodiments, the multi-material direct manufacturing method involves forming an object from multiple materials simultaneously in a single manufacturing step. For example, a multi-tip extrusion device can be used to selectively dispense multiple types of materials from different material supply sources in order 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 multi-material direct manufacturing method can involve forming an object from multiple materials in multiple successive manufacturing steps. For example, a first part of the object can be formed from a first material according to any of the direct manufacturing methods herein, and then a second part of the object can be formed from a second material according to the methods herein, and so on until the entire object is formed.

[0537] Compared with other manufacturing methods, direct manufacturing can offer various advantages. For example, compared with indirect manufacturing, direct manufacturing allows the production of orthodontic appliances without using any molds or templates to form the appliances, thereby reducing the number of manufacturing steps involved and improving the resolution and precision of the final appliance geometry. In addition, direct manufacturing allows precise control of the three-dimensional geometry of the appliance, such as the 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 having very small or fine features, complex geometries, undercuts, abutment structures, shells with variable thicknesses, and / or internal structures (e.g., to increase strength with reduced weight and material use). For example, in some embodiments, the direct manufacturing methods herein allow the manufacture of orthodontic appliances having feature sizes 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.

[0538] The direct manufacturing techniques described herein can be used to produce appliances having substantially isotropic material properties, e.g., substantially the same or similar strength in all directions. In some embodiments, the direct manufacturing methods herein allow the production of orthodontic appliances in which the strength varies by no more than about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% in all directions. In addition, compared with other manufacturing techniques, the direct manufacturing methods herein can be used to produce orthodontic appliances at a faster rate. In some embodiments, the direct manufacturing methods herein allow the production of orthodontic appliances at time intervals 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. Such manufacturing speeds allow for the rapid "chairside" production of custom appliances during routine appointments or examinations.

[0539] In some embodiments, 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. Such precision can be beneficial in ensuring the accurate transmission of the desired force system to the teeth to effectively cause tooth movement. Process control can be implemented to account for process variability caused by multiple sources, such as material properties, machine parameters, environmental variables, and / or post-processing parameters.

[0540] Depending on the nature of the raw materials, the purity of the raw materials, and / or the process variables during the raw material mixing process, the material properties may vary. In many embodiments, the resin or other materials for direct manufacturing should be manufactured under strict process control to ensure little variation in optical properties, material properties (such as viscosity, surface tension), physical properties (such as modulus, strength, elongation), and / or thermal properties (such as glass transition temperature, heat distortion temperature). Process control of the material manufacturing process can be achieved by physically screening the raw materials and / or controlling temperature, humidity, and / or other process parameters during the mixing process. By implementing process control on the material manufacturing procedure, the variability of process parameters can be reduced, and the material properties of each batch of materials can be made more uniform. As further discussed herein, the remaining variation in material properties can be compensated for by process control on the machine.

[0541] Machine parameters can include curing parameters. For digital light processing (DLP)-based curing systems, the curing parameters can include power, curing time, and / or the gray scale of the complete image. For laser-based curing systems, the curing parameters can include power, speed, beam size, beam shape, and / or the power distribution of the beam. For printing systems, the curing parameters can include material droplet size, viscosity, and / or curing power. These machine parameters can be monitored and adjusted regularly (e.g., some parameters every 1 - x layers and some parameters after each build) as part of the 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 through a feedback loop. For DLP machines, the gray scale can be measured and calibrated at the end of each build. Additionally, material properties and / or optical properties can be provided to the manufacturing machine, and the machine process control module can use these parameters to adjust machine parameters (such as power, time, gray scale, etc.) to compensate for the variation in material properties. By implementing process control on the manufacturing machine, the variation in appliance accuracy and residual stress can be reduced.

[0542] In many embodiments, environmental variables (such as temperature, humidity, sunlight, or exposure to other energy / curing sources) are maintained within strict ranges to reduce the variability of appliance thickness and / or other properties. Optionally, machine parameters can be adjusted to compensate for environmental variables.

[0543] In many embodiments, post-treatment of the appliance includes cleaning, post-curing, and / or support removal processes. Associated post-treatment parameters can include the purity of the detergent, 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. Additionally, the physical properties of the appliance can be altered by modifying the post-treatment parameters. Adjusting the post-treatment machine parameters can provide another way to compensate for variations in material properties and / or machine properties.

[0544] The configuration of the orthodontic appliances herein can be determined according to a treatment plan for a patient, e.g., a treatment plan involving the sequential application of multiple appliances for the progressive repositioning of teeth. Computer-based treatment planning and / or appliance manufacturing methods can be used to facilitate the design and manufacture of the appliances. For example, one or more appliance assemblies described herein can be digitally designed and manufactured with the aid of computer-controlled manufacturing devices (e.g., computer numerical control (CNC) milling, computer-controlled rapid prototyping, such as 3D printing, etc.). The computer-based methods presented herein can improve the accuracy, flexibility, and convenience of appliance manufacturing.

[0545] Figure 2 A method 200 for designing an orthodontic appliance for production by direct manufacturing is shown in accordance with multiple embodiments. 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 device, e.g., one or more processors configured with suitable instructions.

