CN117321108A

CN117321108A - Photopolymerisable block polymers and methods of making and using same

Info

Publication number: CN117321108A
Application number: CN202280035546.3A
Authority: CN
Inventors: U·U·乔杜里; J·K·苏; M·C·科勒; J·M·查韦斯
Original assignee: Align Technology Inc
Current assignee: Align Technology Inc
Priority date: 2021-04-23
Filing date: 2022-04-25
Publication date: 2023-12-29
Also published as: CN117440942A

Abstract

Provided herein are curable compositions for high Wen Guangke-based photopolymerization methods, as well as telechelic block polymers, and methods of using such polymers in curable compositions to produce medical devices, such as orthodontic appliances, including polymer compositions comprising telechelic block polymers.

Description

Photopolymerisable block polymers and methods of making and using same

Cross reference

The present application is a continuation of U.S. provisional patent application Ser. No.63/179,007 filed on day 2021, month 4, and 23, month 4, 2021, and U.S. provisional patent application Ser. No.63/179,004, which are incorporated herein by reference in their entireties for all purposes.

Incorporation by reference

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.

Technical Field

Additive manufacturing (e.g., photolithography-based additive manufacturing (L-AM)) techniques include a variety of techniques for manufacturing objects (e.g., three-dimensional objects) from photopolymerisable materials. Appliances and devices having a combination of elasticity and stiffness are desirable in a variety of applications, such as in the manufacture of orthodontic appliances or appliances, where conventional medical devices may lack such advantageous characteristics.

Disclosure of Invention

It has traditionally proven difficult to form many medical devices by additive manufacturing techniques. One problem is that existing materials for additive manufacturing are not biocompatible and are less suitable for use in the intra-oral environment or other parts of the human body. Another problem is that existing materials used in additive manufacturing are often not sufficiently tacky to form the precise and/or customizable features required for many instruments. Moreover, many current additive manufacturing techniques have relatively low curing or reaction temperatures for safety and cost considerations, which detract from the ability to produce products that are stable at and/or above human body temperature for many medical devices, including orthodontic appliances. Another problem is that existing materials used for additive manufacturing do not provide the physical, chemical, and/or thermo-mechanical properties (elongation, temporal stress relaxation, modulus, durability, toughness, etc.) required for appliances, other orthodontic appliances, hearing aids, and/or other medical devices. Thus, existing materials for additive manufacturing lack many of the characteristics required of medical devices, such as the ability to apply forces, torques, moments, and/or other movements that are accurate and consistent with a treatment plan.

Appliances and devices having a combination of resilience and stiffness are desirable in a variety of applications, such as during the manufacture of orthodontic appliances or devices. Polymeric materials may be used to fabricate orthodontic appliances so that fabrication techniques such as 3D printing may be used. Single polymeric materials (e.g., those composed of a single polymeric substance) typically do not have the characteristics, such as modulus (e.g., stiffness) and elasticity, required to meet the devices and instruments currently being manufactured. Some practitioners have attempted to adjust the properties of polymeric materials by adding fillers to the resins from which the polymeric materials are formed. However, fillers (e.g., silica) can increase the viscosity of the resins and render them incompatible with the desired manufacturing technique. Such fillers can also increase modulus, but at the cost of elasticity. Thus, there is a need for a resin that can increase the internal modulus of a material without sacrificing the desired elasticity, and such a resin is desirable for a variety of medical applications.

Orthodontic procedures typically involve repositioning a patient's teeth to a desired arrangement in order to correct malocclusions and/or improve aesthetics. To achieve these objectives, an orthodontist and/or a patient may apply orthodontic appliances, such as braces, retainers, shell aligners, etc., to the teeth of the patient. The appliance is configured to apply a force to one or more teeth to achieve a desired tooth movement. The application of force may be periodically adjusted (e.g., by changing appliances or using different types of appliances) to gradually reposition the teeth to a desired arrangement. The polymeric material may be used to manufacture an appliance for repositioning a patient's teeth. Polymeric materials having both rigid and elastic properties are desirable, as are 3D printed resins that can be formed into such polymeric materials.

In view of the problems mentioned herein, the present disclosure is directed to providing curable compositions for high Wen Guangke-based photopolymerization processes. These curable compositions can be used in a variety of applications, including those used to form medical devices and/or for use in the intraoral environment, such as intraoral devices, e.g., aligners, dilators, or spacers. In particular, considering the challenges of a single polymeric material in a medical device, the present invention provides photocurable resins comprising one or more telechelic block copolymers (comprised of two or more different monomers), wherein such telechelic block copolymers may comprise photopolymerizable end groups and may have a molecular weight of up to about 50kDa, 30kDa, or 25 kDa. Such telechelic block copolymers may provide (e.g., upon photocuring) polymeric materials having properties particularly suitable for application in medical devices (e.g., orthodontic appliances), and thus may satisfy the need for photocurable compositions that allow for the production of materials having a variety of specific mechanical properties.

Accordingly, the present disclosure is directed to compositions, methods, and systems for high Wen Guangke-based photopolymerization, and devices made from the high temperature lithography-based photopolymerization.

In various aspects, provided herein are telechelic polymers comprising monomers, wherein the monomers comprise reactive functional groups, and wherein two or more of the following conditions are satisfied: (i) The monomer has a vapor pressure of at most 8000Pa at 60 ℃ in its monomeric state; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in its monomer state at 90 ℃ per hour is less than 0.25%; (iii) the telechelic polymer has a molecular weight of no greater than 50kDa; and (iv) the reactive functional group comprises a photopolymerizable moiety. In some aspects, the monomer is a terminal monomer. In some aspects, the monomer is an internal monomer. In some aspects, three or more of conditions (i), (ii), (iii), and (iv) are satisfied. In some aspects, all conditions (i), (ii), (iii), and (iv) are satisfied. In some aspects, the monomer has a vapor pressure of 2Pa to 10Pa at 60 ℃ in its monomer state. In some aspects, the monomer has a vapor pressure of 2Pa to 5Pa at 60 ℃ in its monomer state. In some aspects, after heating at 90 ℃ for 2 hours, the monomer has a mass loss rate of 0.05% to 0.225% per hour at 90 ℃ in its monomer state. In some aspects, after heating at 90 ℃ for 2 hours, the monomer has a mass loss rate of 0.025% to 0.125% per hour at 90 ℃ in its monomer state. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 40kDa. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 30kDa. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 20kDa. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 15kDa. In some aspects, the photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some aspects, the photopolymerizable moiety comprises an acrylate or methacrylate moiety. In some aspects, the photopolymerizable moiety is capable of a photoinduced diels-alder click reaction or a photodimerization reaction. In some aspects, the monomer when in its monomer state has a melting point of at least 25 ℃. In some aspects, the monomer is a compound according to formula (I):

Wherein,

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group.

In some aspects, R ¹ Is H or methyl. In some aspects, R ² Is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted ring (C _3-8 ) Alkyl or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In this case, R ² Is a substituted or unsubstituted aryl group. In some cases, R ² Is a substituted or unsubstituted heteroaryl group. In some cases, R ² Is a substituted or unsubstituted ring (C) _5-7 ) An alkyl group. In some cases, R ² Is a substituted or unsubstituted ring(C _5-7 ) A heteroalkyl group.

In various aspects, provided herein are photocurable resins comprising the telechelic polymers of the present invention. In some cases, the photocurable resin is capable of undergoing polymerization-induced phase separation along one or more lateral directions during photocuring. In some cases, the photocurable resin comprises one or more polymer phases upon polymerization. In some cases, at least one of the one or more polymer phases has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g ). In some cases, the telechelic polymer in polymerized form is a component of the at least one polymer phase, T of the polymer phase _g At least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some cases, at least one of the one or more polymer phases comprises a crystalline polymer material. In some cases, the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some cases, the photocurable resin may further comprise a second telechelic polymer comprising a second monomer, wherein the second monomer comprises a second reactive functional group and one or more of the following conditions are satisfied: (v) The second monomer has a vapor pressure of at most 8000Pa at 60 ℃ in its monomeric state; (vi) After heating at 90 ℃ for 2 hours, the second monomer has a mass loss rate of less than 0.25% per hour at 90 ℃ in its monomer state; (vii) the molecular weight of the second telechelic polymer is no greater than 50kDa; and (viii) the second reactive functional group comprises a second photopolymerizable moiety. In some aspects, four or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, five or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, six or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, seven or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, all conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, the second monomer Is a terminal monomer. In some aspects, the second monomer is an internal monomer. In some aspects, the second monomer has a vapor pressure of 2Pa to 10Pa at 60 ℃ in its monomeric state. In some aspects, the second monomer has a vapor pressure of 2Pa to 5Pa at 60 ℃ in its monomeric state. In some aspects, the second monomer has a mass loss rate of 0.05% to 0.225% at 90 ℃ in its monomer state after heating at 90 ℃ for 2 hours. In some aspects, the second monomer has a mass loss rate of 0.025% to 0.125% at 90 ℃ in its monomer state after heating at 90 ℃ for 2 hours. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 40kDa. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 30kDa. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 20kDa. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 15kDa. In some aspects, the second photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some aspects, the second photopolymerizable moiety comprises an acrylate or methacrylate moiety. In some aspects, the second photopolymerizable moiety is capable of performing a photoinduced diels-alder click reaction or a photodimerization reaction. In some aspects, the second monomer when in its monomeric state has a melting point of at least 25 ℃. In some aspects, the second monomer is different from the first monomer, and wherein the second monomer is a compound according to formula (II):

Wherein,

R ³ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

R ⁴ 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 groupSubstituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some aspects, the first monomer and the second monomer are part of a telechelic block copolymer. In some aspects, the telechelic block copolymer has an AB block configuration, where "a" is a first block in the telechelic block copolymer and "B" is a second block in the telechelic block copolymer. In some aspects, the telechelic block copolymer is a compound according to formula (III):

wherein,

R ⁵ and R is ⁸ Independently H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ⁶ and R is ⁷ Independently 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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, and R ⁶ ≠R ⁷ The method comprises the steps of carrying out a first treatment on the surface of the And

n and m are independently positive integers of 1 to 300. In some cases, n and m are independently positive integers from 1 to 100.

In some aspects, the telechelic block copolymer has the configuration of ABA or BAB, where "a" is a block comprised of a first monomer in the telechelic block copolymer and "B" is a block comprised of a second monomer in the telechelic block copolymer. In some aspects, the telechelic block copolymer further comprises a macroinitiator. In some aspects, the macroinitiator is polycaprolactone, polytetrahydrofuran, hydrogenated polyethylene, hydroxyl terminated polystyrene, polyester diol (or diacid), polycarbonate diol, or polystyrene dihalide. In some aspects, the telechelic block copolymer has a polydispersity index (PDI) of about 0.5 to about 3, or about 1 to about 2. In some aspects, the photocurable resin is capable of 3D printing at a temperature of at least 25 ℃. In some aspects, the photocurable resin is capable of 3D printing at a temperature of at least 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, or 100 ℃. In some aspects, the photocurable resin further comprises a reactive diluent. In some aspects, the photocurable resin has a viscosity of 30cP to 50,000cP at the printing temperature. In some aspects, the printing temperature is 20 ℃ to 150 ℃. In some aspects, the photocurable resin comprises less than 20wt% hydrogen bond units. In some aspects, the photocurable resin further comprises a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof. In some aspects, the photocurable resin comprises 0.5-99.5wt%, 1-99wt%, 10-95wt%, 20-90wt%, 25-60wt%, or 35-50wt% of the telechelic polymer, the second telechelic polymer, the telechelic block copolymer, or a combination thereof.

In various aspects, provided herein are polymeric materials formed from the photocurable resins described herein. In some aspects, the polymeric material has one or more of the following characteristics: (a) a tensile modulus greater than or equal to 200MPa; (B) A flexural stress and/or flexural modulus of greater than or equal to 1.5MPa after 24 hours in a humid environment at 37 ℃; (C) elongation at break greater than or equal to 5%; (D) The water absorption measured after 24 hours in a humid environment at 37 ℃ is lower than 25wt%; (E) At least 30% of the visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃; and (F) comprises a plurality of polymer phases, wherein at least one of the one or more polymer phases has a T of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG C _g . In some aspects, the polymeric material has at least two of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has at least three of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has at least four of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has at least five characteristics of (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has all of the characteristics The properties (A), (B), (C), (D), (E) and (F). In some aspects, the polymeric material is characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, when measured after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material has a conversion of double bonds to single bonds of greater than 60% as measured by FTIR compared to the photocurable resin. In some aspects, the polymeric material has an ultimate tensile strength of 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MPa to 40MPa, 30MPa to 45MPa, or 30MPa to 40MPa after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material is characterized by an elongation at break of greater than 10%, an elongation at break of greater than 20%, an elongation at break of greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break of between 40% to 250% after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material is characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃. In some aspects, wherein the polymeric material retains a flexural stress and/or flexural modulus of 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater, or 50MPa or greater after 24 hours in a wet environment at 37 ℃. In some aspects, at least 40%, 50%, 60%, or 70% of the visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material is biocompatible, bioinert, or a combination thereof. In some aspects, the polymeric material is capable of being 3D printed.

Also provided herein are polymeric films comprising the polymeric materials of the present invention. In some aspects, the film has a thickness of at least 100 μm and no greater than 3 mm.

Further provided herein are devices comprising the polymeric materials of the present disclosure or polymeric films of the present disclosure.

Further provided herein are medical devices comprising the polymeric materials of the present disclosure or polymeric films of the present disclosure. In some aspects, the medical device is an orthodontic appliance. In some aspects, the orthodontic appliance is a dental appliance, a dental expander, or a dental spacer. In some aspects, the medical device can be produced by 3D printing.

In various aspects, provided herein are methods of synthesizing a telechelic block copolymer comprising (i) coupling a telechelic polymer (a) with a second telechelic polymer (B) to produce a telechelic block copolymer, wherein the telechelic block copolymer comprises photopolymerizable end groups at its ends, and wherein the telechelic block copolymer has a number average molecular weight of up to about 50 kDa. In some aspects, the telechelic polymer and the second telechelic polymer are produced by Atom Transfer Radical Polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), and/or anionic polymerization.

In various aspects, provided herein is a method of forming a polymeric material, the method comprising: (i) providing a photocurable resin of the present disclosure; (ii) exposing the photocurable resin to a light source; (iii) curing the photocurable resin to form a polymeric material. In some aspects, the method further comprises inducing phase separation in the formed polymeric material in one or more lateral directions during photocuring. In some aspects, the polymeric material comprises one or more polymeric phases. In some aspects, at least one of the one or more polymer phases has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g ). In some aspects, the telechelic polymer in polymerized form is a component of the at least one polymer phase, T of the polymer phase _g At least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some aspects, at least one of the one or more polymer phases comprises a crystalline polymer material. In some aspects, the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some aspects, the polymeric material comprises one or more T _g An amorphous phase of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃, and one or more crystalline phases comprising a melting point of at least 60 ℃, 80 ℃, 90 DEG CCrystallizing the polymeric material at 100 ℃ or at least 110 ℃. In some aspects, the polymeric material is characterized by one or more of the following: (i) a tensile modulus greater than or equal to 200MPa; (ii) A flexural stress greater than or equal to 1.5MPa remains after 24 hours in a humid environment at 37 ℃; (iii) an elongation at break of greater than or equal to 5%. In some aspects, the method further comprises manufacturing the medical device from a polymeric material. In some aspects, the medical device is an orthodontic appliance. In some aspects, the orthodontic appliance is a dental appliance, a dental expander, or a dental spacer.

In various aspects, provided herein are telechelic polymers comprising terminal monomers, wherein the terminal monomers comprise reactive functional groups, and wherein two or more of the following conditions are satisfied: (i) The terminal monomer has a vapor pressure of at most 12Pa at 60 ℃ in its monomeric state; (ii) The mass loss of the terminal monomer after heating for 2 hours at 90 ℃ in the monomer state is less than 0.5%; (iii) the telechelic polymer has a molecular weight of no greater than 50kDa; (iv) the reactive functional group comprises a photoreactive moiety. In some aspects, three or more of conditions (i), (ii), (iii), and (iv) are satisfied. In some aspects, all conditions (i), (ii), (iii), and (iv) are satisfied. In some aspects, the terminal monomer has a vapor pressure of 2Pa to 10Pa at 60 ℃ in its monomeric state. In some aspects, the terminal monomer has a vapor pressure of 2Pa to 5Pa at 60 ℃ in its monomeric state. In some aspects, the terminal monomer has a mass loss of 0.1% to 0.45% after heating at 90 ℃ for 2 hours in its monomeric state. In some aspects, the terminal monomer has a mass loss of 0.05% to 0.25% after heating at 90 ℃ for 2 hours in its monomeric state. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 40kDa. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 30kDa. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 20kDa. In some aspects, the telechelic polymer has a molecular weight of 5kDa to 15kDa. In some aspects, the photoreactive moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some aspects, the photoreactive moiety comprises an acrylate or methacrylate moiety. In some aspects, the photoreactive moiety is capable of performing a photoinduced diels-alder click reaction or a photodimerization reaction. In some aspects, the terminal monomer has a melting point of at least 25 ℃ when in its monomer state. In some aspects, the terminal monomer is a compound according to formula (I):

Wherein,

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

In some aspects, R ¹ Is H or methyl. In some aspects, R ² Is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted ring (C _3-8 ) Alkyl or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In this case, R ² Is a substituted or unsubstituted aryl group. In some cases, R ² Is a substituted or unsubstituted heteroaryl group. In some cases, R ² Is a substituted or unsubstituted ring (C) _5-7 ) An alkyl group. In some cases, R ² Is a substituted or unsubstituted ring (C) _5-7 ) A heteroalkyl group.

In various aspects, provided herein are photocurable resins comprising the telechelic polymers of the present invention. In some cases, the photocurable resin is capable of polymerization-induced phase separation in one or more lateral directions during photocuring. In some cases, the photocurable resin comprises one or more polymer phases upon polymerization. In some cases, at least one of the one or more polymer phases has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g ). In some cases, the telechelic polymer in polymerized form is a component of the at least one polymer phase, T of the polymer phase _g At least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some cases, at least one of the one or more polymer phases comprises a crystalline polymer material. In some cases, the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some cases, the photocurable resin may further comprise a second telechelic polymer comprising a second terminal monomer, wherein the second terminal monomer comprises a second reactive functional group, and wherein one or more of the following conditions are satisfied: (v) The second terminal monomer has a vapor pressure of at most 12Pa at 60 ℃ in its monomeric state; (vi) The second terminal monomer has a mass loss of less than 0.5% after heating at 90 ℃ for 2 hours in its monomeric state; (vii) the molecular weight of the second telechelic polymer is no greater than 50kDa; (viii) The second reactive functional group comprises a second photoreactive moiety. In some aspects, four or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, five or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, six or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, seven or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, all conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii) are satisfied. In some aspects, the second terminal monomer in its monomeric state has a vapor pressure of 2Pa to 10Pa at 60 ℃. In some aspects, the second terminal monomer has a vapor pressure of 2Pa to 5Pa at 60 ℃ in its monomeric state. In some aspects, the second terminal monomer has a mass loss of 0.1% to 0.45% after heating at 90 ℃ for 2 hours in its monomeric state. In some aspects, the second terminal monomer has 0.05% in its monomeric state after heating at 90 ℃ for 2 hours To a mass loss of 0.25%. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 40kDa. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 30kDa. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 20kDa. In some aspects, the second telechelic polymer has a molecular weight of 5kDa to 15kDa. In some aspects, the second photoreactive moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety. In some aspects, the second photoreactive moiety comprises an acrylate or methacrylate moiety. In some aspects, the second photoreactive moiety is capable of undergoing a photoinduced diels-alder click reaction or a photodimerization reaction. In some aspects, the second terminal monomer when in its monomeric state has a melting point of at least 25 ℃. In some aspects, the second terminal monomer is different from the terminal monomer, and wherein the second terminal monomer is a compound according to formula (II):

wherein,

R ³ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

R ⁴ 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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some aspects, the first telechelic polymer and the second telechelic polymer are part of a telechelic block copolymer. In some aspects, the telechelic block copolymer has a block configuration of AB, where "a" is a telechelic polymer and "B" is a second telechelic polymer. In some aspects, the telechelic block copolymer is according to formula (III)A compound:

wherein,

n and m are independently positive integers from 1 to 100.