[0546] In step 210, a movement path for moving one or more teeth from an initial alignment to a target alignment is determined. The initial alignment can be determined based on a mold or scan data of the patient's teeth or oral tissues, e.g., using methods such as wax bite registration, direct contact scanning, x-ray imaging, tomography, ultrasonic imaging, etc., for obtaining information about the position and structure of teeth, jaws, gums, and other orthodontically relevant tissues. From the acquired data, a digital data set can be derived that represents the initial (e.g., pre-treatment) alignment of the patient's teeth and other tissues. Optionally, the initial digital data set is processed to segment the tissue components from each other. For example, a data structure representing an individual tooth crown can be generated. Advantageously, a digital model of an entire tooth can be generated, including measured or extrapolated hidden surfaces and root structures, as well as surrounding bone and soft tissue.

[0547] The target alignment of teeth (e.g., the desired and expected final outcome of orthodontic treatment) can be received from a clinician in the form of a prescription, can be calculated based on basic orthodontic principles, and / or can be inferred computationally from a clinical prescription. From the desired final positions of the teeth and a digital representation of the teeth themselves, the final position and surface geometry of each tooth can be specified to form a complete model of the desired end-of-treatment tooth alignment.

[0548] After obtaining an initial position and a target position for each tooth, a movement path can be defined for the movement of each tooth. In some embodiments, the movement path is configured to move the tooth from its initial position to its desired target position in the fastest way with the fewest number of back-and-forths. Optionally, the tooth path can be segmented, and these segments can be calculated such that the movement of each tooth within a segment remains within threshold limits of linear and rotational translation. In this way, the end points of each path segment can constitute a clinically feasible repositioning, and the set of segment end points can constitute a clinically feasible sequence of tooth positions such that moving from one point to the next in the sequence does not cause tooth collisions.

[0549] In step 220, a force system that produces the movement of one or more teeth along the movement path is determined. The force system can include one or more forces and / or one or more torques. Different force systems can result in different types of tooth movement, such as tipping, translation, rotation, extrusion, intrusion, root movement, etc. Biomechanical principles, modeling techniques, force calculation / measurement techniques, etc., including knowledge and methods commonly used in orthodontics, can be used to determine the appropriate force system to be applied to the teeth to effect tooth movement. When determining the force system to be applied, sources can be considered, including the literature, force systems determined experimentally or through virtual modeling, computer-based modeling, clinical experience, minimizing unwanted forces, etc.

[0550] Determination of the force system can include constraints on the allowable forces, such as allowable directions and magnitudes, and the desired movement caused by the applied forces. For example, in manufacturing palatal expanders, different patients may require different movement strategies. For example, the magnitude of the force required to separate the palate may depend on the patient's age, as very young patients may not have fully developed sutures. Thus, in adolescent patients without fully closed palatal sutures and other patients, palatal expansion can be accomplished with a lower force magnitude. Slower palatal movement also aids in bone growth to fill the expanded sutures. For other patients, a more rapid expansion may be required, which can be achieved by applying a greater force. These requirements can be incorporated as needed to select the structure and materials of the appliance; for example, by selecting a palatal expander capable of applying a greater force to rupture the palatal sutures and / or cause rapid expansion of the palate. Subsequent appliance stages can be designed to apply different force magnitudes, such as first applying a greater force to fracture the sutures and then applying a lesser force to maintain suture separation or to gradually expand the palate and / or arch.

[0551] Determination of the force system can also include modeling of the patient's facial structure, such as the skeletal structure of the jaws and palate. For example, scan data of the palate and arch (e.g., X-ray data or 3D optical scan data) can be used to determine parameters of the skeletal and muscular systems of the patient's oral cavity, and thus to determine the forces sufficient to provide the desired expansion of the palate and / or arch. In some embodiments, the thickness and / or density of the sutures in the palate can be measured or input by a treating professional. In other embodiments, the treating professional can select an appropriate treatment based on the patient's physiological characteristics. For example, the characteristics of the palate can also be evaluated based on factors such as the patient's age; for example, younger adolescent patients generally require a lower force than older patients to expand the sutures, as the sutures are not yet fully developed.

[0552] In step 230, a design of an arch or palatal expander of an orthodontic appliance configured to generate a force system is determined. A treatment or force application simulation environment can be used to determine the design of the arch or palatal expander, the appliance geometry, the material composition, and / or properties. The simulation environment can include, for example, a computer modeling system, a biomechanical system, or a device, etc. Optionally, a digital model of the appliance and / or teeth can be generated, such as a finite element model. Finite element models can be created using computer program application software provided by various vendors. To create a solid geometry model, a computer-aided engineering (CAE) or computer-aided design (CAD) program can be used, such as those provided by Autodesk, Inc. of San Rafael, California Software products. To create and analyze finite element models, program products from multiple vendors can be used, including the finite element analysis software package from ANSYS, Inc. in Canonsburg, Pennsylvania, and the SIMULIA (Abaqus) software product from Dassault Systèmes in Waltham, Massachusetts.

[0553] Optionally, one or more arch or palatal expander designs can be selected for testing or force modeling. As described above, desired tooth movements can be identified, as well as the force system required or desired to cause the desired tooth movement. Using a simulation environment, candidate arch or palatal expander designs can be analyzed or modeled to determine the actual force system generated using the candidate appliance. Optionally, one or more modifications can be made to the candidate appliance, and the force modeling can be further analyzed as described, e.g., to iteratively determine the appliance design that produces the desired force system.

[0554] In step 240, manufacturing instructions for an orthodontic appliance incorporating an arch or palatal expander design are generated. The instructions can be configured to control a manufacturing system or device to produce an orthodontic appliance having the specified arch or palatal expander design. In some embodiments, according to the various methods provided herein, the instructions are configured to manufacture the orthodontic appliance using direct manufacturing (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct manufacturing, multi-material direct manufacturing, etc.). In alternative embodiments, the instructions can be configured to indirectly manufacture the appliance, e.g., by thermoforming.

[0555] Method 200 can include additional steps: 1) performing an intraoral scan of the patient's upper arch and palate to generate three-dimensional data of the palate and upper arch; 2) determining the three-dimensional shape profile of the appliance to provide the gap and tooth engagement structure as described herein.

[0556] Although the above steps illustrate method 200 for designing an orthodontic appliance according to some embodiments, those of ordinary skill in the art will recognize some variations based on the teachings provided herein. Some steps can include sub-steps. Some of these steps can be repeated as needed. One or more steps of method 200 can be performed using any suitable manufacturing system or device (e.g., the embodiments described herein). Some steps may be optional, and the order of the steps can be changed as needed.

[0557] Figure 3 Method 300 for digitally planning orthodontic treatment and / or designing or manufacturing an appliance according to various embodiments is shown. Method 300 can be applied to any treatment procedure described herein and can be performed by any suitable data processing system.

[0558] In step 310, a digital representation of a patient's teeth is received. The digital representation can include surface topography data of the patient's oral cavity (including teeth, gingival tissue, etc.). The surface topography 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 (such as a hand-held scanner, a desktop scanner, etc.).

[0559] In step 320, one or more treatment phases are generated based on the digital representation of the teeth. The treatment phases can be progressive repositioning phases of an orthodontic treatment procedure designed to move one or more of the patient's teeth from an initial tooth alignment to a target alignment. For example, the treatment phases can be generated by determining the initial tooth alignment indicated by the digital representation, determining the target tooth alignment, and determining the movement paths of one or more of the teeth in the initial alignment required to achieve the target tooth alignment. The movement paths can be optimized based on minimizing the total distance of the movement, preventing inter-dental collisions, avoiding more difficult-to-achieve tooth movements, or any other suitable criteria.

[0560] In step 330, at least one orthodontic appliance is manufactured based on the generated treatment phases. For example, a set of appliances can be manufactured, each appliance being formed according to the tooth alignment specified by a treatment phase, such that the patient can sequentially wear the appliances to progressively reposition the teeth from the initial alignment to the target alignment. The set of appliances can include one or more orthodontic appliances as described herein. The manufacture of the appliances may involve creating a digital model of the appliances to be used as an input to a computer-controlled manufacturing system. The appliances can be formed using direct manufacturing methods, indirect manufacturing methods, or a combination thereof as needed.

[0561] In some cases, phasing of the various alignments or treatment phases may not be necessary for the design and / or manufacture of the appliances. As shown by the dashed line in Figure 3 , the design and / or manufacture of the orthodontic appliances and possibly a particular orthodontic treatment can include using a representation of the patient's teeth (e.g., receiving a digital representation 310 of the patient's teeth), followed by designing and / or manufacturing the orthodontic appliances based on the representation of the patient's teeth in the alignment represented by the received representation.

[0562] On-track treatment

[0563] Reference Figure 4, which shows method 400 according to the present disclosure. Various aspects of the method will be discussed in further detail below. The method includes receiving information about a patient's orthodontic condition and / or treatment information (402), generating a case assessment (404), and generating a treatment plan for repositioning the patient's teeth (406). Briefly, the patient / treatment information includes data containing the initial alignment of the patient's teeth, which includes obtaining an impression or scan of the patient's teeth prior to starting treatment, and may also include the identification of one or more treatment goals selected by the practitioner and / or the patient. A case assessment (404) can be generated to assess the complexity or difficulty of moving specific patient teeth generally or specifically corresponding to the identified treatment goals, and may also include the practitioner's experience and / or comfort in performing the desired orthodontic treatment. However, in some cases, the assessment may simply include identifying specific treatment options of interest to the patient and / or practitioner (e.g., appointment scheduling, progress tracking, etc.). The information and / or corresponding treatment plan includes identifying the final or target alignment of the desired patient teeth, and a plurality of planned sequential or intermediate tooth alignments for moving the teeth from the initial alignment to the selected final or target alignment along the treatment path.