In some aspects, the telechelic block copolymer has the configuration of ABA or BAB, where "a" is the telechelic polymer and "B" is the second telechelic polymer. In some aspects, the telechelic block copolymer further comprises a macroinitiator. In some aspects, the macroinitiator is polycaprolactone, polytetrahydrofuran, hydrogenated polyethylene, hydroxyl terminated polystyrene, polyester diol, polycarbonate diol, or polystyrene dihalide. In some aspects, the telechelic block copolymer has a polydispersity index (PDI) of about 0.5 to about 3, or about 1 to about 2. In some aspects, the photocurable resin is capable of 3D printing at a temperature of at least 25 ℃. In some aspects, the photocurable resin is capable of 3D printing at a temperature of at least 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, or 100 ℃. In some aspects, the photocurable resin further comprises a reactive diluent. In some aspects, the photocurable resin has a viscosity of 30cP to 50,000cP at the printing temperature. In some aspects, the printing temperature is 20 ℃ to 150 ℃. In some aspects, the photocurable resin comprises less than 20wt% hydrogen bond units. In some aspects, the photocurable resin further comprises a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof. In some aspects, the photocurable resin comprises 0.5-99.5wt%, 1-99wt%, 10-95wt%, 20-90wt%, 25-60wt%, or 35-50wt% of the telechelic polymer, the second telechelic polymer, the telechelic block copolymer, or a combination thereof.

In various aspects, provided herein are polymeric materials formed from the photocurable resins described herein. In some aspects, the polymeric material has one or more of the following characteristics: (a) a tensile modulus greater than or equal to 200MPa; (B) A flexural stress greater than or equal to 1.5MPa remains after 24 hours in a humid environment at 37 ℃; (C) elongation at break greater than or equal to 5%; (D) The water absorption measured after 24 hours in a humid environment at 37 ℃ is lower than 25wt%; (E) At least 30% of the visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃; (F) Comprising a plurality of polymer phases, wherein at least one of the one or more polymer phases has a T of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG C _g . In some aspects, the polymeric material has at least two of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has at least three of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has at least four of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has at least five of the characteristics (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material has all of properties (a), (B), (C), (D), (E), and (F). In some aspects, the polymeric material is characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, when measured after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material has a conversion of double bonds to single bonds of greater than 60% as measured by FTIR compared to the photocurable resin. In some aspects, the polymeric material has a viscosity of 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MPa to 40MPa, 30MPa to 45MPa, or 30MPa to 45MPa after 24 hours in a humid environment at 37 ℃ Ultimate tensile strength of 40 MPa. In some aspects, the polymeric material is characterized by an elongation at break of greater than 10%, an elongation at break of greater than 20%, an elongation at break of greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break of between 40% to 250% after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material is characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃. In some aspects, wherein the polymeric material retains a flexural stress of 100MPa or less, 80MPa or less, 70MPa or less, 60MPa or less, or 50MPa or less after 24 hours in a humid environment at 37 ℃. In some aspects, at least 40%, 50%, 60%, or 70% of the visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃. In some aspects, the polymeric material is biocompatible, bioinert, or a combination thereof. In some aspects, the polymeric material is capable of being 3D printed.

In various aspects, provided herein is a method of forming a polymeric material, the method comprising: (i) providing a photocurable resin of the present disclosure; (ii) exposing the photocurable resin to a light source; (iii) curing the photocurable resin to form a polymeric material. In some aspects, the method further comprises inducing phase separation in the formed polymeric material in one or more lateral directions during photocuring. In some aspects, the polymeric material comprises one or more polymeric phases. In some aspects, at least one of the one or more polymer phases has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g ). In some aspects, the telechelic polymer in polymerized form is a component of the at least one polymer phase, T of the polymer phase _g T is at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 DEG C _g . In some aspects, at least one of the one or more polymer phases comprises a crystalline polymer material. In some aspects, the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some aspects, the polymeric material comprises one or more T _g T is at least 60 ℃, 80 ℃, 90 ℃, 100 ℃ or at least 110 DEG C _g And one or more crystalline phases comprising a crystalline polymeric material having a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃. In some aspects, the polymeric material is characterized by one or more of the following: (i) a tensile modulus greater than or equal to 200MPa; (ii) A flexural stress greater than or equal to 1.5MPa remains after 24 hours in a humid environment at 37 ℃; (iii) an elongation at break of greater than or equal to 5%. In some aspects, the method further comprises manufacturing the medical device from a polymeric material. In some aspects, the medical device is an orthodontic appliance. In some aspects, the orthodontic appliance is a dental appliance, a dental expander, or a dental spacer.

Also provided herein is a method of repositioning a patient's teeth, the method comprising: (i) Generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving the teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement; (ii) Producing an orthodontic appliance comprising a polymeric material of the present disclosure; (iii) At least one tooth of the patient is intended to be moved in track towards an intermediate or final tooth arrangement using the orthodontic appliance. In some aspects, producing the orthodontic appliance includes 3D printing the orthodontic appliance. In some aspects, the method further includes tracking 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 arrangement of the patient's teeth to a planned arrangement of the patient's teeth. In some aspects, more than 60% of the patient's teeth conform to the treatment plan after 2 weeks of treatment. In some aspects, the orthodontic appliance has a retained repositioning force on at least one tooth of the patient after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the repositioning force originally provided to the at least one tooth of the patient.

Brief description of the drawings

The novel features of the invention are set forth with particularity in the appended claims. The following detailed description sets forth the principles of the present invention, and the features and advantages thereof, are better understood by reference to the following detailed description of exemplary embodiments and the accompanying drawings.

Fig. 1A illustrates a tooth repositioning appliance according to an embodiment.

Fig. 1B illustrates a tooth repositioning system according to an embodiment.

Fig. 1C illustrates an orthodontic treatment method using a plurality of appliances according to an embodiment.

Fig. 2 illustrates a method for designing an orthodontic appliance according to an embodiment.

Fig. 3 illustrates a method for digitally planning orthodontic treatment according to an embodiment.

Fig. 4 shows a protocol for generating and administering a treatment according to an embodiment of the present disclosure.

Fig. 5 shows a schematic diagram of the configuration of a tall Wen Zengcai manufacturing apparatus for curing the curable composition of the present invention by using a 3D printing process.

Fig. 6 illustrates the lateral and vertical dimensions used herein.

Detailed description of the invention

I. Summary of the invention

The present invention provides photopolymerisable polymers, such as telechelic block copolymers, and compositions comprising such polymers, and methods of use thereof (e.g., in the production of medical devices, such as orthodontic appliances). The telechelic polymers provided herein may comprise a monomer, wherein the monomer may comprise a reactive functional group, and wherein one, two, three, or all of the following conditions are satisfied: (i) The monomer has a vapor pressure of up to about 8000Pa at 60 ℃ in its monomeric state; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in its monomer state at 90 ℃ per hour is less than 0.25%; (iii) The telechelic polymer has a molecular weight of no greater than about 50kDa; and (iv) the reactive functional group comprises a photopolymerizable moiety. In various embodiments, the monomer is a terminal monomer. In various embodiments, the monomer is an internal monomer. In some embodiments, the monomers are internal monomers and terminal monomers. In various embodiments, the telechelic polymer is a telechelic block copolymer comprising 2, 3, 4, 5, or more different monomer species. In this case, the photopolymerizable telechelic block copolymer of the invention may comprise (i) a monomer comprising a reactive functional group comprising a photopolymerizable moiety, and (ii) may have a molecular weight of up to about 50kDa, 40kDa, 30kDa, 25kDa, 20kDa, 15kDa, 10kDa, 5 kDa. Also provided herein are curable resins comprising one or more telechelic polymers, and polymeric materials that can be produced from such resins by curing (e.g., photocuring) such resins. Such polymeric materials may be used in the manufacture of medical devices, such as orthodontic appliances.

All terms, chemical names, expressions and names have the usual meaning known to a person skilled in the art. As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended, and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim elements. As used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claims.

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

Furthermore, the term "about" as used herein generally refers to and includes plus or minus 10% of the indicated value unless specifically indicated otherwise. For example, "about 10%" may mean a range of 9% to 11%, and "about 1" may include a range of 0.9-1.1. Numerical ranges are understood to include inclusion, i.e., including the indicated lower and upper limits.

As used herein, the terms "telechelic polymer" and "telechelic oligomer" generally refer to polymers or oligomers whose molecules are capable of entering into further polymerization through reactive groups.

The oligomers and polymer mixtures can be characterized by measuring molecular weight and molecular weight distribution and are distinguished from other oligomers and polymer mixtures.

Unless otherwise indicated herein, the molecular weight of a telechelic polymer refers to the average molecular weight (M) of the telechelic polymer herein, which is the average number n of repeating units multiplied by the molecular weight or molar mass of the repeating units (M _i ). Number average molecular weight (M) _n ) Is an arithmetic mean, representing the total weight of molecules present divided by the total number of molecules.

As used herein, the term "polymer" generally refers to a molecule composed of repeating structural units linked by covalent chemical bonds, characterized by a plurality of repeating units (e.g., equal to or greater than 20 repeating units, typically equal to or greater than 100 repeating units and typically equal to or greater than 200 repeating units) and a molecular weight of greater than or equal to 5,000 daltons (Da) or 5kDa, such as greater than or equal to 10kDa, 15kDa, 20kDa, 30kDa, 40kDa, 50kDa, or 100 kDa. The 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 species. The term polymer also includes copolymers that are formed when two or more different types of monomers are linked in the same polymer. Copolymers may include two or more monomer subunits (subunits) and include random, block, alternating, segmented, grafted, tapered, and other copolymers. The term "crosslinked polymer" generally refers to a polymer having one or more linkages between at least two polymer chains, which may result from the multivalent monomer forming crosslinking sites upon polymerization.

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

Photoinitiators described in the present disclosure can include those that can be activated with light and initiate polymerization of the polymerizable components of the formulation. As used herein, "photoinitiator" generally refers to a compound that is capable of generating free radical species and/or promoting a free radical reaction upon exposure to radiation (e.g., UV or visible light).

As used herein, the term "biocompatible" refers to a material that does not cause immune rejection or deleterious effects (referred to herein as adverse immune reactions) when placed in an in vivo biological environment. For example, in embodiments, the biomarker indicative of an immune response varies by less than 10% or less than 20% or less than 25% or less than 40% or less than 50% from a baseline value when a human or animal is exposed to or contacted with the biocompatible material. Alternatively, the immune response may be determined histologically, wherein the local immune response is assessed by visual assessment of markers within and adjacent to the material, including immune cells or markers involved in the immune response pathway. In one aspect, the biocompatible material or device does not significantly alter the histologically-determined immune response. In some embodiments, the present disclosure provides biocompatible devices configured for long term use, e.g., over a period of about weeks to months, without eliciting an adverse immune response. Biological effects can be initially assessed by measuring cytotoxicity, sensitization, irritation and intradermal reactivity, acute systemic toxicity, pyrogenicity, subacute/sub-chronic toxicity and/or implantation. Biological tests for supplemental assessment include tests for chronic toxicity.

"bioinert" means a material that does not elicit an immune response in humans or animals when placed in a biological environment in the body. For example, when a human or animal is exposed to or contacted with a bioinert material, the biomarker indicative of an immune response remains substantially constant (plus or minus 5% of baseline value). In some embodiments, the present disclosure provides a biologically inert instrument.

As used herein, "crosslinked polymer" generally refers to a polymer having one or more linkages between at least two polymer chains, preferably resulting from multivalent monomers that form crosslinking sites upon polymerization. In various instances herein, a polymer (e.g., a crosslinked polymer) can be synthesized by polymerizing 2, 3, 4, 5, 10, 15, 20, or more prepolymers or telechelic polymers.

When a group of substituents is disclosed herein, it is to be understood that all individual members of the group and all subgroups, including any isomers, enantiomers, and diastereomers of the members of the group, are individually disclosed. When markush groups or other groupings are used herein, all individual members of the group, as well as all combinations and subcombinations possible of the group, are intended to be individually included in this disclosure. When a compound described herein is such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or chemical name, the description is intended to include each isomer and enantiomer of the compound described alone or in any combination. Moreover, unless otherwise specified, all isotopic variations of the compounds disclosed herein are intended to be encompassed by the present disclosure. The specific names of compounds are intended to be exemplary, as it is known to one of ordinary skill in the art that the same compounds may be named differently.

As used herein, the term "group" may refer to a functional group of a compound. The group of the compounds of the present invention refers to an atom or collection of atoms that are part of the compound. The groups of the present disclosure may be attached to other atoms of the compound by one or more covalent bonds. Groups may also be characterized in terms of their valency. The present disclosure includes groups characterized by monovalent, divalent, trivalent equivalent states.

As used herein, the term "substituted" refers to a compound (e.g., an alkyl chain) in which hydrogen is substituted with another functional group or atom, as described herein.

As used herein, a polyline in a chemical structure may be used to indicate a bond with the rest of a molecule. For example, the number of the cells to be processed,in (a) and (b)For designating the 1-position as the point of attachment of the 1-methylcyclopentanoate to the rest of the molecule. Alternatively, for example +.>In (a) and (b)Can be used to indicate that a given moiety, i.e., the cyclohexyl moiety in this example, is attached to the molecule by a bond that is "blocked" with a wavy line.

Alkyl includes straight chain, branched and cyclic alkyl groups unless otherwise defined for a compound or genus of compounds. Alkyl groups include those having 1 to 30 carbon atoms unless otherwise defined. Thus, alkyl groups may include small 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 those having 10 to 30 carbon atoms. The term "cycloalkyl" particularly refers to an alkyl group having a ring structure, e.g., a ring structure comprising 3-30 carbon atoms, optionally 3-20 carbon atoms, and optionally 3-10 carbon atoms, including alkyl groups having one or more rings. Cycloalkyl includes those having a 3-, 4-, 5-, 6-, 7-, 8-, 9-or 10-membered carbocyclic ring, especially those having a 3-, 4-, 5-, 6-, 7-or 8-membered ring. Carbocycles in cycloalkyl groups may also carry alkyl groups. Cycloalkyl groups may include bicycloalkyl and tricycloalkyl groups. Alkyl groups are optionally substituted as described herein. Wherein substituted alkyl groups may include alkyl groups substituted with aryl groups, which in turn may 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 are optionally substituted. Unless otherwise defined herein, substituted alkyl includes perhalogenated or semi-halogenated alkyl groups, such as alkyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms. Thus, substituted alkyl groups may include fully fluorinated or semi-fluorinated alkyl groups, such as alkyl groups in which one or more hydrogens are replaced with one or more fluorine atoms. Alkoxy is an alkyl group modified by attachment to oxygen, may be represented by the formula R-O, and may also be referred to as an alkyl ether group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and heptoxy. Alkoxy includes substituted alkoxy groups in which the alkyl portion of the group is substituted, as provided herein in connection with the description of alkyl. As used herein, meO-refers to CH ₃ O-。

Alkenyl includes straight chain, branched, and cyclic alkenyl. Alkenyl groups include those having 1, 2, or more double bonds, and those in which two or more double bonds are conjugated double bonds. Alkenyl groups include those having 2 to 20 carbon atoms unless otherwise defined herein. Alkenyl groups include small alkenyl groups having 2 to 3 carbon atoms. Alkenyl groups include medium length alkenyl groups having 4 to 10 carbon atoms. Alkenyl groups include alkenyl groups having more than 10 carbon atoms, particularly those having 10 to 20 carbon atoms. Cycloalkenyl groups include those wherein the double bond is in the ring or in an alkenyl group attached to the ring. The term cycloalkenyl refers in particular to alkenyl groups having a ring structure, including those having a 3-, 4-, 5-, 6-, 7-, 8-, 9-or 10-membered carbocyclic ring and in particular having a 3-, 4-, 5-, 6-, 7-or 8-membered ring. Carbocycles in cycloalkenyl groups may also carry alkyl groups. Cycloalkenyl groups may include bicycloalkenyl and tricycloalkenyl. Alkenyl groups are optionally substituted. Unless otherwise defined herein, wherein substituted alkenyl groups include those substituted with alkyl or aryl groups, these groups may in turn be optionally substituted. Specific alkenyl groups include vinyl, prop-1-enyl, prop-2-enyl, cycloprop-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl, pent-1-enyl, pent-2-enyl, branched pentenyl, cyclopent-1-enyl, hex-1-enyl, branched hexenyl, cyclohexenyl, all of which are optionally substituted. Substituted alkenyl groups may include fully halogenated or semi-halogenated alkenyl groups, such as alkenyl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine, and/or iodine atoms. Substituted alkenyl groups include fully fluorinated or semi-fluorinated alkenyl groups, such as alkenyl groups having one or more hydrogen atoms substituted with one or more fluorine atoms.

Aryl includes groups having one or more 5-, 6-, 7-, or 8-membered aromatic rings (including heterocyclic aromatic rings). The term heteroaryl refers in particular to an aryl group having at least one 5-, 6-, 7-or 8-membered heterocyclic aromatic ring. An aryl group may comprise 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, which may be fused or linked by covalent bonds. The heterocyclic aromatic ring may include one or more N, O or S atoms in the ring. The heterocyclic aromatic ring may include those having one, two, or three N atoms, those having one or two O atoms and those having one or two S atoms, or a combination of one or two or three N, O or S atoms. Aryl is optionally substituted. Wherein substituted aryl groups include those substituted with alkyl or alkenyl groups, which groups may in turn be optionally substituted. Specific aryl groups include phenyl, biphenyl, pyrrolidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, and naphthyl, all of which are optionally substituted. Substituted aryl groups may include fully halogenated or semi-halogenated aryl groups, such as aryl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine, and/or iodine atoms. Substituted aryl groups include fully fluorinated or semi-fluorinated aryl groups, such as aryl groups having one or more hydrogens substituted with one or more fluorine atoms. Aryl groups include, but are not limited to, aromatic-or heterocyclic-aromatic-containing groups corresponding to any of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, naphthacene, naphthacenedione, 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 (azulene) or anthracycline (anthracycline). As used herein, groups corresponding to the groups listed above expressly include aromatic or heterocyclic aromatic groups listed herein, including monovalent, divalent, and more polyvalent groups, provided in covalently bonded configurations at any suitable point of attachment in compounds of the present disclosure. In some embodiments, aryl groups contain 5 to 30 carbon atoms. In some embodiments, the aryl group contains one aromatic or heteroaromatic six-membered ring and one or more additional five-or six-membered aromatic or heteroaromatic rings. In embodiments, aryl groups contain 5 to 18 carbon atoms in the ring. The aryl group optionally has one or more aromatic or heterocyclic aromatic rings with one or more electron donating groups, electron withdrawing groups, and/or targeting ligands provided as substituents.

Arylalkyl is an alkyl group substituted with one or more aryl groups, wherein the alkyl group optionally carries additional substituents and the aryl group is optionally substituted. A particular alkylaryl group is a phenyl substituted alkyl group, such as phenylmethyl. Alkylaryl groups may alternatively be described as aryl groups substituted with one or more alkyl groups, wherein the alkyl groups optionally bear additional substituents, and the aryl groups are optionally substituted. Specific alkylaryl groups are alkyl substituted phenyl groups, such as methylphenyl. Substituted arylalkyl groups include fully halogenated or semi-halogenated arylalkyl groups, such as arylalkyl groups having one or more alkyl groups and/or aryl groups having one or more hydrogens substituted with one or more fluorine, chlorine, bromine and/or iodine atoms.