[0564] The method further includes generating customized treatment guidelines (408). The treatment plan can include multiple treatment phases, and a set of customized treatment guidelines corresponding to the phases of the treatment plan is generated. The guidelines can include detailed information about the time and / or content (e.g., specific tasks) to be completed in a given treatment phase, and can be detailed enough to guide the practitioner throughout the treatment phase, including less experienced practitioners or those relatively new to a particular orthodontic treatment process. Since the guidelines are designed to specifically correspond to the treatment plan and provide guidance on the activities clearly defined in the treatment information and / or the generated treatment plan, the guidelines are referred to as being customized. The customized treatment guidelines are then provided to the practitioner to assist in guiding the practitioner on how to provide a given treatment phase. As described above, appliances can be generated based on the planned alignment and provided to the practitioner and ultimately administered to the patient (410). The appliances can be provided and / or administered in sets or batches, e.g., 2, 3, 4, 5, 6, 7, 8, 9 or more appliances, but not limited to any specific administration scheme. The appliances can be provided to the practitioner simultaneously with a given set of guidelines, or the appliances and guidelines can be provided separately.

[0565] After treatment is started according to a plan and after an appliance is applied to a patient, for example, treatment progress is tracked by tooth matching to evaluate the current and actual alignment of the patient's teeth (412) compared to the planned alignment. If it is determined that the patient's teeth are "on track" and progressing according to the treatment plan, then treatment will progress as planned and the treatment moves to the next treatment phase (414). If the patient's teeth have substantially reached the final alignment of the original plan, then the treatment moves to the final treatment phase (414). If it is determined that the patient's teeth are moving according to the treatment plan but have not reached the final alignment, the next set of appliances can be applied to the patient.

[0566] Table 1 below gives the threshold differences between the planned tooth positions and the actual positions, which are selected as an indication 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.

[0567] Table 1

[0568]

[0569]

[0570] By comparing the current position of the patient's teeth with the expected or planned position and confirming that the teeth are within the parameter deviation ranges listed in Table 1, it can be determined whether the patient's teeth are on track. If the patient's teeth are determined to be on track, then treatment can progress according to the existing or initial treatment plan. For example, according to the treatment plan, a patient determined to be progressing on track can be applied one or more subsequent appliances, such as the next set of appliances. Treatment can progress to the final stage and / or can reach a point in the treatment plan where bite matching is repeated to determine whether the patient's teeth are progressing as planned or whether the teeth are off track.

[0571] In some embodiments, as further disclosed herein, the present disclosure provides methods of treating a patient using 3D printed orthodontic appliances. As a non-limiting example, orthodontic appliances including domains, polymer crystals, and / or materials that can form domains or polymer crystals can be 3D printed and used to reposition a patient's teeth. In certain embodiments, methods of repositioning a patient's teeth (or in some embodiments, a single tooth) include: generating a treatment plan for the patient that includes a plurality of intermediate tooth alignments for moving the teeth along a treatment path from an initial alignment to a final alignment; producing a 3D printed orthodontic appliance; and using the orthodontic appliance to move at least one of the patient's teeth on track toward an intermediate alignment or a final tooth alignment. In some embodiments, the 3D printed orthodontic appliance is produced using a crystallizable resin further disclosed herein. The on-track performance can be determined, for example, according to Table 1 above.

[0572] In some embodiments, the method further comprises tracking the progress of the patient's teeth along a treatment path after the orthodontic appliance is applied. In certain embodiments, tracking includes comparing the current alignment of the patient's teeth with the planned alignment of the teeth. As a non-limiting example, after the orthodontic appliance is first applied, after a period of time (e.g., two weeks), the current alignment of the patient's teeth (i.e., at two weeks of treatment) can be compared with the tooth alignment of the treatment plan. In some embodiments, progress can also be tracked by comparing the current alignment of the patient's teeth with the initial alignment of the patient's teeth. For example, the time period can be greater than 3 days, greater than 4 days, greater than 5 days, greater than 6 days, greater than 7 days, greater than 8 days, greater than 9 days, greater than 10 days, greater than 11 days, greater than 12 days, greater than 13 days, greater than 2 weeks, greater than 3 weeks, greater than 4 weeks, or greater than 2 months. In some embodiments, the time period can be from at least 3 days to at most 4 weeks, from at least 3 days to at most 3 weeks, from at least 3 days to at most 2 weeks, from at least 4 days to at most 4 weeks, from at least 4 days to at most 3 weeks, or from at least 4 days to at most 2 weeks. In certain embodiments, after a new orthodontic appliance is applied, the time period can start over.

[0573] In some embodiments, after the orthodontic appliance further disclosed herein is used for a period of time, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of the patient's teeth are on the treatment plan's track. In some embodiments, 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 greater than 4 weeks.

[0574] As further disclosed herein, the orthodontic appliances disclosed herein have advantageous properties such as increased durability and are capable of maintaining the elastic force on the patient's teeth for an extended period of time. In some embodiments of the methods disclosed above, the 3D printed orthodontic appliance has a maintained repositioning force (i.e., the repositioning force after the orthodontic appliance has been applied to the patient or worn by the patient for a period of time), and after this period of time, the maintained repositioning force on 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 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% of the repositioning force initially provided to at least one tooth of the patient (i.e., when the orthodontic appliance is first applied). In some embodiments, the period of time is 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks or greater than 4 weeks. In some embodiments, the period of time during which the repositioning force applied to at least one tooth of the patient exists is 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 greater than 2 months. In some embodiments, the repositioning force applied to at least one tooth of the patient exists for about 24 hours, about 3 days, about 7 days, about 14 days, about 2 months or greater than 2 months.

[0575] In some embodiments, the orthodontic appliances disclosed herein can provide in - track movement of at least one tooth of the patient. In - track movement is further described herein, as shown in Table 1. In some embodiments, the orthodontic appliances disclosed herein can be used to effect in - track movement of at least one tooth of the patient towards the intermediate tooth alignment. In some embodiments, the orthodontic appliances disclosed herein can be used to effect in - track movement of at least one tooth of the patient towards the final tooth alignment.

[0576] In some embodiments, prior to moving at least one tooth of a patient into midline alignment or final tooth positioning using an orthodontic appliance, the orthodontic appliance has a characteristic that is retained after use of the orthodontic appliance. In some embodiments, prior to the moving step, the orthodontic appliance includes a first flexural modulus. In certain embodiments, after the moving step, the orthodontic appliance includes a second flexural modulus. In some embodiments, the second flexural modulus is at least 99%, at least 98%, at least 97%, at least 96%, at least 95%, at least 94%, at least 93%, at least 92%, at least 91%, at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, at least 50%, or at least 40% of the first flexural modulus. In some embodiments, the second flexural modulus is greater than 50% of the first flexural modulus. In some embodiments, the comparison is made after a period of time following application of the appliance. In some embodiments, the period of time 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.

[0577] In some embodiments, prior to the moving step, the orthodontic appliance includes a first elongation at break. In some embodiments, after the moving step, the orthodontic appliance includes a second elongation at break. In some embodiments, the second elongation at break is at least 99%, at least 98%, at least 97%, at least 96%, at least 95%, at least 94%, at least 93%, at least 92%, at least 91%, at least 90%, at least 85%, at least 80%, at least 75%, at least 70%, at least 65%, at least 60%, at least 50%, or at least 40% of the first elongation at break. In some embodiments, the second elongation at break is greater than 50% of the first elongation at break. In some embodiments, the comparison is made after a period of time following application of the appliance. In some embodiments, the period of time 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.

[0578] As provided herein, the disclosed methods can use the orthodontic appliances further disclosed herein. The orthodontic appliances can be manufactured directly, for example, using a crystallizable resin as disclosed herein. In certain embodiments, direct manufacturing includes crosslinking the crystallizable resin.

[0579] Devices formed from the crystalline resins disclosed herein provide improved durability, strength, and flexibility, which in turn increase the rate of in-track progress in treatment planning. In some embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated with the orthodontic devices (e.g., aligners) disclosed herein are classified as being on track at a given treatment stage. In certain embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated with the orthodontic devices (e.g., calibrators) disclosed herein have greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, or greater than 95% of tooth movement classified as being on track.

[0580] As further disclosed herein, the cured polymeric materials contain advantageous properties, which at least in part result from the presence of polymer crystals. When compared to similar polymeric materials, these cured polymeric materials can have increased resistance to breakage, can be tough, and can have reduced water absorption. The cured polymeric materials can be used in devices within and outside the orthodontic field. For example, the cured polymeric materials disclosed herein can be used to manufacture devices for aerospace applications, automotive manufacturing, prototyping, and / or for the production of durable parts.

[0581] VI. Experimental Methods

[0582] Unless otherwise noted, all chemicals were purchased from commercial sources and used without further purification.

[0583] Recorded on a BRUKER AC-E-200FT-NMR spectrometer or a BRUKER Avance DRX-400FT-NMR spectrometer 1 1H NMR and 13 13C NMR spectra. Chemical shifts are in ppm (s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet). The solvents used were deuterochloroform (CDCl3, 99.5% deuterated) and deutero-DMSO (d6-DMSO, 99.8% deuterated).

[0584] In some embodiments, in some aspects, the stress relaxation of a material or device can be measured by monitoring the time-dependent stress caused by a steady strain. The degree of stress relaxation can also depend on temperature, relative humidity, and other applicable conditions (e.g., the presence of water). In various aspects, 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.

[0585] The dynamic viscosity of a fluid indicates its resistance to shear flow. The SI unit of dynamic viscosity is the pascal-second (Pa·s). Dynamic viscosity is usually given in centipoise, where 1 centipoise (cP) is equal to 1 mPa·s. Kinematic viscosity is the ratio of dynamic viscosity to the density of the fluid; the SI unit is m 2 / s. Devices for measuring viscosity include viscometers and rheometers. For example, the MCR 301 rheometer from Anton Paar can be used for rheological measurements in rotational mode (PP-25, 50 s-1, 50 - 115 °C, 3 °C / min).

[0586] Determining the water content when completely saturated at the use temperature can include exposing the polymeric material to 100% humidity for 24 hours at the use temperature (e.g., 40 °C), and then determining the water content by methods known in the art, e.g., by weight.