As used herein, the terms "alkylene" and "alkylene group" are used synonymously and refer to the divalent group "-CH" derived from an alkyl group as defined herein ₂ - ". The present disclosure includes compounds having one or more alkylene groups. The alkylene groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure may have substituted and/or unsubstituted C ₁ -C ₂₀ Alkylene, C ₁ -C ₁₀ Alkylene and C ₁ -C ₆ An alkylene group.

As used herein, the terms "cycloalkylene" and "cycloalkylene group" are used synonymously and refer to a divalent group derived from a cycloalkyl group as defined herein. The present disclosure includes compounds having one or more cycloalkylene groups. Cycloalkyl groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure may have substituted and/or unsubstituted C ₃ -C ₂₀ Cycloalkylene, C ₃ -C ₁₀ Cycloalkylene and C ₃ -C ₅ Cycloalkylene radicals.

As used herein, the terms "arylene" and "arylene group" are used synonymously and refer to an aryl group as defined hereinIs a divalent group of (a). The present disclosure includes compounds having one or more arylene groups. In some embodiments, arylene is a divalent group derived from an aryl group by removing a hydrogen atom from two ring carbon atoms of the aryl ring of the aryl group. Arylene groups in some compounds act as linking groups and/or spacer groups. Arylene groups in some compounds act as chromophores, fluorophores, aromatic antenna(s), dyes, and/or imaging groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₃ -C ₃₀ Arylene group, C ₃ -C ₂₀ Arylene group, C ₃ -C ₁₀ Arylene and C ₁ -C ₅ Arylene groups.

As used herein, the terms "heteroarylene" and "heteroarylene group" are used synonymously and refer to a divalent group derived from a heteroaryl group as defined herein. The present disclosure includes compounds having one or more heteroarylenes. In some embodiments, a heteroaryl group is a divalent group derived from a heteroaryl group by removing a hydrogen atom from a carbon atom or a nitrogen atom within two rings of the heteroaromatic or aromatic ring of the heteroaryl group. The heteroarylene group in some compounds acts as a linking group and/or a spacer group. The heteroarylene group in some compounds acts as a chromophore, aromatic tentacle, fluorophore, dye, and/or imaging group. The compounds of the present disclosure include substituted and/or unsubstituted C ₃ -C ₃₀ Heteroarylene, C ₃ -C ₂₀ Heteroarylene, C ₁ -C ₁₀ Heteroarylene and C ₃ -C ₅ Heteroaryl groups.

As used herein, the terms "alkenylene" and "alkenylene group" are used synonymously and refer to a divalent group derived from an alkenyl group as defined herein. The present invention includes compounds having one or more alkenylene groups. Alkenylene groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₂ -C ₂₀ Alkenylene, C ₂ -C ₁₀ Alkenylene and C ₂ -C ₅ Alkenylene radicals.

As used herein, the terms "cycloalkenyl" and "cycloalkenyl radical"Synonymously used and refers to a divalent group derived from a cycloalkenyl group as defined herein. The present disclosure includes compounds having one or more cycloalkenyl groups. The cycloalkenyl groups in some compounds act as linking and/or spacer groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₃ -C ₂₀ Cycloalkenyl, C ₃ -C ₁₀ Cycloalkenyl and C ₃ -C ₅ Cycloalkenyl groups.

As used herein, the terms "alkynylene" and "alkynylene group" are used synonymously and refer to a divalent group derived from an alkynyl group as defined herein. The present disclosure includes compounds having one or more alkynylene groups. Alkynylene groups in some compounds act as linking groups and/or spacer groups. The compounds of the present disclosure include substituted and/or unsubstituted C ₂ -C ₂₀ Alkynylene, C ₂ -C ₁₀ Alkynylene and C ₂ -C ₅ Alkynylene groups.

As used herein, the terms "halo" and "halogen" are used interchangeably and refer to a halogen group, such as fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I)

The term "heterocycle" refers to a ring structure that contains at least one other atom in the ring in addition to carbon. Examples of such heteroatoms include nitrogen, oxygen, and sulfur. Heterocyclic rings include heterocyclic alicyclic rings and heterocyclic aromatic rings. Examples of heterocyclic rings include, but are not limited to, pyrrolidinyl, piperidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl, and tetrazolyl. The atoms of the heterocyclic ring may be combined with a wide variety of other atoms and functional groups, for example provided as substituents.

The term "carbocycle" refers to a ring structure that contains only carbon atoms in the ring. Carbon atoms of the carbocycle may be bonded to a variety of other atoms and functional groups, for example, provided as substituents.

The term "cycloaliphatic ring" refers to a ring or condensed rings that are not aromatic. Alicyclic rings include carbocyclic and heterocyclic rings.

The term "aromatic ring" refers to a ring or multiple condensed rings comprising at least one aromatic ring group. The term aromatic ring includes aromatic rings comprising carbon, hydrogen and heteroatoms. Aromatic rings include carbocyclic and heterocyclic aromatic rings. An aromatic ring is a component of an aryl group.

The term "fused ring" or "fused ring structure" refers to a plurality of cycloaliphatic 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.

As used herein, the term "alkoxyalkyl" refers to a substituent of the formula alkyl-O-alkyl.

As used herein, the term "polyhydroxyalkyl" refers to substituents 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 residues.

As used herein, the term "polyalkoxyalkyl" refers to a formula alkyl- (alkoxy) _n -substituents of alkoxy groups, wherein n is an integer from 1 to 10, such as 1-4, and in some embodiments from 1 to 3.

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

For any of the groups described herein that contain one or more substituents, it is to be understood that these groups do not contain any substitution or pattern of substitution that is sterically impractical and/or synthetically infeasible. Furthermore, the compounds of the present disclosure include all stereochemical isomers resulting from the substitution of these compounds.

Unless otherwise defined herein, any optional substituents of alkyl, alkenyl, and aryl groups include substitution with one or more of the following substituents, and the like:

halogen, including fluorine, chlorine, bromine or iodine;

pseudohalides, including-CN, -OCN (cyanate), -NCO (isocyanate), -SCN (thiocyanate), and-NCS (isothiocyanate);

-COOR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted;

-COR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted;

–CON(R) ₂ wherein each R is independently of each other R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

–OCON(R) ₂ wherein each R is independently of each other R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

–N(R) ₂ Wherein each R is independently of each other R is hydrogen or alkyl or acyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl, phenyl or acetyl, all of which are optionally substituted; and wherein R and R may form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

-SR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is hydrogen, methyl, ethyl, propyl, butyl or phenyl, which is optionally substituted;

–SO ₂ r or-SOR, wherein R is alkyl or aryl, more specifically wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

-OCOOR, wherein R is alkyl or aryl;

–SO ₂ N(R) ₂ wherein each R is independently of each other R is hydrogen or alkyl or aryl, all of which are optionally substituted, and wherein 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

-OR, wherein R is H, alkyl, aryl OR acyl, all of which are optionally substituted. In one particular example, R may be an acyl-generating-OCOR ", wherein R" is hydrogen or alkyl or aryl, more particularly wherein R "is methyl, ethyl, propyl, butyl or phenyl, all of which groups are optionally substituted.

Specific substituted alkyl groups include haloalkyl groups, particularly trihalomethyl groups and particularly trifluoromethyl groups. Specific substituted aryl groups include mono-, di-, tri-, tetra-and pentahalo-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa-, and heptahalo-substituted naphthyl; 3-or 4-halo-substituted phenyl, 3-or 4-alkyl-substituted phenyl, 3-or 4-alkoxy-substituted phenyl, 3-or 4-RCO-substituted phenyl, 5-or 6-halo-substituted naphthyl. More specifically, substituted aryl groups include acetylphenyl, especially 4-acetylphenyl; fluorophenyl, in particular 3-fluorophenyl and 4-fluorophenyl; chlorophenyl, in particular 3-chlorophenyl and 4-chlorophenyl; methylphenyl, in particular 4-methylphenyl; and methoxyphenyl, in particular 4-methoxyphenyl.

With respect to any of the above groups containing one or more substituents, it is to be understood that these groups do not contain any substitution or pattern of substitution that is sterically impractical and/or synthetically infeasible. Furthermore, the compounds of the present disclosure include all stereochemical isomers resulting from the substitution of these compounds.

Telechelic block copolymers

The present disclosure provides telechelic polymers and compositions (e.g., resins) comprising such telechelic polymers. In various instances, provided herein are telechelic polymers (i.e., polymers composed of a single monomer species a) and telechelic copolymers (i.e., polymers comprising 2, 3, 4, 5, or more different monomer species). In each case, the telechelic copolymers described herein are telechelic block copolymers, wherein each monomer species is present in a "block" configuration within the copolymer structure. As further described herein, such block configurations can yield a variety of polymer configurations, for example, where the telechelic block copolymer comprises 2 different monomer species a and B, block configurations such as AB, ABA, ABAB, AABB are possible.

Thus, throughout this disclosure, the term "telechelic polymer" is further defined to include polymers comprised of (i) only one monomer species and (ii) copolymers comprising 2, 3, 4, 5 or more different species of monomers. Such copolymers may be block copolymers as described herein. Furthermore, the term "telechelic" as used herein in the context of polymers and block copolymers generally refers to a polymer or oligomer capable of further polymerization through reactive functional groups at its ends. As used herein, telechelic polymers are generally characterized by a number average molecular weight of up to about 50kDa, 40kDa, 30kDa, 25kDa, 20kDa, or 15kDa. Thus, in various instances, the telechelic block copolymers of the present disclosure are capable of photopolymerization via their monomers with one or more other telechelic polymers, telechelic block copolymers, telechelic oligomers, or monomers (e.g., reactive diluents). In each case, the monomer comprises a photoreactive moiety capable of undergoing further photopolymerization. Such photopolymerization of the telechelic block copolymer with other polymers, oligomers, and/or monomers may occur during photocuring, for example, where the components are part of a photocurable resin as further described herein.

As further described herein, the telechelic polymers (e.g., telechelic block copolymers) of the present disclosure can enhance polymerization-induced phase separation (e.g., formation of one or more crystalline and/or amorphous phases) in a polymeric material, wherein the telechelic polymers are incorporated into the polymeric material, for example, during photocuring. Thus, in some cases, the telechelic polymers herein may be used to at least partially control the number and/or size of domains formed in a polymeric material upon photocuring, and thereby provide a material having certain advantageous properties, as described herein. Such phase control may be used to alter the clarity or clarity of the resulting polymeric material and the physical and mechanical properties. In addition, the chemical structure, monomer block configuration (e.g., AB, ABA, ABAB, etc.), and molecular weight of telechelic polymers comprising 2 monomer species a and B may allow for control of the morphology and properties of the resulting polymeric material into which the telechelic polymer is incorporated.

The present invention provides telechelic polymers comprising monomers, wherein the monomers comprise reactive functional groups (e.g., in polymerized form when in terminal positions of the telechelic polymer; or when in internal positions of the telechelic polymer), and wherein one, two, three, or all of the following conditions are satisfied: (i) The monomer has a vapor pressure of up to about 8000Pa at 60 ℃ in its monomeric state; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in its monomer state at 90 ℃ per hour is less than 0.25%; (iii) The telechelic polymer has a molecular weight of no greater than about 50kDa; and (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (i) the monomer has a vapor pressure of at most about 8000Pa in its monomer state at 60 ℃, and (ii) after heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in its monomer state at 90 ℃ per hour is less than 0.25%. In some cases, (i) the monomer has a vapor pressure of at most about 8000Pa in its monomeric state at 60 ℃, and (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa. In some cases, (i) the monomer has a vapor pressure of at most about 8000Pa at 60 ℃ in its monomer state, and (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (ii) after heating at 90 ℃ for 2 hours, the monomer has a mass loss rate of less than 0.25% per hour at 90 ℃ in its monomer state; (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa. In some cases, (ii) after heating at 90 ℃ for 2 hours, the monomer has a mass loss rate of less than 0.25% per hour at 90 ℃ in its monomer state; (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa and (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (i) the monomer has a vapor pressure of up to about 8000Pa in its monomeric state at 60 ℃; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in the monomer state at 90 ℃ per hour is less than 0.25%; and (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa. In some cases, (i) the monomer has a vapor pressure of up to about 8000Pa in its monomeric state at 60 ℃; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in the monomer state at 90 ℃ per hour is less than 0.25%; (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (i) the monomer has a vapor pressure of up to about 8000Pa in its monomeric state at 60 ℃; (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa; (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (ii) after heating at 90 ℃ for 2 hours, the monomer has a mass loss rate of less than 0.25% per hour at 90 ℃ in its monomer state; (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa; (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, (i) the monomer has a vapor pressure of up to about 8000Pa in its monomeric state at 60 ℃; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in the monomer state at 90 ℃ per hour is less than 0.25%; (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa; (iv) the reactive functional group comprises a photopolymerizable moiety.

In some embodiments, the monomer that may be part of the telechelic polymer may have a vapor pressure of about 0.1Pa to about 20Pa in its monomer state at 60 ℃ (e.g., when the monomer is in at least 98% pure form). In some cases, the monomer may have a vapor pressure of from 0.1Pa to 1Pa, from about 0.5Pa to about 5Pa, from about 1Pa to about 5Pa, from about 2Pa to about 5Pa, from about 10Pa to about 200Pa, from about 50Pa to about 300Pa, from about 100Pa to about 500Pa, from about 200Pa to about 800Pa, from about 500Pa to about 3000Pa, from about 1000 Pa to about 5000Pa, or from about 2000 to about 8000Pa at about 60 ℃. In some cases, the mass loss rate at 90 ℃ in its monomeric state after heating for 2 hours at 90 ℃ may be from about 0.005% to about 0.5% per hour of the monomer that may be part of the telechelic polymer. In some cases, after heating at 90 ℃ for 2 hours, the monomer may have a mass loss rate of about 0.0-5% to about 0.05%, about 0.025% to about 0.075%, about 0.025% to about 0.125%, or about 0.05% to about 0.225% in its monomer state. In some embodiments of the present disclosure, the monomer in its monomer state may have a melting point of at least about 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, or 50 ℃. In some cases, the monomer has a melting point of at least 25 ℃ in its monomer state.

The telechelic polymers of the present disclosure may comprise a range of degrees of end functionalization. In some cases, a population of telechelic polymers has complete or near complete terminal substitution (e.g., with acrylate or methacrylate moieties). For example, a population of telechelic polymers may have a terminal substitution of greater than 95%, greater than 97.5%, or greater than 99%. In some cases, a population of telechelic polymers has partial terminal substitution, for example, between 60% and 95%, between 70% and 90%, between 80% and 95%, between 75% and 85%, or between 60% and 80%. In some cases, the terminal substitution of a population of telechelic polymers is greater than 95%, greater than 90%, greater than 80%, greater than 70%, greater than 60%, or greater than 50%. In some cases where partial terminal substitution is optimal, the terminal substitution of a population of telechelic polymers is at most 90%, at most 85%, at most 80%, at most 70%, or at most 60%.

The telechelic polymers described herein may comprise monomers containing photoreactive moieties. Such photoreactive moieties at one end (or both ends) of the telechelic polymer may effect any photoreaction with other polymers or monomers known in the art, including, but not limited to, free radical photopolymerization, photo-induced diels-alder click reactions, or photodimerization reactions. In some cases, the photopolymerizable moiety as part of the monomer may include an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, epoxide, oxetane, thiol, or styryl moiety. In each case, the photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, alkynyl, alkenyl, vinyl ether, or styryl moiety. In each case, the photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, vinyl ether, or olefin moiety. In each case, the photopolymerizable moiety comprises an acrylate or methacrylate moiety. In some embodiments, the photoreactive diels-alder functional moiety can include furan, maleimide, conjugated alkylene, pentadiene, carbonyl, anthracene, and the like. In further embodiments, the monomer may be photodimerizable. The photodimerizable functional moiety may include uracil, thymine, maleimide, coumarin, anthracene, acenaphthylene (acenaphthates), or maleate moieties. In other cases, other photoreactive moieties may be considered, such as carbanes (carnes) and nitrenes.

In various embodiments, the monomers of the present disclosure in their monomeric form may be compounds according to formula (I):

wherein,

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl groupOr a substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group.

In some cases, R ¹ Is H or C ₁ -C ₃ An alkyl group. In some cases, R ¹ Is H or methyl. In some cases, R ² Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some cases, R ² Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Carbonyl, or substituted or unsubstituted aryl. In some cases, R ² Is unsubstituted C _1-6 Alkyl, unsubstituted C _1-6 Carbonyl or unsubstituted aryl. In some cases, R ² Is C _1-6 Alkyl, C _1-6 A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. In some cases, R ² By one or more halogens, -OH, -NH ₂ 、-NH(C ₁ -C ₃ Alkyl), -N (C) ₁ -C ₃ Alkyl) (C) ₁ -C ₃ Alkyl group, C ₁ -C ₃ Alkyl or a combination thereof. In some cases, R ² By one or more halogens, -OH, -NH ₂ Or a combination thereof. In some cases, R ² By halogen, -OH or-NH ₂ Is substituted by one of the above.

In some embodiments, the second telechelic polymer may comprise a second monomer that is different from the monomer according to formula (I) of the (first) telechelic polymer. In this case, the second monomer may be a compound according to formula (II):

wherein,

R ³ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

R ⁴ 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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group.

In some cases, R ³ Is H or C ₁ -C ₃ An alkyl group. In some cases, R ³ Is H or methyl. In some cases, R ³ Is H. In some cases, R ³ Is methyl.

In some cases, R ⁴ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Carbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some cases, R ⁴ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Carbonyl, or substituted or unsubstituted aryl. In some cases, R ⁴ Is unsubstituted C _1-6 Alkyl, unsubstituted C _1-6 Carbonyl or unsubstituted aryl. In some cases, R ⁴ Is C _1-6 Alkyl, C _1-6 A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. In some cases, R ⁴ By one or more halogens, -OH, -NH ₂ 、-NH(C ₁ -C ₃ Alkyl), -N (C) ₁ -C ₃ Alkyl) (C) ₁ -C ₃ Alkyl group, C ₁ -C ₃ Alkyl or a combination thereof. In some cases, R ⁴ By one or more halogens, -OH, -NH ₂ Or a combination thereof. In some cases, R ⁴ By halogen, -OH or-NH ₂ Is substituted by one of the above.

In some cases, the internal monomer of the telechelic polymer may be a compound according to formula (I), formula (II), or a combination thereof. For example, the telechelic polymers of the present invention may comprise 50 repeat units of the compound of formula (I) in polymerized form, as well as reactive terminal monomers, such as acrylate or methacrylate moieties.

In other cases, and as an alternative to the monomers according to formulas (I) and (II), the telechelic polymer or block copolymer described herein may comprise structurally modified or unmodified styrene monomers, structurally modified or unmodified vinyl monomers, structurally modified or unmodified epoxy monomers, structurally modified or unmodified urethane monomers, structurally modified or unmodified urea monomers, structurally modified or unmodified amide monomers, structurally modified or unmodified imide monomers, structurally modified or unmodified carbonate monomers, structurally modified or unmodified olefin monomers, structurally modified or unmodified acetal monomers, structurally modified or unmodified diene monomers, structurally modified or unmodified ester monomers, structurally modified or unmodified ether monomers, or combinations thereof; or consist of, it. In some cases, the telechelic polymers or block copolymers described herein may comprise structurally modified or unmodified styrene monomers, structurally modified or unmodified vinyl monomers, or combinations thereof; or consist of, it.