[0587] In some embodiments, the presence of the crystalline and amorphous phases provides advantageous material properties for the polymeric material. For example, the characteristic values of the cured polymeric material can be determined by using the following methods: [[ID=१०]]

[0588] The RSA-G2 instrument from TA Instruments can be used to evaluate the flexural modulus, residual flexural stress, and stress relaxation properties by the three-point bending method according to ASTM D790; 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;

[0589] The storage modulus can be measured at 37 °C and reported in MPa;

[0590] The T of the cured polymeric material g can be evaluated using dynamic mechanical analysis (DMA) and provided herein in the form of the tanδ peak;

[0591] The tensile modulus, tensile strength, yield elongation, and elongation at break can be evaluated according to ISO 527-25B; and the yield tensile strength, elongation at break, tensile strength, and Young's modulus can be evaluated according to ASTM D1708.

[0592] The molecular weight can be measured by size exclusion chromatography or gel permeation chromatography.

[0593] The additive manufacturing or 3D printing method for generating the devices herein (e.g., orthodontic appliances) can be carried out using a prototype of a thermal lithography device from Cubicure (Vienna, Austria), which can be configured substantially as Figure 9 schematically shown. In this case, the photocurable resin according to the present disclosure (e.g., the resin) can be filled intoFigure 9 In the transparent material urn of the device shown, the urn can be 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. By irradiating the composition with UV radiation at 375 nm using a diode laser from Soliton, the diode laser can have an output power of 70 mW, which can be controlled to track a predetermined prototyping, and by alternately raising the build platform, the composition can be cured layer by layer through the photopolymerization process according to the present disclosure, thereby obtaining a polymer material according to the present disclosure. Examples

[0594] The following examples are given to illustrate various embodiments of the present invention and are not meant to limit the present disclosure in any way. These examples, as well as the methods described herein, currently represent some embodiments, are exemplary, and are not intended to limit the scope of the present invention. Those skilled in the art will envision variations and other...

Claims

1. A curable composition for forming a medical device by additive manufacturing, comprising: an initiator; and a polymerizable monomer, wherein the polymerizable monomer is a substituted phenyl (meth)acrylate having a vapor pressure of at most about 12 Pa at 60 °C, and at least one ortho position of the benzene ring is substituted with a group containing at least one heteroatom selected from N, O, and S or a group containing a silicon atom, wherein the content of the polymerizable monomer is such that the composition has a viscosity of 30 cP to 50,000 cP at the printing temperature.

2. The curable composition according to claim 1, wherein the polymerizable monomer has the following structure according to formula (I): wherein: X is O, S, NR 6 or SiR 7 R 8 ; R 1 is H, substituted or unsubstituted C 1-3 alkyl, or halogen; R 2 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl, a substituted or unsubstituted cyclo(C 3-8 )alkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; R 3 、R 4 and R 5 are each independently H, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 thioalkoxy, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxyl or -Y-(CH2) n -R 9 ; or R 4 and R 5 together form a 4-, 5-, 6-, 7- or 8-membered ring selected from substituted or unsubstituted cyclo(C 4-8 )alkyl, substituted or unsubstituted cyclo(C 4-8) heteroalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Y is O, S, NH, or C(O)O; n is an integer from 0 to 6; R 6 、R 7 and R 8 are independently H or substituted or unsubstituted C 1-6 alkyl; and R 9 is a substituted or unsubstituted cyclo(C 3-8 )alkyl, a substituted or unsubstituted cyclo(C 3-8 )heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

3. The curable composition according to claim 2, wherein X is O.

4. The curable composition according to any one of claims 2-3, wherein R 1 is H or methyl.

5. The curable composition according to any one of claims 2-3, wherein R 2 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 carbonyl, or a substituted or unsubstituted C 1-6 carboxyl.

6. The curable composition according to claim 5, wherein R 2 is an unsubstituted C 1-6 alkyl group.

7. The curable composition according to claim 6, wherein R 2 is methyl or ethyl.

8. The curable composition according to any one of claims 2 - 7, wherein R 3 is H.

9. The curable composition according to any one of claims 2-7, wherein R 3 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl, or -Y-(CH2) n -R 9 .

10. The curable composition according to claim 9, wherein R 3 is methyl or ethyl.

11. The curable composition according to any one of claims 2-10, wherein R 4 is H.

12. The curable composition according to any one of claims 2-10, wherein R 4 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl, or -Y-(CH2) n -R 9 .

13. The curable composition according to any one of claims 2-12, wherein R 5 is H.

14. The curable composition according to any one of claims 2-12, wherein R 5 is a substituted or unsubstituted C 1-6 alkyl, a substituted or unsubstituted C 1-6 heteroalkyl, a substituted or unsubstituted C 1-6 alkoxy, a substituted or unsubstituted C 1-6 thioalkoxy, a substituted or unsubstituted C 1-6 carbonyl, a substituted or unsubstituted C 1-6 carboxyl, or -Y-(CH2) n -R 9 .

15. The curable composition according to claim 14, wherein R 5 is a methoxy group.

16. The curable composition according to any one of claims 2 - 15, wherein the polymerizable monomer has one of the following structures:

17. The curable composition according to any one of claims 1 - 16, wherein the curable composition comprises 10 - 80 wt% of the polymerizable monomer.

18. The curable composition according to any one of claims 1 - 17, wherein the polymerizable monomer reduces the viscosity of the curable composition by at least 5% compared to a composition not containing the polymerizable monomer.