In various embodiments, the telechelic polymers herein are telechelic block copolymers comprising 2 different monomers a and B, and thus 2 different monomers, for example, AB or ABAB block configurations. In other cases, the compositions herein (e.g., photocurable compositions) comprise a first telechelic polymer comprised of a single monomer species a (thus comprising a first monomer a) and a second telechelic polymer comprised of a single monomer species B (comprising a second monomer B). In each of the above embodiments, the different monomer may be a compound according to formula (I).

In various instances, a telechelic polymer provided herein, e.g., a telechelic block copolymer, can have a molecular weight of greater than about 5kDa, 6kDa, 7kDa, 8kDa, 9kDa, 10kDa, 11kDa, 12kDa, 13kDa, 14kDa, 15kDa, 16kDa, 17kDa, 18kDa, 19kDa, 20kDa, 21kDa, 22kDa, 23kDa, 24kDa, 25kDa, 30kDa, 35kDa, 40kDa, or greater than about 45kDa but no greater than about 50 kDa. In such a case, the telechelic polymers provided herein can have a molecular weight of about 5kDa to about 40kDa, about 5kDa to about 30kDa, about 5kDa to about 20kDa, or about 5kDa to about 15 kDa. In each case, the telechelic polymer, such as a telechelic block copolymer, has a molecular weight of about 5kDa to about 25kDa or about 5kDa to about 15 kDa. As further described herein, telechelic polymers provided herein include photopolymerizable telechelic polymers and photopolymerizable telechelic block copolymers. The telechelic polymer may comprise or consist of a single monomer species. The telechelic block copolymers herein may comprise or consist of 2, 3, 4, 5, or more different (e.g., chemically different) monomer species.

In such cases, the telechelic polymers described herein may comprise monomer a. Such telechelic polymers may be described as A _x Wherein x represents the copy number of monomer A in the telechelic polymer and is a positive integer of 1-10, 1-20, 1-50, 1-100, 1-200, 1-500, or 1-1000, or at least about 5, 10, 15, 20, 25, 30, 40, 50, 75, or at least about 100. In the case where the telechelic polymer is a block copolymer comprising 2 different monomer species A and B, such block copolymer may be composed of A _x B _y Or A _x B _y A _z These multiple (multiples thereof) block configurations consist of or comprise A _x B _y Or A _x B _y A _z And wherein x, y and z represent the amounts of monomers A, B and a, respectively, and are independently a positive integer of 1-10, 1-20, 1-50, 1-100, 1-200, 1-500 or 1-1000, or a positive integer of at least about 5, 10, 15, 20, 25, 30, 40, 50, 75 or at least about 100. In the case where the telechelic block copolymer comprises 3 different monomers A, B and C, such block copolymer may be composed of A _x B _y C _z Block configuration of (a) or comprises A _x B _y C _z Wherein x, y and z represent the copy number of monomers A, B and C, respectively, and are independently a positive integer of 1-10, 1-20, 1-50, 1-100, 1-200, 1-500 or 1-1000, or a positive integer of at least about 5, 10, 15, 20, 25, 30, 40, 50, 75 or at least about 100. A first part In general, the telechelic block copolymers of the present disclosure may comprise a plurality (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) of different monomer species, wherein such different monomer species may form monomer blocks within the polymer chain, and wherein the telechelic block copolymer may comprise one or more blocks of a particular monomer species.

In telechelic polymer A _x Composed of a single kind of monomer A and x is>In the case of a positive integer of 1, the monomers (at both ends) of this polymer are identical to all other monomers present in the polymer. In which the telechelic polymer is composed of 2 different monomer species A and B and A _x B _y Where x and y are independently positive integers from 1 to 50, the telechelic polymer comprises two different monomers a and B, one at each end. In some cases, such different monomers a and B may comprise the same or different photoreactive moieties. In some cases, such photoreactive moieties may be acrylate or methacrylate moieties, or derivatives thereof. In the case of telechelic polymers consisting of A _x B _y A _z Telechelic block copolymers composed of block configurations, and where x, y and z are independently positive integers from 1 to 50, such telechelic polymers comprise two identical monomers a when the photoreactive moieties of such monomers are also identical. In some cases, such photoreactive moieties may be acrylate or methacrylate moieties, or derivatives thereof.

In some embodiments, the telechelic polymer is a polymer having a _n B _m Telechelic block copolymers in block configuration. Such telechelic block copolymers may be compounds according to formula (III):

wherein,

In some embodiments, R ⁵ And R is ⁸ Independently H or C ₁ -C ₃ An alkyl group. In some embodiments, R ⁵ And R is ⁸ And may independently be H or methyl. In some cases, R ⁵ And R is ⁸ The same applies. In other cases, R ⁵ And R is ⁸ Different. In some aspects, R ⁶ And R is ⁷ Independently selected from substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted C _1-6 Heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and n and m are independently positive integers from about 10 to about 50. In some cases, R ⁶ And R is ⁷ Independently substituted or unsubstituted C _1-6 Alkyl or substituted or unsubstituted aryl. In some cases, R ⁶ And R is ⁷ Independently unsubstituted C _1-6 Alkyl or unsubstituted aryl. In some cases, R ⁶ 、R ⁷ Or combinations thereof are independently substituted with one or more halogens, -OH, -NH ₂ 、-NH(C ₁ -C ₃ Alkyl), -N (C) ₁ -C ₃ Alkyl) (C) ₁ -C ₃ Alkyl group, C ₁ -C ₃ Alkyl or a combination thereof. In some cases, R ⁶ 、R ⁷ Or combinations thereof are independently substituted with one or more halogens, -OH, -NH ₂ Or a combination thereof. In some cases, R ⁶ 、R ⁷ Or combinations thereof are independently substituted with halogen, -OH or-NH ₂ Is substituted by one of the above.

In some embodiments, the telechelic polymers herein may also comprise a macroinitiator. Such macroinitiators may be used to initiate polymerization, for example, to prepare telechelic polymers or telechelic block copolymers. In some cases, the macroinitiator is polycaprolactone (e.g., having a molecular weight of about 2000-10000 g/mol), polytetrahydrofuran (e.g., having a molecular weight of about 2000-10000 g/mol), hydrogenated polyethylene, hydroxyl-terminated polystyrene, polyester diol, polycarbonate diol, or polystyrene dihalide. Three telechelic block copolymer macroinitiators consistent with the present disclosure are summarized in scheme 3 below:

Polymeric diols, such as polytetrahydrofuran, can be used to initiate ring opening polymerization of lactones, such as caprolactone, to synthesize polyester-polyether-polyester, BAB, triblock copolymers. The polystyrene synthesized by atom transfer radical polymerization may be end-functionalized to have hydroxyl groups, which may also further initiate polymerization to synthesize a block copolymer from vinyl monomers and lactones.

In some cases, the telechelic polymers described herein can be characterized by a polydispersity index (PDI). In some cases, the telechelic polymers described herein can have a PDI of about 0.05 to about 0.3, about 0.1 to about 0.5, about 0.25 to about 0.75, about 0.5 to about 5, about 0.5 to about 3, about 1 to about 3, or about 1 to about 2.

When incorporated into the polymeric structure of a polymeric material during photocuring, the telechelic polymers, e.g., telechelic block copolymers, of the present invention can alter the physical and/or mechanical properties (e.g., toughness, residual stress, etc.) of the polymeric material as compared to materials that do not include such polymers. Thus, in some cases herein, the telechelic polymers of the present disclosure can be characterized as toughness modifiers, glass transition temperatures (T _g ) A modulator, or a combination thereof, and the like.

In some embodiments, the telechelic polymer may be a compound according to formula (IV):

wherein,

R ⁹ each is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹⁰ each is H, substituted or unsubstituted C _1-3 Alkyl or halogen;

R ¹¹ 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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-12 ) Alkyl, or substituted or unsubstituted ring (C) _3-12 ) A heteroalkyl group; and

p is a positive integer from 1 to 200.

In some cases, R ⁹ Each H or unsubstituted C _1-3 An alkyl group. In some cases, R ⁹ Is H or methyl. In some cases, R ¹⁰ Each H or unsubstituted C _1-3 An alkyl group. In some cases, R ¹⁰ Each is H or methyl.

In some cases, R ¹¹ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-12 ) Alkyl or substituted or unsubstituted ring (C) _3-12 ) A heteroalkyl group. In some cases, R ¹¹ Is substituted or unsubstituted C _1-6 Alkyl, substituted or unsubstituted ring (C) _3-12 ) Alkyl, or substituted or unsubstituted ring (C) _3-12 ) A heteroalkyl group. In some cases, R ¹¹ Is a substituted or unsubstituted ring (C _3-12 ) Alkyl or substituted or unsubstituted ring (C) _3-12 ) A heteroalkyl group. In some cases, R ¹¹ Is a substituted or unsubstituted ring (C) _3-12 ) An alkyl group. In some cases, the ring (C _3-12 ) Alkyl groups are bicyclic. In one placeIn some cases, R ¹¹ Is substituted or unsubstituted and is selected from the group consisting of:

wherein the method comprises the steps ofRepresents the remainder attached to formula (IV).

In some cases, R ¹¹ Is substituted or unsubstituted and is selected from the group consisting of:

in some cases, R ¹¹ Selected from the group consisting of:

in some cases, R ¹¹ Is thatIn some cases, R ¹¹ By one or more halogens, -OH, -NH ₂ 、-NH(C ₁ -C ₃ Alkyl), -N (C) ₁ -C ₃ Alkyl) (C) ₁ -C ₃ Alkyl group, C ₁ -C ₃ Alkyl or a combination thereof. In some cases, R ¹¹ By halogen, -OH, -NH ₂ 、C ₁ -C ₃ Alkyl groups, or combinations thereof. In some cases, R ¹¹ Is one or more C ₁ -C ₃ Alkyl substitution. In some cases, R ¹¹ Is covered by C ₁ -C ₃ Alkyl substitution.

In some cases, p is 10 to 200. In some cases, p is 50 to 200. In some cases, p is 100 to 200. In some cases, p is 5 to 25. In some cases, p is 10 to 50. In some cases, p is 20 to 60. In some cases, p is 30 to 80.

In some embodiments, the telechelic polymer is a polymer having a _n B _m Telechelic block copolymers in block configuration. Such telechelic block copolymers may be compounds according to formula (V):

wherein R is ⁵ 、R ⁶ 、R ⁷ 、R ⁸ N and m are as defined above.

III photo-curable resins

The present invention provides photocurable resin compositions that may comprise one or more telechelic polymers described herein, such as those comprising, in polymerized form, one or more monomers according to formulas (I) and (II). Such photocurable resins may comprise photopolymerizable (e.g., photocurable) compositions. Such photopolymerizable compositions may comprise a photopolymerizable telechelic polymer (or telechelic polymers) as described herein. As further described herein, the telechelic polymer may be a telechelic block copolymer comprising 2, 3, 4, 5 or more different monomer species, e.g., one according to formula (III). In various cases herein, the photocurable resin can comprise 1, 2, 3, 4, 5, or more different telechelic polymers and/or telechelic oligomers. One or more such telechelic polymers may be a telechelic block copolymer.

Resin component

The photocurable resin of the present invention may comprise one or more photopolymerizable components. The one or more photopolymerizable components may include one or more telechelic polymers, such as telechelic block copolymers, one or more telechelic oligomers, one or more polymerizable monomers (e.g., reactive diluents), and combinations thereof.

In various cases, the photocurable resin of the present invention may comprise a first telechelic polymer. The first telechelic polymer may comprise a first monomer, wherein the first monomer comprises a first reactive functional group comprising a first photopolymerizable moiety, and wherein one or more of the following conditions are satisfied: (i) The first monomer has a vapor pressure of at most about 8000Pa at 60 ℃ in its monomeric state; (ii) After heating at 90 ℃ for 2 hours, the first monomer has a mass loss rate of less than about 0.25% per hour at 90 ℃ in its monomer state; (iii) The first telechelic polymer has a molecular weight of no greater than about 50kDa; (iv) The first reactive functional group comprises a first photopolymerizable moiety.

In some cases, the photocurable resins herein may comprise a second telechelic polymer. The second telechelic polymer may comprise a second monomer, wherein the second monomer comprises a second reactive functional group, comprises a second photopolymerizable moiety, and satisfies one or more of the following conditions: (v) The second monomer has a vapor pressure of at most about 8000Pa at 60 ℃ in its monomeric state; (vi) After heating at 90 ℃ for 2 hours, the second monomer has a mass loss rate of less than 0.25% per hour at 90 ℃ in its monomer state; (vii) The second telechelic polymer has a molecular weight of no greater than about 50kDa; (viii) The second reactive functional group comprises a second photopolymerizable moiety.

In some embodiments, provided herein are photocurable resins that meet 2, 3, 4, 5, 6, 7, or all of the conditions of the first and/or second telechelic polymers.

In some cases, the first photopolymerizable portion of the first telechelic polymer and the second photopolymerizable portion of the second telechelic polymer are selected from the group consisting of acrylates and methacrylates. In some cases, the first photopolymerizable portion and the second photopolymerizable portion are different. In other cases, the first photopolymerizable portion and the second photopolymerizable portion are the same.

In some cases, the first telechelic polymer consists of a single monomer species a, so the terminal monomers of such telechelic polymer are the same as all other monomers present in the polymer. In other embodiments, the first telechelic polymer is a telechelic block copolymer comprising blocks of at least 2 different monomer species, wherein one of such 2 different monomers is the same as the first terminal monomer. The two terminal monomers may be the same or different depending on the block configuration of the telechelic block copolymer. For example, a first telechelic block copolymer is prepared from A _x B _y Wherein x and y are independently positive integers from 1 to 50, such first telechelic polymer comprising two different terminal monomers a and B. In another example, the first telechelic block copolymer is prepared from A _x B _y A _z And wherein x, y and z are independently positive integers from 1 to 50, such telechelic polymers comprising two identical terminal monomers a. In some embodiments, the second telechelic polymer present in the photocurable polymer may be composed of a single monomer species B, so that the terminal monomers (including the second monomer) of such telechelic polymer are the same as all other monomers present in the polymer. In other embodiments, the second telechelic polymer is a telechelic block copolymer comprising blocks of at least 2 different monomer species, wherein one of such 2 different monomers is the same as the second monomer. The two terminal monomers may be the same or different depending on the block configuration of the telechelic block copolymer. For example, a second telechelicBlock copolymer of A _x B _y Wherein x and y are independently positive integers from 1 to 50, such second telechelic polymer comprising two different terminal monomers a and B. In another example, the second telechelic block copolymer is prepared from A _x B _y A _z Block configuration composition of (C) _， And wherein x, y and z are independently positive integers from 1 to 50, such second telechelic polymer comprising two identical terminal monomers A. However, 2 chemically different terminal monomers a and B may still have the same photopolymerizable moiety. Such photopolymerizable moieties may be acrylates or methacrylates.

In some cases, the terminal monomers of the telechelic polymers herein may be further modified after synthesis of the polymers as described herein, for example, by the introduction of specific photopolymerizable moieties. For example, the telechelic polymer may include terminal functional groups (e.g., hydroxyl, amine, etc.) that may be used to couple the photopolymerizable moiety to terminal monomers of the polymer. Any coupling chemistry can be used to perform such end modifications, including nucleophilic substitution reactions and click chemistry. After such modification, the terminal monomers are chemically different from the internal monomers of the telechelic polymer. Example 3 herein shows such end modifications that introduce photoreactive moieties at the ends of telechelic polymers.

In some aspects, the photocurable resins provided herein comprise 0.5-99.5wt% telechelic polymer, 1-99wt% telechelic polymer, 10-95wt% telechelic polymer, 20-90wt% telechelic polymer, 25-60wt% telechelic polymer, or 35-50wt% telechelic polymer. In some aspects, the photocurable resin comprises 25-60wt% of the telechelic polymer. In some aspects, the photocurable resin comprises 99.5wt% or less of the telechelic polymer.

The photocurable resins described herein may also comprise one or more photoinitiators. Such photoinitiators, when activated with light of an appropriate wavelength (e.g., UV/VIS), can initiate polymerization reactions (e.g., during photocuring) between the telechelic polymer, monomers, and other potentially polymerizable components that may be present in the photocurable resin to form the polymeric materials described further herein. Generally, photoinitiators described in the present disclosure can include those that can be activated with light and initiate polymerization of the polymerizable components of the formulation. As used herein, a "photoinitiator" may generally refer to a compound that can generate free radical species and/or promote a free radical reaction upon exposure to radiation (e.g., UV or visible light).

In some embodiments, the photocurable resins herein further comprise 0.05wt% to 1wt%, 0.05wt% to 2wt%, 0.05wt% to 3wt%, 0.05wt% to 4wt%, 0.05wt% to 5wt%, 0.1wt% to 1wt%, 0.1wt% to 2wt%, 0.1wt% to 3wt%, 0.1wt% to 4wt%, 0.1wt% to 5wt%, 0.1wt% to 6wt%, 0.1wt% to 7wt%, 0.1wt% to 8wt%, 0.1wt% to 9wt% or 0.1wt% to 10wt% of a photoinitiator, based on the total weight of the composition. In some embodiments, the photoinitiator is a free radical photoinitiator. In certain embodiments, the free radical photoinitiator comprises an alpha-hydroxy ketone moiety (e.g., 2-hydroxy-2-methylbenzophenone or 1-hydroxycyclohexyl phenyl ketone), an alpha-amino ketone (e.g., 2-benzyl-2- (dimethylamino) -4' -morpholinophenone or 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one), 4-methylbenzophenone, an azo compound (e.g., 4' -azobis (4-cyanovaleric acid), 1' -azobis (cyclohexanecarbonitrile, azobisisobutyronitrile, 2' -azobis (2-methylpropanenitrile) or 2,2' -azobis (2-methylpropanenitrile)), an inorganic peroxide, an organic peroxide, or any combination thereof, in some embodiments, the composition comprises a photoinitiator comprising speedcure tpo-L ((2, 4, 6-trimethylbenzoyl) phenylphosphinate). In some embodiments, the photocurable composition comprises a mixture selected from benzophenone, and an aromatic-containing at least one direct bond to a tertiary amine such as Irgare, a photoinitiator of Irgacure907 (2-methyl-1- [4- (methylthio) -phenyl ] -2-morpholino-propanone-1) or Irgacure651 (2, 2-dimethoxy-1, 2-diphenylethan-1-one). In some embodiments, the photoinitiator comprises an acetophenone photoinitiator (e.g., 4' -hydroxyacetophenone, 4'0 phenoxyacetophenone, 4' -ethoxyacetophenone), benzoin derivatives, benzil derivatives, benzophenone (e.g., 4-benzoylbiphenyl, 3,4- (dimethylamino) benzophenone, 2-methylbenzophenone), a cationic photoinitiator (e.g., diphenyliodonitrate.(4-iodophenyl) diphenylsulfonium triflate, triphenylsulfonium triflate), anthraquinone, quinone (e.g., camphorquinone), phosphine oxide, phosphinate, 9, 10-phenanthrenequinone, thioxanthone, any combination thereof, or any derivative thereof.

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

The photocurable resins described herein may also include one or more reactive diluents. As used herein, the term "reactive diluent" generally refers to a substance that reduces the viscosity of another substance. In each case, the reactive diluent herein is a monomeric species, such as a compound according to formula (I) or (II) herein. The reactive diluent may become part of another substance, such as a polymer, by, for example, a polymerization (e.g., photopolymerization) reaction. In some embodiments, the reactive diluent is a curable monomer that, when mixed with the curable resin, reduces the viscosity of the resulting formulation and is incorporated into the polymer resulting from the polymerization of the formulation. In some cases, the monomer of the telechelic polymer herein can be a reactive diluent. In this case, a monomer having reactive diluent properties may be coupled to the end of the telechelic polymer chain such that the monomer becomes the terminal monomer. In some cases, coupling of such monomers to the telechelic polymer may occur prior to curing (e.g., photopolymerization) such that the telechelic polymer comprising such terminal monomers is the photopolymerizable component of the curable resin. In other cases, monomers having reactive diluent properties may be coupled to the ends of the telechelic polymer chains during curing (e.g., photopolymerization) such that the monomers having reactive diluent properties are incorporated into the formed polymeric structure during the curing process.