19. The curable composition according to any one of claims 1 - 18, wherein the initiator comprises a photoinitiator.

20. The curable composition according to claim 19, wherein the photoinitiator comprises a free radical photoinitiator.

21. The curable composition according to any one of claims 1 - 20, wherein the initiator further comprises a thermal initiator.

22. The curable composition according to claim 21, wherein the thermal initiator comprises azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), or a combination thereof.

23. The curable composition according to any one of claims 1 - 22, wherein the curable composition comprises 0.01 wt% to 10 wt% of the initiator.

24. The curable composition according to any one of claims 1 - 23, further comprising a telechelic oligomer, a telechelic polymer, or a combination thereof.

25. The curable composition according to claim 24, wherein the number average molecular weight of the telechelic oligomer is greater than 500 Da but less than 3 kDa.

26. The curable composition according to claim 25, wherein the number average molecular weight of the telechelic polymer is greater than 5 kDa but less than 50 kDa.

27. The curable composition according to claim 24, wherein the telechelic oligomer or the telechelic polymer comprises photoreactive moieties at both of its ends.

28. The curable composition according to claim 27, wherein the photoreactive moiety is an acrylate, methacrylate, acryloyloxyethylene, methacryloyloxyethylene, allyl ether, silene, alkyne, alkene, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety.

29. The curable composition according to claim 28, wherein the photo-reactive moiety is an acrylate or methacrylate moiety.

30. The curable composition according to any one of claims 24-29, wherein the curable composition comprises 0.5-99.5 wt%, 1-99 wt%, 10-95 wt%, 20-90 wt%, 25-60 wt% or 35-50 wt% of polymerizable monomers and telechelic polymers and / or oligomers.

31. The curable composition according to any one of claims 2-30, wherein the polymerizable monomer according to formula (I) is a first polymerizable monomer, and the curable composition further comprises a second polymerizable monomer different from the polymerizable monomer of formula (I).

32. The curable composition according to claim 31, wherein the second polymerizable monomer comprises an alkyl acrylate, an alkyl methacrylate, a homosalicylic acid acrylate, a homosalicylic acid methacrylate or a combination thereof.

33. The curable composition according to claim 32, wherein the second polymerizable monomer is a homosalicylic acid acrylate, a homosalicylic acid methacrylate or a combination thereof.

34. The curable composition according to any one of claims 31-33, wherein the curable composition comprises 25-35 wt% of the first polymerizable monomer and 10-50% of the second polymerizable monomer.

35. The curable composition according to any one of claims 1-34, further comprising one or more polymerizable components or additives selected from crosslinking modifiers, glass transition temperature modifiers, toughness modifiers, polymerization catalysts, polymerization inhibitors, photoresists, plasticizers, surface energy modifiers, pigments, dyes, fillers, biologically significant chemicals and solvents.

36. The curable composition according to any one of claims 1 to 35, wherein the curable composition is capable of 3D printing at a printing temperature higher than 25 °C.

37. The curable composition according to claim 35, wherein the printing temperature is at least 30 °C, 40 °C, 50 °C, 60 °C, 80 °C or 100 °C.

38. The curable composition according to claim 37, wherein the printing temperature is from 20 °C to 150 °C.

39. The curable composition according to any one of claims 1 to 38, wherein the curable composition comprises less than 20 wt% of hydrogen-bonding units.

40. The curable composition according to any one of claims 1 to 39, wherein the curable composition is liquid at a temperature of about 40 °C to about 100 °C.

41. The curable composition according to claim 40, wherein the curable composition is liquid at a temperature higher than about 40 °C and has a viscosity of less than about 20 PaS.

42. The curable composition according to claim 40, wherein the curable composition is liquid at a temperature higher than about 40 °C and has a viscosity of less than about 1 PaS.

43. The curable composition according to any one of claims 1-42, wherein at least a portion of the curable composition melts at a temperature between about 60 °C and about 0 °C.

44. A polymeric material formed from the curable composition according to any one of claims 1-43.

45. The polymeric material according to claim 44, wherein the polymeric material has one or more of the following properties: (A) Storage modulus greater than or equal to 200 MPa; (B) After being placed in a humid environment at 37 °C for 24 hours, the remaining flexural stress and / or flexural modulus is greater than or equal to 1.5 MPa; (C) Before and after being placed in a humid environment at 37 °C for 24 hours, the elongation at break is greater than or equal to 5%; (D) When measured after being placed in a humid environment at 37 °C for 24 hours, the water absorption rate is less than 25 wt%; and (E) After being placed in a humid environment at 37 °C for 24 hours, at least 30% of visible light passes through the polymeric material; and (F) Comprises a plurality of polymer phases, wherein the Tg of at least one polymer phase in one or more polymer phases is at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C.

46. The polymeric material according to any one of claims 44-45, wherein the polymeric material is characterized in that when measured after being placed in a humid environment at 37 °C for 24 hours, 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%.

47. The polymeric material according to any one of claims 44 - 46, wherein, Compared with the curable composition, the polymeric material has a conversion rate of double bonds to single bonds greater than 60% as measured by FTIR.

48. The polymeric material according to any one of claims 44-47, wherein after being placed in a humid environment at 37 °C for 24 hours, the ultimate tensile strength of the polymeric material 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.