In various aspects, the present disclosure provides a curable resin comprising a telechelic polymer and a reactive diluent, wherein the reactive diluent comprises reactive functional groups, and wherein one, two, three, or all of the following conditions are satisfied: (i) The reactive diluent has a vapor pressure of at most about 8000Pa at 60 ℃ in its monomeric state; (ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the reactive diluent in its monomeric state at 90 ℃ per hour is less than 0.25%; (iii) the telechelic polymer has a molecular weight of no greater than about 50kDa; (iv) the reactive functional group comprises a photopolymerizable moiety. In some cases, two of (i), (ii), (iii), and (iv) are satisfied. In some cases, three of (i), (ii), (iii), and (iv) are satisfied. In some cases, all four conditions of (i), (ii), (iii) and (iv) are satisfied

The reactive diluents provided herein can reduce the viscosity of the photocurable composition, for example, to less than the viscosity of the composition in the absence of the reactive diluent. The reactive diluent may reduce the viscosity of the photocurable composition by at least 10%, such as at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%. The curable composition may comprise 5 to 80wt%, 5 to 70wt%, 5 to 60wt%, 5 to 50wt%, 5 to 40wt%, 5 to 30wt%, 5 to 25wt%, 5 to 20wt%, 10 to 70wt%, 10 to 60wt%, 10 to 50wt%, 10 to 40wt%, 10 to 30wt%, 10 to 25wt%, 20 to 70wt%, 20 to 60wt%, 20 to 50wt%, 20 to 40wt%, 20 to 35wt%, or 20 to 30wt% of the reactive diluent based on the total weight of the composition. In certain embodiments, the curable composition may comprise 5 to 80wt% of the reactive diluent, based on the total weight of the composition. In certain embodiments, the curable composition may comprise 5 to 50wt% of the reactive diluent, based on the total weight of the composition. The reactive diluent of the curable composition may be monofunctional. In some embodiments, the reactive diluent comprises a methacrylate moiety. In some embodiments, the reactive diluent comprises a dimethacrylate moiety. In some cases, the reactive diluent may be selected from the group consisting of dimethacrylates, hydroxybenzoates (meth) acrylates of polyglycols, and mixtures thereof. Optionally, the reactive diluent is a cycloalkyl 2-, 3-, or 4- ((meth) acryloyloxy) -benzoate.

In some embodiments, the photocurable resins of the present invention may comprise a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof. In some aspects, the photocurable resin comprises from 0 to 25wt% of a crosslinking modifier having a number average molecular weight equal to or less than 1,500 da. In some aspects, the photocurable resin comprises 0 to 10wt%, 0 to 9wt%, 0 to 8wt%, 0 to 7wt%, 0 to 6wt%, 0 to 5wt%, 0 to 4wt%, 0 to 3wt%, 0 to 2wt%, 0 to 1wt%, or 0 to 0.5wt% of the light blocker. In some embodiments, the photocurable resin comprises a solvent. In some embodiments, the solvent comprises a non-polar solvent. In certain embodiments, the non-polar solvent comprises pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane, derivatives thereof, or combinations thereof. In some embodiments, the solvent comprises a polar aprotic solvent. In certain embodiments, the polar aprotic solvent comprises tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, DMSO, propylene carbonate, derivatives thereof, or combinations thereof. In some embodiments, the solvent comprises a polar protic solvent. In certain embodiments, the polar protic solvent comprises formic acid, n-butanol, isopropanol, n-propanol, t-butanol, ethanol, methanol, acetic acid, water, derivatives thereof, or combinations thereof. In a preferred embodiment, the photocurable resin comprises less than 90wt% solvent.

In some embodiments, the added components (e.g., crosslinking modifiers, polymerization catalysts, polymerization inhibitors, glass transition temperature modifiers, light blockers, plasticizers, solvents, surface energy modifiers, pigments, dyes, fillers (or biologically significant chemicals) are functionalized so that they can be incorporated into the polymeric material and thus not readily extracted from the final cured material.

In some embodiments, the glass transition temperature modifier (also referred to herein as T _g Modifiers, glass transition modifiers, crosslinkers, and crosslinkers) may be present in the photocurable composition from about 0 to 50 weight percent. T (T) _g The modifier may have a high glass transition temperature, which results in a high heat distortion temperature, which may be necessary for using the material at high temperatures. In some embodiments, the curable composition comprises 0 to 80wt%, 0 to 75wt%, 0 to 70wt%, 0 to 65wt%, 0 to 60wt%, 0 to 55wt%, 0 to 50wt%, 1wt% to 50wt%, 2wt% to 50wt%, 3wt% to 50wt%, 4wt% to 50wt%, 5wt% to 50wt%, 10wt% to 50wt%, 15wt% to 50wt%, 20wt% to 50wt%, 25wt%50wt%, 30 to 50wt%, 35 to 50wt%, 0 to 40wt%, 1 to 40wt%, 2 to 40wt%, 3 to 40wt%, 4 to 40wt%, 5 to 40wt%, 10wt% to 40wt%, 15wt% to 40wt%, or 20wt% to 40wt% T _g And (3) a regulator. In certain embodiments, the curable composition comprises 0 to 50wt% glass transition modifier. T (T) _g The regulator generally has a higher T than the toughness regulator or telechelic polymer _g . Optionally T _g The number average molecular weight of the modulator is 0.4 to 5kDa. In some embodiments, T _g The number average molecular weight of the modulator is 0.1kDa to 5kDa, 0.2kDa to 5kDa, 0.3kDa to 5kDa, 0.4kDa to 5kDa, 0.5kDa to 5kDa, 0.6kDa to 5kDa, 0.7kDa to 5kDa, 0.8kDa to 5kDa, 0.9kDa to 5kDa, 1.0kDa to 5kDa, 0.1kDa to 4kDa, 0.2kDa to 4kDa, 0.3kDa to 4kDa, 0.4kDa to 4kDa, 0.5kDa to 4kDa, 0.6kDa to 4kDa, 0.7kDa to 4kDa, 0.8kDa to 4kDa, 0.9kDa to 4kDa, 1kDa to 4kDa, 0.1kDa to 3kDa, 0.2kDa to 3kDa, 0.3kDa to 3kDa, 0.4kDa to 3kDa, 0.6kDa to 3kDa, 0.7kDa to 3kDa, 0.8kDa to 3kDa, 0.9kDa to 3kDa or 1kDa to 3kDa. Toughness regulator and reactive thinReleasing agent and T _g The modulator is generally miscible and compatible in the methods described herein. When used in the compositions described herein, T _g The modulator may provide a high T _g And strength values, sometimes at the expense of elongation at break. The ductility modifier provides high elongation at break and ductility by enhancing the effect, and the reactive diluent improves the processability of the formulation, particularly those containing high amounts of ductility modifier, while maintaining high strength and T _g Values.

The photocurable resin may contain a filler material that does not participate in polymerization but is fixed within the cured resin upon curing, affecting its material properties. For example, the addition of filler materials to photocurable resins can reduce vapor pressure and increase viscosity prior to curing and enhance the strength, storage modulus, and stiffness of the polymeric materials printed therefrom. In addition, in some cases, the filler material may inhibit crack or deformation propagation, preventing small cracks from propagating throughout the printed material. For dental appliances and other practical applications, the filler material can reduce overall quality and thickness requirements and extend service life. Such enhancement is particularly important for orthodontic appliances, such as dental attachments, which may require continuous or repeated use over a longer period of time. For example, dental correction programs may rely on a set of dental attachments to maintain shape, strength, and integrity over many years of treatment.

The filler material may be unevenly distributed throughout the photocurable resin or the material printed therefrom. In some cases, the filler material is uniformly dispersed throughout the photocurable resin. Such uniform dispersion may be achieved, for example, by stirring or mixing the photocurable resin prior to or during curing. In some cases, the filler material is uniformly distributed along a first dimension or set of dimensions and is unevenly distributed along a second dimension or set of dimensions. For example, the filler material may be randomly dispersed throughout the length and width of the photocurable resin and unevenly distributed along the height of the photocurable resin. The fill material may be patterned, for example, along a transverse or longitudinal wave, or along a concentration gradient. The filler material may also be concentrated within the interior space or along the surface of the photocurable resin or material printed therefrom. In some cases, the filler material is patterned within the photocurable resin. In this case, the filler material may be concentrated along longitudinal or transverse waves, complex patterns, gradients, or combinations thereof. In some cases, the filler material may be provided in the form of a braid (e.g., overlapping, non-parallel fibers), a tuft, a sheet, or a combination thereof.

The photocurable resin may contain a filler material in a range of weight percentages. The filler material may be a minor component of the photocurable resin, for example, less than 5 weight percent (wt%), or may comprise a majority of the weight of the photocurable resin. In some cases, the filler material is present at 0.05 to 60wt%, 1 to 5wt%, 1 to 10wt%, 1 to 20wt%, 2 to 5wt%, 2 to 10wt%, 2 to 20wt%, 3 to 6wt%, 3 to 10wt%, 3 to 20wt%, 5 to 10wt%, 5 to 25wt%, 8 to 20wt%, 10 to 60wt%, 12 to 25wt%, 15 to 30wt%, 15 to 40wt%, 20 to 35wt%, 25 to 50wt%, 30 to 50wt%, 35wt% to 65wt%, 40wt% to 80wt%, 50wt% to 75wt%, or 60wt% to 80wt% of the photocurable resin.

In some cases, the photocurable resin comprises a wetting agent. Since the wetting agent may change the surface characteristics of the printing material, inclusion of the wetting agent may enhance applicability of 3D printing. In some cases, the wetting agent may affect the resin surface properties to improve its printability. The wetting agent may comprise a hydrophilic material such as a siloxane, polyamide, polylactone, phosphate, polylactam, or combinations thereof. In particular instances, the wetting agent comprises a silicone. In some cases, the siloxane is a polyether modified polydimethylsiloxane.

In some cases, the photocurable resin comprises about 0.01 to about 3 weight percent of a wetting agent. In some cases, the photocurable resin comprises from about 0.05wt% to about 1.5wt%, from about 0.1wt% to about 1.5wt%, from about 0.3wt% to about 1.5wt%, from about 0.1wt% to about 1wt%, from about 0.1wt% to about 0.5wt%, from about 0.2 to about 1wt%, from about 0.3 to about 0.7wt%, or from about 0.4 to about 1wt% of the wetting agent.

Resin Properties

The photocurable resins herein may be characterized by having one or more properties.

The resins of the present disclosure may have a viscosity of 30cP to 50,000cP at the printing temperature. In some cases, the printing temperature is about 20 ℃ to about 150 ℃. In some embodiments, the photocurable resin has a low viscosity at ambient temperature. In some embodiments, the photocurable resin has a viscosity of less than or equal to 30,000cp, less than or equal to 25,000cp, less than or equal to 20,000cp, less than or equal to 19,000cp, less than or equal to 18,000cp, less than or equal to 17,000cp, less than or equal to 16,000cp, less than or equal to 15,000cp, less than or equal to 14,000cp, less than or equal to 13,000cp, less than or equal to 12,000cp, less than or equal to 11,000cp, less than or equal to 10,000cp, less than or equal to 9,000cp, less than or equal to 8,000cp, less than or equal to 7,000cp, less than or equal to 6,000cp, or less than or equal to 5,000cp at 25 ℃. In a preferred embodiment, the resin has a viscosity of less than 15,000cp at 25 ℃.

In some embodiments, the photocurable resin has a viscosity of less than or equal to 100,000cP, less than or equal to 90,000cP, less than or equal to 80,000cP, less than or equal to 70,000cP, less than or equal to 60,000cP, less than or equal to 50,000cP, less than or equal to 40,000cP, less than or equal to 35,000cP, less than or equal to 30,000cP, less than or equal to 25,000cP, less than or equal to 20,000cP, less than or equal to 15,000cP, less than or equal to 10,000cP, less than or equal to 5,000cP, less than or equal to 4,000cP, less than or equal to 3,000cP, less than or equal to 2,000cP, less than or equal to 1,000cP, less than or equal to 750cP, less than or equal to 500cP, less than or equal to 250cP, less than or equal to 100cP, less than or equal to 90cP, less than or equal to 80cP, less than or equal to 70cP, less than or equal to 60cP, less than or equal to 50cP, less than or equal to 40cP, or equal to 30 cP. In some embodiments, the photocurable resin has a viscosity of 50,000cP to 30cP, 40,000cP to 30cP, 30,000cP to 30cP, 20,000cP to 30cP, 10,000cP to 30cP, or 5,000cP to 30cP at the printing temperature. In some embodiments, the printing temperature is from 0 ℃ to 25 ℃, from 25 ℃ to 40 ℃, from 40 ℃ to 100 ℃, or from 20 ℃ to 150 ℃. In a preferred embodiment, the photocurable resin has a viscosity of 30cP to 50,000cP at a printing temperature, wherein the printing temperature is 20 ℃ to 150 ℃.

In a preferred embodiment, the photocurable resin has a viscosity of less than 20,000cp at the printing temperature. In some embodiments, the printing temperature is 10 ℃ to 200 ℃, 15 ℃ to 175 ℃, 20 ℃ to 150 ℃, 25 ℃ to 125 ℃, or 30 ℃ to 100 ℃. In a preferred embodiment, the printing temperature is 20 ℃ to 150 ℃.

In certain embodiments, the photocurable resin has a viscosity of less than 1,000cp at 110 ℃. In some embodiments, the photocurable resin has a viscosity of less than 1,000cp at 90 ℃. In some embodiments, the photocurable resin has a viscosity of less than 500cP at 70 ℃. In some embodiments, the photocurable resin has a viscosity of less than 200cP at 90 ℃. In some embodiments, the photocurable resin has a viscosity of less than 10,000cp at 25 ℃.

The photocurable resins of the present disclosure may contain less than 20wt% hydrogen bond units. In some aspects, the photocurable resin comprises less than 15wt%, less than 10wt%, less than 9wt%, less than 8wt%, less than 7wt%, less than 6wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, or less than 1wt% of hydrogen bond units, wherein wt% is the weight percent of a species capable of forming at least one hydrogen bond, the species comprising polymerized, oligomeric, and monomeric forms of monomer units.

In some embodiments, the photocurable composition has a melting temperature above room temperature. In some embodiments, the photocurable composition has a melting temperature greater than 20 ℃, greater than 25 ℃, greater than 30 ℃, greater than 35 ℃, greater than 40 ℃, greater than 45 ℃, greater than 50 ℃, greater than 55 ℃, greater than 60 ℃, greater than 65 ℃, greater than 70 ℃, greater than 75 ℃, or greater than 80 ℃. In some embodiments, the photocurable composition has a melting temperature of 20 ℃ to 250 ℃, 30 ℃ to 180 ℃, 40 ℃ to 160 ℃, or 50 ℃ to 140 ℃. In some embodiments, the photocurable composition has a melting temperature greater than 60 ℃. In other embodiments, the photocurable composition has a melting temperature of 80 ℃ to 110 ℃. In some cases, the photocurable composition may have a melting temperature of about 80 ℃ prior to polymerization, and after polymerization, the resulting polymeric material may have a melting temperature of about 100 ℃.

In some cases, it may be advantageous for the photocurable composition (e.g., resin) or the polymeric material that the composition may form upon exposure to electromagnetic radiation of the appropriate wavelength to be in the liquid phase at elevated temperatures. As an example, conventional photocurable resins may contain polymers and/or polymer crystals that may be tacky and thus may be difficult to use in the manufacture of objects (e.g., using 3D printing). As a solution to this technical problem, the present disclosure provides photocurable resins comprising polymers and/or polymer crystals that can melt at elevated temperatures, e.g., at manufacturing temperatures (e.g., during 3D printing), and have reduced viscosities at elevated temperatures, which can make such resins more suitable and useful for applications such as 3D printing. Thus, in some embodiments, provided herein are photocurable resins that are liquid at elevated temperatures. In some embodiments, the elevated temperature is equal to or greater than Yu Keguang the melting temperature (T _m) . In certain embodiments, elevated temperature refers to a temperature in the range of 40 ℃ to 100 ℃, 60 ℃ to 100 ℃, 80 ℃ to 100 ℃, 40 ℃ to 150 ℃, or 150 ℃ to 350 ℃. In some embodiments, the elevated temperature is a temperature above 40 ℃, above 60 ℃, above 80 ℃, or above 100 ℃. In some embodiments, the photocurable resins herein are liquid at elevated temperatures with a viscosity of less than 50PaS, less than 20PaS, less than 10PaS, less than 5PaS, or less than 1PaS. In some embodiments, the photocurable resins herein are liquids having a viscosity of less than 20PaS at elevated temperatures. In still other embodiments, the photocurable resins herein are liquids having a viscosity of less than 1PaS at elevated temperatures.

In some embodiments, at least a portion of the photocurable resins herein have a melting temperature of less than 100 ℃, less than 90 ℃, less than 80 ℃, less than 70 ℃, or less than 60 ℃. In some embodiments, at least a portion of the photocurable resins herein melt at an elevated temperature of 100 ℃ to 20 ℃, 90 ℃ to 20 ℃, 80 ℃ to 20 ℃, 70 ℃ to 20 ℃, 60 ℃ to 10 ℃, or 60 ℃ to 0 ℃. In some embodiments, the photocurable resins herein are liquid at elevated temperatures with a viscosity of less than 50PaS, less than 20PaS, less than 10PaS, less than 5PaS, or less than 1PaS.

In some embodiments, the photocurable resins of the present invention may comprise a variety of crystallizable polymeric materials, at least some of which melt at different temperatures. Such crystallizable polymeric materials may comprise the block copolymers described herein. In certain embodiments, at least one crystallizable polymeric material melts at a temperature of less than 100 ℃, less than 90 ℃, less than 80 ℃, less than 70 ℃, or less than 60 ℃. In some embodiments, the at least one crystallizable polymeric material melts at an elevated temperature of between 100 ℃ and 20 ℃, 90 ℃ and 20 ℃, 80 ℃ and 20 ℃, 70 ℃ and 20 ℃, 60 ℃ and 10 ℃, or 60 ℃ and 0 ℃. In some embodiments, the crystalline domains of the photocurable resin may melt at a temperature greater than 60 ℃, greater than 80 ℃, greater than 100 ℃, greater than 120 ℃, or greater than 140 ℃. In some embodiments, the crystallizable polymeric material of the photocurable resins herein may be liquid at elevated temperatures and may have a viscosity of less than 50PaS, less than 20PaS, less than 10PaS, less than 5PaS, or less than 1 PaS. In certain embodiments, the crystallizable polymeric material of the photocurable resins herein may be liquid in general in nature, but may contain at least one unmelted polymeric crystal or a plurality of unmelted polymeric crystals (e.g., in some cases, the crystallizable polymeric material may contain domains that melt above the melting temperature, as well as domains that remain crystalline at the same temperature). In some embodiments, the unmelted polymer crystals can have a melting temperature greater than 60 ℃, greater than 70 ℃, greater than 80 ℃, greater than 90 ℃, greater than 100 ℃, or greater than 110 ℃. In some embodiments, at least one crystallizable polymeric material of the photocurable resin melts at a temperature that is greater than the use temperature. As a non-limiting example, a material having a use temperature of about 37 ℃ may comprise at least one crystallizable polymeric material that crystallizes at 37 ℃ and melts when warmed to a temperature of greater than 37 ℃ (e.g., 60 ℃). As used herein, the use temperature may be a temperature of less than or equal to 20 ℃, 20 ℃ to 40 ℃, or greater than or equal to 40 ℃. In a preferred embodiment, the use temperature comprises a temperature of 20 ℃ to 40 ℃. In other preferred embodiments, the temperature used is from 50 ℃ to 100 ℃. In still other embodiments, the use temperature is between 100 ℃ and 150 ℃. In still other embodiments, the use temperature is greater than 150 ℃. In some embodiments, the resin has a melting temperature at which at least a portion of the resin melts, and the melting temperature is less than 100 ℃, less than 90 ℃, less than 80 ℃, less than 70 ℃, less than 60 ℃, less than 50 ℃, or less than 40 ℃. In some embodiments, the resin has a melting temperature greater than 60 ℃, greater than 80 ℃, greater than 100 ℃, greater than 120 ℃, or greater than 140 ℃.

In certain embodiments, the photocurable resins herein may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the photo-crystallizable polymeric material in the liquid phase (i.e., having a melting point that is lower than the elevated temperature) at elevated temperature. In some embodiments, the photocurable resin at 60 ℃ comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the photocurable polymeric material in the liquid phase. In some embodiments, the photocurable resin at 70 ℃ comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the crystallizable photopolymer material in the liquid phase. In some embodiments, the photocurable resin at 80 ℃ comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the photocurable polymeric material in the liquid phase. In some embodiments, the crystallizable resin at 90 ℃ comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the crystallizable photopolymer material in the liquid phase. In some embodiments, the crystallizable resin at 100 ℃ comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the crystallizable polymer in the liquid phase.

The photocurable resins of the present disclosure are capable of 3D printing at temperatures above 25 ℃. In some cases, the printing temperature is at least about 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, or 100 ℃. As described herein, the photopolymerizable monomers of the present disclosure, which may be part of the photocurable resin, may have a low vapor pressure and/or mass loss at the printing temperature, thereby providing improved printing conditions compared to resins conventionally used in additive manufacturing. The vapor pressure of the monomer may be the vapor pressure of the pure (e.g., at least 98% pure) photopolymerizable monomer as measured by a pressure gauge or by gravimetric analysis.

In some embodiments, provided herein are photocurable compositions comprising a telechelic polymer having a molecular weight of about 5kDa to about 25kDa described herein, a photoinitiator, and wherein the photocurable resin comprises less than 20wt% hydrogen bond units, and a viscosity of less than or equal to 15,000cp at 25 ℃. In some aspects, the photocurable resin comprises 15-55wt% of the telechelic polymer, 10-75wt% of the reactive diluent, 15-60wt% of the reactive diluent, 20-50wt% of the reactive diluent, 25-45wt% of the reactive diluent, or 30-40wt% of the reactive diluent. In some aspects, the photocurable resin comprises 20-50wt% of a reactive diluent. In some aspects, the crosslinking modifier is a reactive diluent. In some cases, the photocurable resin comprises 0.5-99.5wt%, 1-99wt%, 10-95wt%, 20-90wt%, 25-60wt%, or 35-50wt% of the telechelic polymer, the second telechelic polymer, the telechelic block copolymer, or a combination thereof.

In some embodiments, a photocurable resin composition useful in a photopolymerization process may include: (i) 1 to 70wt% of a photopolymerizable telechelic polymer, based on the total weight of the composition, wherein the telechelic polymer is a telechelic block copolymer having a number average molecular weight of greater than 5kDa but no greater than 50 kDa; (ii) From 5wt% to 80wt% of a reactive diluent, based on the total weight of the composition, wherein the reactive diluent is a photopolymerizable compound having a molecular weight of from 0.1kDa to 1.0 kDa; (iii) 0.1 to 5wt% of a photoinitiator based on the total weight of the composition, wherein the resin has a viscosity of 1 to 70 Pa-s at 110 ℃.

Polymeric materials

The photocurable resins described herein may form polymeric materials, for example, upon exposure to electromagnetic radiation of an appropriate wavelength. In various instances, polymeric materials formed from photocurable resins may have various characteristics and properties that make them particularly useful in the use and manufacture of medical devices (e.g., orthodontic appliances). The photocurable resins used to produce the polymeric materials herein may comprise one or more telechelic polymers of the present disclosure, such as those comprising monomers according to formulas (I) and (II) in polymerized form, as well as telechelic block copolymers, such as one according to formula (III) herein. The polymeric materials provided herein may be biocompatible, bioinert, or a combination thereof. Further, the characteristics and properties of the initial photocurable composition may be altered by varying the amount and/or type of components present therein. In various cases, the polymeric materials of the present disclosure may be produced using additive manufacturing.

Phase separation in polymeric materials

In some aspects herein, the photocurable compositions or resins herein may be cured by exposing such compositions or resins to electromagnetic radiation of an appropriate wavelength to produce a polymeric material. Such curing or polymerization may cause phase separation in the photocurable composition and/or the formed polymeric material. Such polymerization-induced phase separation may occur along one or more of the lateral and vertical directions (see, e.g., fig. 6). Polymerization-induced phase separation may produce one or more polymer phases in the resulting polymer material. The photocurable composition that undergoes polymerization and polymerization-induced phase separation may comprise one or more telechelic polymers (e.g., telechelic block copolymers) of the present invention. Thus, in some cases, at least one of the one or more polymer phases that are generated during the curing process and present in the resulting polymeric material may comprise at least one of one or more such telechelic polymers in polymerized form. In one example, a photocurable resin comprising a telechelic polymer (e.g., a telechelic block copolymer) is cured by exposure to electromagnetic radiation of an appropriate wavelength. The cured polymeric material contained 2 polymer phases a and B. In some cases, at least one of phases a or B may comprise a telechelic polymer as a component in its polymeric structure. In some cases, both phase a and phase B may comprise a telechelic polymer as a component in its polymeric structure. Phase a and phase B may contain different amounts or concentrations of telechelic polymer. Thus, in some cases herein, two or more phases comprising a telechelic polymer herein may be separated by a concentration gradient of such telechelic polymer.

The polymer phase of the polymeric materials of the present disclosure may have a certain size or volume. In some embodiments, the polymer phase is 3-dimensional and may have at least one dimension 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 of 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 of 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 polymeric material comprises an average polymeric phase size of less than about 5 μm in at least one spatial dimension.

In various aspects, the present disclosure provides a polymeric material that may include one or more polymeric phases, wherein at least one of the one or more polymeric phases is a crystalline phase. In various aspects, the present disclosure provides a polymeric material that may include one or more polymeric phases, wherein at least one of the one or more polymeric phases is amorphous. In some cases, provided herein are polymeric materials that can include two or more polymeric phases, wherein at least one of the one or more polymeric phases is a crystalline phase and at least one of the one or more polymeric phases is an amorphous phase.

Accordingly, in some cases, provided herein is a polymeric material comprising: (i) At least one crystalline phase comprising at least one polymer crystal having a melting temperature above 20 ℃; (ii) At least one amorphous phase comprising at least one amorphous polymer having a glass transition temperature greater than 40 ℃. In some cases, at least one crystalline phase may comprise one or more telechelic polymers of the present invention in polymerized form. In some cases, at least one amorphous phase may comprise one or more telechelic polymers of the present invention in polymerized form. In some aspects, such amorphous phases have a glass transition temperature greater than 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or greater than 110 ℃. In some cases, such amorphous phases may comprise one or more telechelic polymers of the present invention in polymerized form. In some aspects, at least one polymer crystal has a melting temperature above 30 ℃, 40 ℃, 50 ℃, 60 ℃, or above 70 ℃. In some cases, such crystalline phases may comprise one or more telechelic polymers of the present invention in polymerized form.

Amorphous polymer phase

The present invention provides polymeric materials comprising one or more amorphous phases, such as an amorphous phase produced by polymerization-induced phase separation. Such polymeric materials or regions of such materials comprising a polymeric phase may provide a fast response time to external stimuli, which may impart advantageous properties to polymeric materials comprising crystalline and/or amorphous phases, for example for use with polymeric materials in medical devices (e.g., orthodontic appliances). In some cases, a polymeric material comprising one or more amorphous polymeric phases may, for example, provide flexibility to the cured polymeric material, which may increase its durability (e.g., the material may be stretched or bent while maintaining its structure, while a similar material without an amorphous phase may fracture). In certain embodiments, the amorphous phase may be characterized by randomly oriented polymer chains (e.g., stacked non-parallel or stacked in a crystalline structure). In some embodiments, such amorphous polymer phases of the polymeric material may have a glass transition temperature greater than about 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or greater than about 110 ℃. In some embodiments, the amorphous polymer phase may have a glass transition temperature of about 40 ℃ to about 60 ℃, about 50 ℃ to about 70 ℃, about 60 ℃ to about 80 ℃, or about 80 ℃ to about 110 ℃. In some aspects, the amorphous phase has a glass transition temperature of less than 10 ℃, 0 ℃, -10 ℃, -20 ℃, -30 ℃, -40 ℃, -50 ℃, -60 ℃, or-70 ℃. In some aspects, the one or more amorphous phases will have multiple glass transition temperatures. In some preferred aspects, one or more phases will have a glass transition temperature of less than 0 ℃.

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

In some embodiments, the amorphous polymer phase herein may comprise one or more polymer types formed during curing from polymerizable telechelic polymers, telechelic oligomers, polymerizable monomers, and any other polymerizable components that may be present in the curable composition for use in producing polymeric materials containing such amorphous polymer phase. In some cases, such one or more polymer types may include one or more of homopolymers, linear copolymers, block copolymers, alternating copolymers, periodic copolymers, statistical copolymers, random copolymers, gradient copolymers, branched copolymers, brush copolymers, comb copolymers, dendritic polymers, or any combination thereof. In some cases, the amorphous polymeric material comprises a random copolymer. In some embodiments, the amorphous polymeric material may comprise poly (ethylene glycol) glycol (PEG), poly (ethylene glycol) diacrylate, PEG-THF, polytetrahydrofuran, poly (t-butyl acrylate), polyethylene-maleic anhydride copolymer, any derivative thereof, or any combination thereof.

In some cases, the polymerizable component of the resin that can form the crystalline material can form an amorphous phase when exposed to conditions that prevent crystallization thereof. Thus, in some cases, a material that is generally considered to be crystalline may be used as the amorphous material. As a non-limiting example, polycaprolactone can be a crystalline polymer, but when mixed with other polymerizable monomers and telechelic polymers, can prevent crystal formation and can form an amorphous phase.

In addition to one or more telechelic polymers, the amorphous phase herein may comprise, in polymerized form, one or more of the following moieties: acrylic acid monomers, acrylamide, methacrylamide, acrylonitrile, bisphenol acrylic acid, carbohydrates, fluorinated acrylic acid, maleimide, acrylic acid esters, 4-acetoxyphenethyl acrylic acid esters, acrylic acid chloride, 4-acryloylmorpholine, 2- (acryloyloxy) ethyl ] trimethylammonium chloride, ethyl 2- (4-benzoyl-3-hydroxyphenoxy) acrylate, benzyl 2-propyl acrylate, butyl acrylate, t-butyl acrylate, ethyl 2[ [ (butylamino) carbonyl ] oxy ] acrylate, t-butyl 2-bromoacrylate, ethyl 2-carboxyacrylate, ethyl 2-chloroacrylate, ethyl 2- (diethylamino) acrylate, diethyl glycol) diethyl ether acrylate ethyl 2- (dimethylamino) acrylate, propyl 3- (dimethylamino) acrylate, dipentaerythritol penta-/hexa-acrylate, ethyl acrylate, 2-ethyl acryloyl chloride, ethyl 2- (bromomethyl) acrylate, cis- (. Beta. -cyano) ethyl acrylate, ethylene glycol dicyclopentene ether acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, ethyl 2-ethylacrylate, 2-ethylhexyl acrylate, 2-propyl acrylate, ethyl 2- (trimethylsilyl methyl) acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, isobutyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetamido acrylate, methyl acrylate, methylene malonate (e.g., dibutyl, dihexyl or dicyclohexyl methylene malonate), methylene malonate macromers (e.g., polyesters of 2-methylene malonate, for example, forzaB3000 XP), alpha-bromomethyl acrylate, methyl 2- (bromomethyl) acrylate, methyl 2- (chloromethyl) acrylate, methyl 3-hydroxy-2-methylenebutanoate, methyl 2- (trifluoromethyl) acrylate, octadecyl acrylate, pentabromobenzyl acrylate, pentabromophenyl acrylate, pentafluorophenyl acrylate, poly (ethylene glycol) diacrylate, poly (ethylene glycol) methyl ether acrylate, poly (propylene glycol) acrylate, epoxidized soybean oil acrylate, 3-sulfopropyl acrylate, tetrahydrofurfuryl acrylate, 2-tetrahydropyranyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3, 5-trimethylhexyl acrylate, 10-undecylenate, urethane acrylate methacrylate, tricyclodecane diacrylate, isobornyl acrylate, methacrylate, allyl methacrylate, benzyl methacrylate, (2-boc-amino) ethyl methacrylate, t-butyl methacrylate, 9H-carbazole-9-ethyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 1, 10-decanediol dimethacrylate, ethylene glycol dicyclopentenyl ether methacrylate, ethylene glycol methyl ether methacrylate, 2-ethylhexyl methacrylate, furfuryl methacrylate, glycidyl methacrylate, glycoxyethyl methacrylate, hexyl methacrylate, hydroxybutyl methacrylate, 2-hydroxy-5-N-methacrylamidobenzoic acid, isobutyl methacrylate, methacryloyl chloride, methyl methacrylate, mono-2-methacryloyloxy) ethyl succinate, 2-N-morpholinoethyl methacrylate, 1-naphthalene methacrylate, pentabromophenyl methacrylate, phenyl methacrylate, pentabromophenyl methacrylate, TEMPO methacrylate, 3-sulfopropyl methacrylate, triethylene glycol methyl ether methacrylate, 2- [ (1 ',1',1 '-trifluoro-2' - (trifluoromethyl) -2'0 hydroxy) propyl ] -3-methyl methacrylate norbornyl ester, 3, 5-trimethyl cyclohexyl methacrylate, (trimethylsilyl) methacrylate, vinyl methacrylate, isobornyl methacrylate, bisphenol A dimethacrylate, omnilaneOC, t-butyl acrylate, isodecyl acrylate, tricyclodecane diacrylate, multifunctional acrylate, N' -methylenebisacrylamide, 3- (acryloyloxy) -2-hydroxypropyl) methacrylate, bis [2- (methacryloyloxy) ethyl ] phosphate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, di-polyurethane dimethacrylate, N' -ethylenebis (acrylamide), glycerol 1, 3-glycerolate diacrylate, 1, 6-hexanediol diacrylate, hydroxypivalyl hydroxypivalate 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.

In some embodiments, the amorphous phase of the polymeric materials described herein may include one or more reactive functional groups, which may allow further modification of the polymeric material, such as additional polymerization (e.g., post-curing). In some embodiments, the amorphous polymeric material comprises a plurality of reactive functional groups, and the reactive functional groups may be located at one or both ends of the amorphous material, in a chain, at a side chain (e.g., a side group attached to the polymeric backbone), or any combination thereof. Non-limiting examples of reactive functional groups include free radically polymerizable functional groups, photoactive groups, groups that promote step-growth polymerization, thermally reactive groups, and/or groups that promote bond formation (e.g., covalent bond formation). In some embodiments, the functional groups include acrylates, methacrylates, acrylamides, vinyl ethers, thiols, allyl ethers, norbornene, vinyl acetate, maleates, fumarates, maleimides, epoxides, cyclic ethers (a ring-strained cyclic ether), cyclic sulfides (a ring-strained thioether), cyclic esters, cyclic carbonates, cyclic silanes, cyclic siloxanes, hydroxyl groups, amines, isocyanates, blocked isocyanates, acid chlorides, activated esters, diels-alder reactive groups, furans, cyclopentadiene, anhydrides, groups that facilitate photodimerization (e.g., anthracene, acenaphthylene, or coumarin), groups that photodegradation to reactive species (e.g., norrish type 1 and type 2 materials), azides, derivatives thereof, or combinations thereof.

Crystalline polymer phase

As further described herein, the polymeric materials of the present disclosure may include one or more crystalline phases, for example, produced by polymerization-induced phase separation during curing. As described herein, the crystalline phase is a polymeric phase of a cured polymeric material comprising at least one polymeric crystal. As disclosed herein, the crystalline phase may consist of a single polymer crystal, or may comprise a plurality of polymer crystals.

In some embodiments, the crystalline polymer phase may have a melting temperature equal to or greater than about 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, or equal to or greater than about 150 ℃. In some cases, at least two of the plurality of crystalline phases may have different melting temperatures due to differences in, for example, crystalline phase size, impurities, degree of crosslinking, chain length, thermal history, rate at which polymerization occurs, degree of phase separation, or any combination thereof. In some aspects, the at least two crystalline phases of the polymeric material may each have a polymer crystal melting temperature within about 5 ℃ of each other. In some cases, this difference in melting temperature may be less than about 5 ℃. In other cases, this difference in melting temperature may be greater than about 5 ℃. In some aspects, each polymer crystal of the polymeric material may have a melting temperature of about 40 ℃ to about 100 ℃. In some aspects, at least about 80% of the crystalline domains of the polymeric material may comprise polymer crystals having a melting temperature of about 40 ℃ to about 100 ℃.

In some embodiments, at least 80% of the crystalline phase has a crystalline melting point at a temperature between 0 ℃ and 100 ℃. In some embodiments, at least 80% of the crystalline phase has a crystalline melting point at a temperature between 40 ℃ and 60 ℃, between 40 ℃ and 80 ℃, between 40 ℃ and 100 ℃, between 60 ℃ and 80 ℃, between 60 ℃ and 100 ℃, between 80 ℃ and 100 ℃, or greater than 100 ℃. In some embodiments, at least 90% of the crystalline phase has a crystalline melting point at a temperature between 0 ℃ and 100 ℃. In some embodiments, at least 90% of the crystalline phase has a crystalline melting point at a temperature between 40 ℃ and 60 ℃, between 40 ℃ and 80 ℃, between 40 ℃ and 100 ℃, between 60 ℃ and 80 ℃, between 60 ℃ and 100 ℃, between 80 ℃ and 100 ℃, or greater than 100 ℃. In some embodiments, at least 95% of the crystalline phase has a crystalline melting point at a temperature between 0 ℃ and 100 ℃. In some embodiments, at least 95% of the crystalline phases have a crystalline melting point at a temperature between 40 ℃ and 60 ℃, between 40 ℃ and 80 ℃, between 40 ℃ and 100 ℃, between 60 ℃ and 80 ℃, between 60 ℃ and 100 ℃, between 80 ℃ and 100 ℃, or greater than 100 ℃.

In certain embodiments, the temperature at which the crystalline phase of the cured polymeric material melts may be controlled, for example, by using different amounts and types of polymerizable components in the curable resin, such as different amounts and types of telechelic polymers, e.g., block copolymers having various block configurations and/or different types of monomers, different amounts and types of telechelic polymers and/or oligomers comprising certain types of substituents (e.g., large groups having a molecular radius greater than hydrogen, methyl, etc.), and/or by using polymer blocks having different crystalline melting points (e.g., in telechelic block copolymers).

In some embodiments, curing of the resin may occur at an elevated temperature (e.g., about 90 ℃) and when the cured polymeric material cools to room temperature (e.g., 25 ℃), the cooling may trigger the formation and/or growth of polymer crystals in the polymeric material. In some cases, the polymeric material may be solid at room temperature and may be non-crystalline, but may form a crystalline phase over time. In this case, the crystalline phase may be formed 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 solidified polymeric material is in a cooled environment, a crystalline phase may form, for example, in an environment having a temperature of about 40 ℃ to about 30 ℃, about 30 ℃ to about 20 ℃, about 20 ℃ to about 10 ℃, about 10 ℃ to about 0 ℃, about 0 ℃ to about-10 ℃, about-10 ℃ to about-20 ℃, about-20 ℃ to about-30 ℃, or less than about-30 ℃. In some cases, the polymeric material may be heated to an elevated temperature to induce crystallization or the formation of a crystalline phase. As a non-limiting example, a polymeric material near its glass transition temperature may include polymer chains that are insufficient to move to organize into crystals, so further heating the material may increase the mobility of the chains and induce the formation of crystals.