49. The polymeric material according to any one of claims 44-48, wherein the polymeric material is characterized in that before and after being placed in a humid environment at 37 °C for 24 hours, the elongation at break is greater than 10%, the elongation at break is greater than 20%, the elongation at break is greater than 30%, the elongation at break is 5% to 250%, the elongation at break is 20% to 250%, or the elongation at break value is 40% to 250%.

50. The polymeric material according to any one of claims 44 - 49, wherein the polymeric material is characterized in that after being placed in a humid environment at 37 °C for 24 hours, the storage modulus is from 0.1 MPa to 4000 MPa, from 300 MPa to 3000 MPa, or from 750 MPa to 3000 MPa.

51. The polymeric material according to any one of claims 44 - 50, wherein after being placed in a humid environment at 37 °C for 24 hours, the flexural stress and / or flexural modulus of the polymeric material 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, 60 MPa or higher.

52. The polymeric material according to any one of claims 44 - 51, wherein after being placed in a humid environment at 37 °C for 24 hours, at least 40%, 50%, 60% or 70% of visible light passes through the polymeric material.

53. The polymeric material according to any one of claims 44 to 52, wherein the polymeric material is biocompatible, bioinert or a combination thereof.

54. A polymeric film comprising the polymeric material according to any one of claims 44 - 53.

55. The polymeric film according to claim 54, wherein the thickness of the polymeric film is at least 100 μm and not more than 3 mm.

56. An orthodontic appliance comprising the polymeric material according to any one of claims 44 - 53 or the polymeric film according to any one of claims 54 - 55.

57. The orthodontic appliance according to claim 56, wherein the orthodontic appliance is an aligner, an expander or a spacer.

58. A method of forming the polymeric material according to any one of claims 44 - 53, the method comprising: providing a curable composition according to any one of claims 1 - 43; exposing the curable composition to a light source; and curing the curable composition to form a polymeric material.

59. The method according to claim 58, wherein the light source is an ultraviolet (UV) or visible light source.

60. The method according to any one of claims 58 - 59, further comprising inducing phase separation during photocuring.

61. The method according to claim 60, wherein inducing phase separation comprises generating one or more polymer phases in the polymeric material during photocuring.

62. The method according to claim 61, wherein at least one of the one or more polymer phases is an amorphous phase having a glass transition temperature (Tg) of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C.

63. The method according to claim 61, wherein at least 25%, 50% or 75% of the polymer phases generated during photocuring are amorphous phases having a glass transition temperature (Tg) of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C.

64. The method according to any one of claims 62 and 63, wherein the at least one glass transition temperature (Tg) of the amorphous phase of at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C comprises polymerizable monomers incorporated into its polymer structure.

65. The method according to claim 64, wherein at least one of the one or more polymer phases is a crystalline phase comprising a crystalline polymer material.

66. The method according to claim 64, wherein the melting point of the crystalline polymer material is at least 60 °C, 80 °C, 90 °C, 100 °C or at least 110 °C.

67. The method according to any one of claims 60 - 66, wherein at least one of the one or more polymer phases is three-dimensional and the length of at least one of its dimensions is less than 1000 μm, less than 500 μm, less than 250 μm or less than 200 μm.

68. The method according to any one of claims 58 - 67, further comprising manufacturing an orthodontic appliance using the polymer material.

69. A method of preparing an article by an additive manufacturing process, comprising: providing a curable composition according to any one of claims 1 - 43; heating the curable composition to a processing temperature; exposing the curable composition to radiation; curing the curable composition layer by layer according to a predetermined design so that the polymerizable monomers polymerize and crosslink to form a polymer material; and manufacturing an article using the polymer material.

70. The method according to claim 69, wherein the processing temperature is from about 50 °C to about 120 °C.

71. The method according to claim 70, wherein the processing temperature is from about 90 °C to about 110 °C, from about 100 °C to about 120 °C, from about 105 °C to about 115 °C or from about 108 °C to about 110 °C.

72. The method according to any one of claims 69 - 71, wherein the additive manufacturing process is a 3D printing process.

73. The method according to any one of claims 69 - 72, wherein the article is a medical device.

74. The method according to claim 73, wherein the medical device is an orthodontic appliance.

75. A method of repositioning a patient's teeth, comprising: developing a treatment plan for the patient, the plan comprising a plurality of intermediate tooth alignments for moving the teeth along a treatment path from an initial tooth alignment towards a final tooth alignment ； producing an orthodontic appliance according to claim 68 or 74, or an orthodontic appliance comprising a polymer material according to any one of claims 58 - 67; and using the orthodontic appliance to move at least one tooth of the patient towards an intermediate tooth alignment or a final tooth alignment in orbit.

76. The method according to claim 75, wherein producing the orthodontic appliance comprises 3D printing the orthodontic appliance.

77. The method according to any one of claims 75 - 76, 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.

78. The method according to any one of claims 75 - 77, wherein after 2 weeks of treatment, more than 60% of the patient's teeth are on track with the treatment plan.

79. The method according to any one of claims 75 - 78, wherein the orthodontic appliance has a retained repositioning force on at least one of the patient's teeth after 2 days, the retained repositioning force being 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.

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