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 promoted by triggering. In some embodiments, the initiator includes the addition of seed particles (also referred to herein as "seeds") that can induce crystallization. Such seeds may include, for example, finely ground solid materials having at least some properties similar to the crystals formed. In some embodiments, the trigger includes a temperature decrease. In certain embodiments, the lowering of the temperature may include cooling the solidified material to a temperature of 40 ℃ to 30 ℃, 30 ℃ to 20 ℃, 20 ℃ to 10 ℃, 10 ℃ to 0 ℃, 0 ℃ to-10 ℃, 10 ℃ to-20 ℃, 20 ℃ to-30 ℃, or below-30 ℃. In some embodiments, the trigger may include an increase in temperature. In certain embodiments, the raising of the temperature may include heating the polymer cured material to a temperature of 20 ℃ to 40 ℃, 40 ℃ to 60 ℃, 60 ℃ to 80 ℃, 80 ℃ to 100 ℃, or above 100 ℃. In some embodiments, triggering includes a force exerted on the cured polymeric material. In certain embodiments, the force comprises pressing, compacting, pulling, twisting, or providing any other physical force to the material. In some embodiments, the trigger includes an electrical charge and/or an electrical field applied to the material. In some embodiments, the formation of one or more crystalline phases may be induced by more than one trigger (i.e., more than one type of trigger may promote the generation, formation, and/or growth of crystals). In some embodiments, the polymeric material comprises a plurality of crystalline phases, and at least two crystalline phases may be induced by different triggers.

In some embodiments, the polymeric materials herein comprise a crystalline phase having a discontinuous phase transition (e.g., a first order phase transition). In some cases, the polymeric material has a discontinuous phase change, in part, due to the presence of one or more crystalline domains (crystalline domains). As a non-limiting example, a solidified polymeric material comprising one or more crystalline domains may have one or more portions that melt at an elevated temperature when heated to that elevated temperature, and one or more portions that remain solid.

In some embodiments, the cured polymeric material comprises a crystalline phase of a continuous and/or discontinuous phase. The continuous phase may be a phase that can be traced from one side of the polymeric material to or connected to the other side of the material; for example, closed cell foam materials comprise foam that can be tracked throughout the sample, while closed cells (bubbles) represent the discontinuous phase of air pockets. In some embodiments, at least one crystalline phase forms a continuous phase, while 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, the at least one crystalline phase and the at least one amorphous phase are continuous throughout the material. In some embodiments, the polymeric material comprises a plurality of crystalline phases, wherein one or more of the plurality of crystalline phases has a high melting point (e.g., at least about 50 ℃, 70 ℃, or 90 ℃) and is in the discontinuous phase, and another one or more of the plurality of crystalline phases has a low melting point (e.g., at less than about 50 ℃, 70 ℃, or 90 ℃) and is in the continuous phase.

In some aspects, the polymeric material comprises 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.

In some aspects, the polymer crystals of the crystalline phase may comprise greater than about 40wt%, greater than about 50wt%, greater than about 60wt%, greater than about 70wt%, greater than about 80wt% or greater than about 90wt% of a linear polymer and/or linear oligomer, wherein such linear polymer and/or linear oligomer may comprise one or more telechelic polymers and/or telechelic oligomers, respectively, in polymerized form.

In some aspects, the polymeric materials described herein can have a crystalline phase content of 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 polymeric materials herein may comprise a weight ratio of crystalline phase to amorphous phase of about 1:99 to about 99:1.

In various aspects, the present disclosure provides a polymeric material produced from a photocurable resin comprising: an amorphous phase; and a crystalline phase comprising a polymer having stereoregular properties (tactic properties). In some aspects, the stereotactic property comprises isotactic (isotic), syndiotactic (syndiotactic), having a plurality of meso diads, having a plurality of racemic diads, having a plurality of isotactic triads (triads), having a plurality of syndiotactic triads, or having a plurality of syndiotactic triads. In some aspects, a polymeric material comprising a crystalline phase comprising a polymer having stereoregular properties has increased crystallinity compared to a comparable polymeric material comprising a comparable atactic polymer. 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 comprises a stereoregular property. 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 comprises stereoregular properties. In some aspects, a polymeric material comprising a polymer having stereoregular properties is characterized by at least one of: elongation at break greater than or equal to 5%; a storage modulus greater than or equal to 500MPa; a tensile modulus greater than or equal to 500MPa; and residual stress of greater than or equal to 0.01MPa. In some aspects, a comparable polymeric material comprising an atactic polymer comparable to a polymer having stereoregular properties is characterized by at least one of: elongation at break less than 5%; storage modulus less than 500MPa; a tensile modulus of less than 500MPa; and residual stress less than 0.01MPa. In some aspects, the polymeric material is at least partially crosslinked. In some aspects, the polymeric material is thermoset or thermoplastic. In some aspects, the polymeric material comprises a semi-crystalline segment.

In some embodiments, the cured polymer (e.g., crosslinked polymer) may be characterized by a tensile stress-strain curve that exhibits a yield point after which the specimen continues to elongate, but without (detectable) or with only a very low increase in stress. This yield point behavior may occur "near" the glass transition temperature, where the material is between glassy and rubbery, and may be characterized as having viscoelastic behavior. In some embodiments, viscoelastic behavior is observed over a temperature range of about 20 ℃ to about 40 ℃. 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 as a secant modulus at 1% strain (e.g., when there is no linear portion of the stress-strain curve). The elongation at yield is determined by the strain of the yield point. When the yield point occurs at the maximum of the stress, the ultimate tensile strength is less than the yield strength. For tensile test specimens, the strain is defined by ln (l/l ₀ ) Definition, which can be approximated as (l-l) at small strains (e.g., less than about 10%) ₀ )/l ₀ And elongation is l/l ₀ Wherein l is the gauge length after a certain deformation, and l ₀ Is the initial gauge length. The mechanical properties may depend on the temperature at which they are measured. The test temperature may be lower than the intended use temperature of the orthodontic appliance, for example 35 ℃ to 40 ℃. In some embodiments, the test temperature is 23±2 ℃.

As further provided herein, polymeric materials comprising crystalline phases (also referred to herein as crystalline domains) and amorphous phases (also referred to herein as amorphous domains) may have improved properties, such as the ability to act rapidly (e.g., vibrate rapidly and react upon application of strain due to the elastic properties of the amorphous domains), and the ability to provide a strong modulus (e.g., be hard and provide strength due to the crystalline domains). The polymer crystals disclosed herein may comprise tightly stacked and/or packed polymer chains. In some embodiments, the polymer crystals comprise long oligomers or long polymer chains stacked in an organized manner, overlapping in parallel. In some cases, the polymer crystals may be pulled from the crystalline phase, thereby producing elongation as the polymer chains of the polymer crystals are pulled (e.g., application of force may pull long polymer chains of the polymer crystals, thereby introducing disorder to the stacked chains, pulling at least a portion from its crystalline state without damaging the polymer chains). This is in contrast to fillers conventionally used to form resins of materials having a high flexural modulus, which can simply slip through an amorphous phase when a force is applied to the polymeric material, or when the filler is covalently bonded to the polymer, resulting in a reduced elongation at break of the material. Thus, the use of polymer crystals in the resulting polymeric material may provide a less brittle product that retains more of its original physical properties (i.e., is more durable) after use and retains elastic characteristics through a combination of amorphous and crystalline phases.

In some embodiments, the polymeric materials herein include a ratio (wt/wt) of crystalline to amorphous polymeric phase of 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 polymeric material comprises a ratio of crystallizable polymeric material to amorphous polymeric material (wt/wt) of 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 polymeric material comprises a ratio (wt/wt) of crystalline to amorphous polymeric phase of 1:9 to 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.

In some embodiments, the polymeric materials of the present disclosure include a ratio (vol/vol) of crystalline to amorphous polymeric phase of 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 polymeric material comprises a ratio (vol/vol) of crystalline to amorphous polymeric phase of 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 polymeric material comprises a ratio (vol/vol) of crystalline to amorphous polymeric phase of 1:9 to 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.

Properties of the Polymer Material

Polymeric materials of the present disclosure formed from polymerization of the curable resins disclosed herein may provide advantageous properties compared to conventional polymeric materials. In some cases, and as described herein, the polymeric material may include a percentage of crystallinity, which may impart increased toughness and high modulus to the polymeric material, while in some cases being a 3D printable material. In addition, the polymeric materials herein may also include one or more amorphous phases, which may provide increased durability, prevent crack formation, and prevent crack propagation. In some cases, the polymeric material may also have a low water absorption and may be solvent resistant. In some cases, the polymeric material may be characterized by one or more properties selected from elongation at break, storage modulus, tensile modulus, residual bending stress, glass transition temperature, water absorption, hardness, color, transparency, hydrophobicity, lubricity, surface texture, percent crystallinity, phase composition ratio, domain size, and domain size and morphology. Furthermore, as described herein, the polymeric materials provided herein can be used in a variety of applications, including 3D printing, to form materials with advantageous elastic and stiffness properties.

In some cases, the polymeric materials of the present disclosure may have one or more of the following characteristics and properties: (a) a tensile modulus greater than or equal to 200MPa; (B) A flexural stress and/or flexural modulus greater than or equal to 1.5MPa after 24 hours in a humid environment at 37 ℃; (C) elongation at break greater than or equal to 5%; (D) The water absorption is lower than 25wt% measured after 24 hours in a humid environment at 37 ℃; and (E) at least 30% of visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃. In some cases, the polymeric materials of the present disclosure have 2, 3, 4, or all of these features.

In some embodiments, the polymeric material is characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, when measured after 24 hours in a humid environment at 37 ℃.

In some embodiments, the ultimate tensile strength of the polymeric material after 24 hours in a humid environment at 37 ℃ is from 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MP to 40MPa, 30MPa to 45MPa, or 30MPa to 40MPa.

In some embodiments, the polymeric material is characterized by an elongation at break of greater than 10%, an elongation at break of greater than 20%, an elongation at break of greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break of between 40% to 250% after 24 hours in a humid environment at 37 ℃.

In some embodiments, the polymeric material is characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃.

In some embodiments, the polymeric material retains a flexural stress and/or flexural modulus of 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater, or 50MPa or greater after 24 hours in a humid environment at 37 ℃. In some embodiments, the polymeric material retains a flexural stress of 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater, or 50MPa or greater after 24 hours in a humid environment at 37 ℃.

In some embodiments, the polymeric material has a conversion of double bonds to single bonds of greater than 60% as compared to the photocurable resin as measured by FTIR. Further, in some cases, at least about 40%, 50%, 60%, or 70% of the visible light passes through the polymeric material after the material is stored in a humid environment at 37 ℃ for 24 hours.

In some examples, the polymeric material may have a lower amount of hydrogen bonds than conventional polymeric materials having a greater amount of hydrogen bonds, which may facilitate a reduction in water absorption. Thus, in some examples, the polymeric materials herein may comprise less than about 10wt%, less than about 9wt%, less than about 8wt%, less than about 7wt%, less than about 6wt%, less than about 5wt%, less than about 4wt%, less than about 3wt%, less than about 2wt%, less than about 1wt%, or less than about 0.5wt% water when fully saturated at the use temperature (e.g., about 20 ℃, 25 ℃, 30 ℃, or 35 ℃). In some examples, the use temperature may include a temperature of a person's mouth (e.g., about 35-40 ℃). The application temperature can be selected from-100-250deg.C, 0-90deg.C, 0-80deg.C, 0-70 deg.C, 0-60 deg.C, 0-50deg.C, 0-40 deg.C, 0-30 deg.C, 0-20 deg.C, 0-10 deg.C, 20-90 deg.C, 20-80 deg.C, 20-70 deg.C, 20-60 deg.C, 20-50 deg.C, 20-40 deg.C, 20-30 deg.C or below 0deg.C.

In some embodiments, the polymeric material produced from the photocurable compositions described herein may have a melting temperature above room temperature. In some embodiments, the polymeric material has a melting temperature that is greater than the temperature of the human mouth. As a non-limiting example, it is advantageous that each of the plurality of polymer crystals present in the polymer material may have a melting temperature above the human mouth temperature such that the polymer crystals remain solid in such a state. In some embodiments, the polymeric material has a melting temperature greater than 20 ℃, greater than 25 ℃, greater than 30 ℃, greater than 35 ℃, greater than 40 ℃, greater than 45 ℃, greater than 50 ℃, greater than 55 ℃, greater than 60 ℃, greater than 65 ℃, greater than 70 ℃, greater than 75 ℃, or greater than 80 ℃. In some embodiments, the polymeric material has a melting temperature of 20 ℃ to 250 ℃, 30 ℃ to 180 ℃, 40 ℃ to 160 ℃, or 50 ℃ to 140 ℃. In some embodiments, the polymeric material has a melting temperature greater than 60 ℃. In some embodiments, the polymeric material has a melting temperature of 80 ℃ to 110 ℃.

In various instances herein, the polymeric materials of the present disclosure may be biocompatible, bioinert, or a combination thereof. In this case, no or only a very limited amount of the monomer material that may be present in the photocurable resin will leach out of the polymeric material formed from such photocurable resin. This may be particularly important for the use of orthodontic appliances used in the intra-oral environment.

In various embodiments herein, the polymer chains of the polymeric material may form linear portions, wherein the linear chain portions of the plurality of polymer molecules are arranged to form crystals. In some cases, the polymer chains of the polymer material may form crystals, wherein different portions of the same polymer chain are arranged linearly such that the polymer chains fold upon themselves. As described elsewhere herein

In some embodiments, the polymeric materials herein comprise at least one crystalline phase and at least one amorphous phase, wherein the at least one crystalline phase, the at least one amorphous phase, or both comprise one or more telechelic polymers of the present invention. In some cases, a combination of these two types of phases or domains may produce a high modulus phase (e.g., crystalline polymeric material may provide a high modulus) and a low modulus phase (e.g., provided by the presence of amorphous polymeric material). By having these two phases, the polymeric material can have a high modulus and high elongation, as well as a high stress that remains after stress relaxation.

In various cases, the one or more amorphous phases of the polymeric material may have a glass transition temperature of at least about 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, or at least about 110 ℃. In this case, at least one of the one or more amorphous phases having a glass transition temperature of at least about 50 ℃ comprises one or more telechelic polymers of the present disclosure, such as one or more telechelic block copolymers as described herein, incorporated into its polymeric structure.

In some cases, the polymeric material may include polymer crystals attached to an amorphous polymer. As non-limiting examples, the polymer crystals may be covalently bonded, entangled, crosslinked, and/or otherwise associated with the amorphous polymer material (e.g., by hydrophobic interactions, pi stacking, or hydrogen bonding interactions).

In some embodiments, the polymeric materials herein may comprise crystalline and/or amorphous phases having smaller dimensions (e.g., less than about 1 μm). The smaller polymer phase in the polymeric material may facilitate the passage of light and provide a polymeric material that appears transparent. In contrast, larger polymer phases (e.g., those greater than about 1 μm) may scatter light, for example, when the refractive index of the polymer crystal differs from the amorphous phase (e.g., amorphous material) adjacent to the polymer crystal. In some cases, at least 40%, 50%, 60%, or 70% of the visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃.

Thus, in some cases, it may be advantageous to have a polymeric material that contains a small polymeric phase, e.g., crystalline or amorphous phase, e.g., as measured by the longest length of the phase. In some embodiments, such polymeric materials comprise an average polymeric phase size of less than 5 μm. In some embodiments, such polymeric materials comprise an average polymeric phase size of less than 1 μm. In some cases, the maximum polymer phase size of the polymeric material may 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 material has a polymer phase size of less than about 5 μm. In yet other embodiments, the polymeric material comprises an average polymeric phase size of less than about 1 μm. In some embodiments, the cured polymeric material has a maximum polymeric polymer phase size of 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 material has a polymer phase size less than about 1 μm. In yet other embodiments, the polymeric material comprises an average polymer phase size of less than about 500nm. In some embodiments, the cured polymeric material has a maximum polymer phase size of about 500nm. 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 material has a polymer phase size less than 500nm.

In some embodiments, the size of at least one or more polymer phases (e.g., crystalline and amorphous phases) of the polymeric material may be controlled. Non-limiting examples of ways in which the size of the polymer phase may be controlled include: rapidly cooling the solidified polymeric material, annealing the solidified polymeric material at an elevated temperature (i.e., above room temperature), annealing the solidified polymeric material at a temperature below room temperature, controlling the rate of polymerization, controlling the intensity of light during the solidification step using light, controlling and/or adjusting the polymerization temperature, exposing the solidified polymeric material to acoustic vibrations, and/or controlling the presence and amount of impurities, particularly for crystalline phases, adding crystallization inducing chemicals or particles (e.g., crystallization seeds).

In some embodiments, the refractive index of one or more crystalline phases and/or one or more amorphous phases of the polymeric materials herein may be controlled. A decrease in the index of refraction difference between the different phases (e.g., a decrease in the index of refraction difference between the crystalline polymer and the amorphous polymer) may increase the transparency of the cured polymeric material, thereby providing a transparent or near 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 polymer phase and an adjacent phase (e.g., crystalline phase and adjacent amorphous phase) may be less than about 0.1, less than about 0.01, or less than about 0.001.

In some cases, the polymeric materials described herein can form a polymeric film. Such polymer films may have a thickness of at least about 50 μm, 100 μm, 250 μm, 500 μm, 1mm, 2mm and no greater than 3 mm.

Polymeric materials in medical devices

The invention also provides devices comprising the polymeric materials of the invention. As described herein, such polymeric materials may comprise one or more telechelic polymers of the present invention incorporated into their polymeric structure, such as one or more telechelic block copolymers described herein. In various cases, the instrument may be a medical instrument. The medical device may be an orthodontic appliance. The orthodontic appliance may be a dental appliance, a dental expander, or a dental spacer.

Methods of making and using telechelic polymers

The present invention provides a method of using the telechelic polymer, a photocurable resin comprising the telechelic polymer, and a polymeric material formed from the photocurable resin, and a method of making the same. Telechelic polymers of the present invention, such as those comprising monomers according to formulas (I) and (II) in polymerized form, as well as telechelic block copolymers, such as one according to formula (III) herein, may be components useful as materials for many different industries, such as transportation (e.g., aircraft, trains, ships, automobiles, etc.), hobbies, prototyping, medical, artistic and design, microfluidics, molds, and the like. In various embodiments, the telechelic polymers of the present disclosure may be used in the production of medical devices. In various embodiments herein, such medical devices include orthodontic appliances.

Synthesis of monomers and telechelic polymers

The present disclosure provides synthetic methods for producing monomers (e.g., terminal monomers) described herein. In some embodiments, monomers according to formula (I) of the present disclosure can be prepared as shown in exemplary scheme 1 below:

wherein,

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl, or halogen; and

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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) A heteroalkyl group. In some cases, R ¹ Is H or methyl. In some cases, R ² Is C _1-6 Alkyl, C _1-6 A heteroalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

In some embodiments, any such method can comprise isolating (e.g., terminal) the monomer in a chemical yield of at least about 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or at least about 95%, and at least about 90%, 95%, or 99% pure.

Those skilled in the art will appreciate that substituents (e.g., R ¹ 、R ² Etc.) may be changed before, during, or after the preparation of the phenyl acrylate backbone and may be suitably adjusted under exemplary conditions (e.g., temperature, solvent, etc.). In addition, one skilled in the art will recognize that protecting groups may be necessary to prepare certain compounds, and will be aware of those conditions that are compatible with the protecting group selected.

In some embodiments, provided herein are methods for synthesizing telechelic polymers. In some cases, a method of synthesizing a telechelic block copolymer, comprising coupling a telechelic polymer (a) with a second telechelic polymer (B), thereby producing a telechelic block copolymer, wherein the telechelic block copolymer comprises photopolymerisable end groups at its ends, and wherein the telechelic block copolymer has a number average molecular weight of up to about 50 kDa. Telechelic polymers composed of a single monomer species a or B may be synthesized using a variety of polymerization techniques, such as any known controlled living polymerization method, such as Atom Transfer Radical Polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), anionic polymerization.

The first telechelic polymer comprised of a single monomer species a may be coupled with the second telechelic polymer comprised of a single monomer species B to produce a telechelic block copolymer that may be used as a component in a photocurable resin. Such coupling methods may include condensation and substitution reactions, diels-alder reactions, and photodimerization reactions to couple preformed polymer blocks.

The methods provided herein for producing the polymeric materials of the present disclosure may include using telechelic polymers as the sole polymeric component in the photocurable resin, or as a polymeric component in addition to various other polymerizable compounds present in such photocurable resins. As described herein, the method of producing a polymeric material contemplates the use of only one telechelic polymer or a plurality of different telechelic polymers. Any one or more of such telechelic polymers may be a telechelic block copolymer as described herein. Such telechelic block copolymers may comprise blocks of 2, 3, 4, 5 or more monomer species, wherein such monomer blocks are arranged in a particular configuration within the polymer. Any such monomer blocks may also vary in size, for example, in the number of monomers coupled within one block. For example, a telechelic block copolymer as used herein may comprise 2, 3, 4, 5, or more blocks of monomer species, wherein each monomer block may comprise or consist of 5, 10, 15, 20, 25, 50, 75, 100, or more identical monomers coupled linearly to each other to form a monomer block.

In some embodiments, telechelic polymers of the present disclosure (e.g., di (meth) acryl-capped poly (isobornyl acrylate) (4)) can be modified as shown in example scheme 2 below using monomer (1) of formula (I) according to the present disclosure and a terminal group to produce a telechelic polymer capable of further polymerization (e.g., photopolymerization) and comprising a terminal monomer comprising a reactive moiety (e.g., photoreactive moiety):

Method for forming polymer material

The present disclosure provides a method of forming a polymeric material, the method comprising: providing a photocurable resin of the present invention comprising one or more telechelic polymers of the present invention; exposing the photocurable resin to a light source; the photocurable resin is cured to form a polymeric material. In some cases, the photocurable resins herein may optionally comprise one or more components selected from telechelic oligomers, polymerizable monomers (e.g., reactive diluents), polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, colorants, surface modifying agents (surface modifiers), and mixtures thereof to obtain an optionally crosslinked polymer, and thus the methods herein may further comprise the step of mixing the curable composition, optionally after heating. As described herein, such methods of forming polymeric materials may further include inducing the production of one or more polymeric phases by polymerization. Thus, in some embodiments, the polymeric materials of the present invention may comprise one or more polymeric phases. In some cases, at least one of the one or more polymer phases may comprise an amorphous polymer material. In some cases, at least one of the one or more polymer phases generated during photocurable may comprise a crystalline polymer material. In this case, the crystalline polymeric material may have a melting point of at least about 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least about 110 ℃. In some cases, at least one of the one or more polymer phases may have a glass transition temperature (T) of at least about 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least about 110 ° _g ). In some cases, at least one of the one or more polymer phases may comprise a crystalline polymer material and may have a melting point of at least about 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least about 110 ℃, or at least about 50 ℃,60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least about 110 ℃ (T) _g ) Or a combination thereof. In some aspects, the glass transition temperature (T) of at least about 50 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g ) May comprise a telechelic polymer of the polymeric forms of the present disclosure, such as a telechelic block copolymer. As described herein, the photopolymerizable composition present in the photocurable composition can alter the degree of phase separation in the polymeric material formed during polymerization, as well as the number, size, and/or physicochemical properties of such phases. For example, the block configuration of the telechelic block polymer used as part of the photocurable resin may alter intramolecular and intermolecular interactions within the polymer chain or between different polymer chains, respectively. In some cases, the design of a particular copolymer structure may be used to control the relative orientation and arrangement of polymer chains within the polymeric material, thereby controlling phase separation and mechanical properties of the resulting polymeric material downstream. Furthermore, the chemical structure and molecular dimensions of the backbone and particularly the monomer pendant groups can be influenced and rationally designed to control (e.g., by steric effects) the polymer chain alignment and interactions, thereby controlling the mechanical properties of the phase separated and photocurable polymer material, such as tensile modulus, flexural stress, or elongation at break.

In some embodiments, the photocurable includes a single curing step. In some embodiments, the photocurable includes multiple curing steps. In yet another embodiment, the photocurable includes at least one curing step that exposes the curable resin to light. Exposure of the curable resin to light may initiate and/or promote photopolymerization. In some cases, a photoinitiator may 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, the cured polymeric material is formed from a photocurable resin using at least one step that includes exposure to a light source, wherein the light source includes UV light, visible light, and/or IR light. In some embodiments, the light source comprises a wavelength of 10nm to 200nm, 200nm to 350nm, 350nm to 450nm, 450nm to 550nm, 550nm to 650nm, 650nm to 750nm, 750nm to 850nm, 850nm to 1000nm, or 1000nm to 1500 nm.

The methods provided herein can be used to produce polymeric materials characterized by one or more of the following properties as further described herein: (i) a tensile modulus greater than or equal to 200MPa; (ii) A flexural stress and/or flexural modulus greater than or equal to 1.5MPa after 24 hours in a humid environment at 37 ℃; (iii) an elongation at break of greater than or equal to 5%. In various cases, such methods may further include fabricating the medical device from a polymeric material. In various cases, the medical device produced is an orthodontic appliance. Such orthodontic appliances may be dental appliances, dental dilators or dental spacers. Such fabrication may include additive manufacturing.

Thus, in some embodiments, the methods provided herein may be part of a high Wen Guangke-based photopolymerization method, wherein the curable composition, such as those comprising the telechelic block copolymers described herein, may further comprise at least one photopolymerization initiator that is cleaved upon irradiation with light of the appropriate wavelength to be absorbed, which results in a cleavage product, wherein at least one is capable of initiating polymerization of the curable composition, preferably as part of an additive manufacturing method, more preferably a 3D printing process. Thus, the photoinitiator should be compatible with at least one polymerizable species and a reactive diluent (i.e., the polymerizable monomers of the present invention). As part of the high temperature photopolymerization process, some embodiments of such methods may include a heating step that heats the curable formulation containing the polymerizable monomer of the present invention as a reactive diluent to a predetermined elevated process temperature of 50 ℃ to 120 ℃, e.g., 90 ℃ to 120 ℃, followed by irradiation to initiate polymerization to produce an optionally crosslinked polymer.

In certain aspects, a solid or high viscosity resin formulation comprising a photocurable composition and at least one photoinitiator is heated to a predetermined elevated process temperature and subsequently irradiated with light of a suitable wavelength to be absorbed by the photoinitiator, thereby polymerizing and/or crosslinking the curable composition to obtain the crosslinked polymer or polymeric material. In some aspects, the elevated process temperature is in the range of 50 ℃ to 120 ℃. In certain aspects, the elevated process temperature is in the range of 90 ℃ to 120 ℃. In some aspects, the photopolymerization process is a direct or additive manufacturing process. In certain aspects, the photopolymerization process is a 3D printing process.

In further embodiments, the methods herein may include polymerizing a curable composition comprising at least one multivalent monomer and polymerizing to obtain a crosslinked polymer comprising as repeating units a moiety derived from the polymerizable monomers of the present invention. In order to obtain a crosslinked polymer that may be particularly suitable as an orthodontic appliance, the at least one polymerizable substance used in the method according to the invention may be selected according to several thermo-mechanical properties of the resulting polymer. First, at least one, but preferably more than one, multivalent polymerizable species may be included. Second, the amounts of polymerizable material and reactive diluent (i.e., polymerizable monomers of the present invention) can be well balanced. Third, the polymerizable monomers of the present disclosure used as reactive diluents can be selected to contribute to the thermo-mechanical properties of the polymer.

In some embodiments, the crosslinked polymer may be characterized by a tensile stress-strain curve that exhibits a yield point after which the specimen continues to elongate, but without (detectable) or with only a very low increase in stress. This yield point behavior may occur "near" the glass transition temperature, where the material is between glassy and rubbery, and may be characterized as having viscoelastic behavior. In some embodiments, viscoelastic behavior is observed over a temperature range of about 20 ℃ to about 40 ℃. 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 as a secant modulus at 1% strain (e.g., when there is no linear portion of the stress-strain curve). The elongation at yield is determined by the strain of the yield point. When the yield point occurs at the maximum of the stress, the ultimate tensile strength is less than the yield strength. For tensile test specimens, the strain is defined by ln (l/l ₀ ) Definition, which can be approximated as (l-l) at small strains (e.g., less than about 10%) ₀ )/l ₀ Elongation atIs l/l ₀ Wherein l is the gauge length after a certain deformation, and l ₀ Is the initial gauge length. The mechanical properties may depend on the temperature at which they are measured. The test temperature may be lower than the intended use temperature of the orthodontic appliance, for example 35 ℃ to 40 ℃. In some embodiments, the test temperature is 23±2 ℃.

When a suitable formulation is exposed to radiation (e.g., UV or visible light) of sufficient power and wavelength to initiate polymerization, the various components (e.g., polymers and monomers) present in the photocurable resin may photopolymerize. The wavelength and/or power of the radiation that can be used to initiate polymerization can depend on the photoinitiator used. As used herein, "light" generally includes any wavelength and power capable of initiating polymerization. Some wavelengths of light include Ultraviolet (UV) or visible light. The UV light source includes UVA (wavelength about 400 nanometers (nm) to about 320 nm), UVB (about 320nm to about 290 nm), or UVC (about 290nm to about 100 nm). Any suitable source may be used, including a laser source. The source may be broadband or narrowband or a combination thereof. The light source may provide continuous light or pulsed light during the process. The length of time the system is exposed to ultraviolet light and the intensity of the ultraviolet light can be varied to determine the desired reaction conditions.

Additive manufacturing, as used herein, includes a variety of techniques by which three-dimensional objects can be manufactured directly from digital models by additive processes. In some aspects, successive layers of material are deposited and "cured in place". Various techniques for additive manufacturing are known in the art, including Selective Laser Sintering (SLS), fused Deposition Modeling (FDM), and jetting or extrusion. In many embodiments, selective laser sintering involves using a laser beam to selectively melt and fuse a layer of powder material according to a desired cross-sectional shape in order to build an object geometry. In many embodiments, fused deposition modeling involves fusing and selectively depositing filaments of thermoplastic polymer in a layer-by-layer fashion to form an object. In yet another example, 3D printing may be used to manufacture the appliances herein. In many embodiments, 3D printing involves jetting or extruding one or more materials onto a build surface to form a continuous layer of object geometry. In some embodiments, the polymerizable monomers described herein can be used in inkjet or coating applications.

In some cases, the photopolymer may be manufactured by a "slot" process in which light is used to selectively cure a slot or reservoir of photopolymer. Each layer of photopolymer may be selectively exposed in a single exposure or by scanning a light beam across the layer. Specific techniques include Stereolithography (SLA), digital Light Processing (DLP), and two-photon induced photopolymerization (TPIP).

The direct fabrication process may enable continuous build of the object geometry by continuous movement of the build platform (e.g., along the vertical or Z direction) during the irradiation stage such that the depth of hardening of the irradiated photopolymer is controlled by the speed of movement. Thus, a continuous polymerization of the material on the build surface can be achieved. Such methods are described in U.S. Pat. No.7,892,474, the disclosure of which is incorporated herein by reference in its entirety. In yet another example, a continuous direct fabrication method utilizes a "solar lithography" method in which a focused radiation is utilized to cure a liquid photopolymer while continuously rotating and raising a build platform. Thus, the geometry of the object can be continuously built along the spiral build path. Such methods are described in U.S. patent publication No. 2014/0265034, the disclosure of which is incorporated herein by reference in its entirety. Continuous liquid interface production of 3D objects is also reported (j. Tuneston et al, science,2015,347 (6228), pp 1349-1352), the entire contents of which are incorporated herein by reference for the description of the process. Another example of a continuous direct manufacturing process may involve extruding a composite material composed of a curable liquid material surrounding a solid wire. The composite material may 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.

As used herein, "high temperature lithography" may refer to any lithography-based photopolymerization process involving heating of a photopolymerizable material. The heating may reduce the viscosity of the photopolymerizable material prior to and/or during curing. Non-limiting examples of high temperature lithographic processes include those described in WO 2015/075094, WO 2016/078838 and WO 2018/03022. In some embodiments, the high Wen Guangke can involve applying heat to the material to reach a temperature between 50-120 ℃, such as 90-120 ℃, 100-120 ℃, 105-115 ℃, 108-110 ℃, and the like. The material may be heated to a temperature above 120 ℃. Note that other ranges may be used without departing from the scope and spirit of the inventive concepts described herein.

Manufacture and use of orthodontic appliances

Provided herein are methods of manufacturing medical devices, such as orthodontic appliances (e.g., dental appliances, dental dilators, or dental spacers), using telechelic polymers, curable resins, and compositions comprising such polymers, and polymeric materials produced from such resins and compositions.

Thus, in some embodiments, the methods herein further comprise the step of using an additive manufacturing apparatus to manufacture the device or object, wherein the additive manufacturing apparatus facilitates curing. In some embodiments, curing of the polymerizable resin produces a cured polymeric material. In certain embodiments, an additive manufacturing apparatus is used to cure a polymerizable resin to produce a cured polymeric material. In some embodiments, the method further comprises the step of cleaning the cured polymeric material. In certain embodiments, the cleaning of the cured polymeric material includes washing and/or rinsing the cured polymeric material with a solvent, which may remove uncured resin and undesirable impurities from the cured polymeric material. In some embodiments, the polymerizable resins herein may be curable and have a melting point of <100 ℃ so as to be liquid so as to be processable at temperatures typically employed in the currently available additive manufacturing techniques described herein.

Since in some cases the polymerizable monomers of the present invention may be part of a photocurable resin, copolymerization occurs during polymerization according to the methods of the present invention, the result may be an optionally crosslinked polymer comprising portions of one or more polymerizable monomers as repeating units. In some cases, such a polymer is a crosslinked polymer that is generally suitable and useful for applications in orthodontic appliances.

VI orthodontic appliance

The photopolymerisable telechelic polymers (e.g. block copolymers) according to the invention, such as those comprising monomers according to formulae (I) and (II) in polymerized form, and telechelic block copolymers, such as those according to formula (III), may be used as part of a photocurable resin and in some cases may produce polymeric materials with advantageous thermo-mechanical properties for use in medical devices, such as orthodontic appliances, for example for moving one or more teeth. Accordingly, provided herein are medical devices comprising the polymeric materials or polymeric films of the present disclosure. In various cases, the medical device is an orthodontic appliance. Such orthodontic appliances may include dental appliances, dental dilators, and dental spacers. In various cases, such orthodontic appliances may be used to move one or more teeth of a human subject. In various embodiments, the medical devices (e.g., orthodontic appliances) herein may be produced by additive manufacturing. In some aspects, manufacturing a medical device (e.g., an orthodontic appliance) from a polymeric material includes printing with a 3D printer. In some aspects, fabricating the device from the polymeric material includes digital light projection. In some aspects, the device is made from a polymeric material that includes a height Wen Guangke.

As described herein, the present disclosure also provides a method of repositioning teeth of a patient, the method comprising: (i) Generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving the teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement; (ii) Producing a dental appliance comprising a polymeric material as described herein, e.g., a polymeric material comprising one or more telechelic polymers of the invention; and using the dental appliance to track at least one tooth of the patient toward the intermediate tooth arrangement or the final tooth arrangement. Such dental appliances may be produced using processes that include 3D printing, as further described herein. The method of repositioning the patient's teeth may further include tracking progress of the patient's teeth along the treatment path after the dental appliance is applied to the patient, the tracking including comparing the current arrangement of the patient's teeth to the planned arrangement of the patient's teeth. In this case, more than 60% of the patient's teeth may be in compliance with the treatment plan after 2 weeks of treatment. In some cases, the dental appliance has a retained repositioning force on at least one tooth of the patient after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the repositioning force originally provided to the at least one tooth of the patient.

As used herein, the terms "stiffness" and "stiffness" are used interchangeably, as are the corresponding terms "stiffness" and "stiffness".

As used herein, "plurality of teeth" includes two or more teeth.

In many embodiments, the one or more posterior teeth comprise one or more of molar teeth, premolars, or canine teeth, and the one or more anterior teeth comprise one or more of a middle incisor, a side incisor, a cuspid, a first bicuspid, or a second bicuspid.

In some embodiments, the compositions and methods described herein can be used to couple one or more sets of teeth to each other. The one or more sets of teeth may include a first set of one or more anterior teeth and a second set of one or more posterior teeth. The first set of teeth may be coupled to the second set of teeth by the polymeric shell appliance disclosed herein.

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

The embodiments disclosed herein are well suited for combination with one or more known commercially available tooth movement assemblies (e.g., attachments and polymeric shell appliances). In many embodiments, the appliance and the one or more attachments are configured to move one or more teeth along a tooth motion vector comprising six degrees of freedom, wherein three degrees of freedom are rotational and three degrees of freedom are translational.

The present disclosure provides orthodontic systems and related methods for designing and providing improved or more efficient tooth movement systems for causing desired tooth movement and/or repositioning of teeth in a desired arrangement.

Although references are made to appliances comprising polymeric shell appliances, the embodiments disclosed herein are well suited for use with many tooth-receiving appliances, such as appliances that do not have one or more polymers or shells. The appliance may be manufactured using one or more of a variety of materials such as, for example, metal, glass, reinforcing fibers, carbon fibers, composites, reinforced composites, aluminum, biological materials, and combinations thereof. In some cases, the reinforced composite may include a polymer matrix reinforced with, for example, ceramic or metal particles. The appliance may be shaped in a variety of ways, such as, for example, thermoforming or direct manufacturing as described herein. Alternatively or in combination, the appliance may be manufactured by machining, for example by computer numerical control machining, from a block of material. Preferably, the device is manufactured using a polymerizable monomer according to the present disclosure, for example using the monomer as a reactive diluent for the curable resin.

Turning now to the drawings, in which like numerals denote like elements in different drawings, FIG. 1A illustrates an exemplary tooth repositioning appliance or appliance 100 that a patient may wear in order to effect incremental repositioning of individual teeth 102 in the mandible. The appliance may include a shell (e.g., a continuous polymer shell or a segmented shell) having a tooth receiving cavity that receives and resiliently repositions the teeth. The appliance or part thereof may be indirectly manufactured using a physical model of the tooth. For example, a physical model of a tooth and a sheet of suitable polymer material layer may be used to form an appliance (e.g., a polymer appliance). In some embodiments, the physical appliance is fabricated directly from a digital model of the appliance, for example using rapid prototyping techniques. The appliance may be mounted on all, or not all, of the teeth of the upper or lower jaw. The appliance may be specifically designed to conform to the patient's teeth (e.g., the topography of the tooth receiving cavity matches the topography of the patient's teeth), and may be based on the use of a stampA die, scan, etc. Alternatively, the appliance may be a universal appliance configured to receive teeth, but it need not be shaped to match the topography of the patient's teeth. In some cases, only the particular tooth held by the appliance is repositioned by the appliance, while other teeth may provide a base or anchor area for securing the appliance in place when the appliance applies a force to the one or more teeth repositioned by the target. In some cases, at some point during treatment, some, most, or even all of the teeth may be repositioned. The moving teeth may also act as bases or anchors for the fixture when the fixture is worn by the patient. Typically, no wires or other means for securing the appliance in place over the teeth are provided. However, in some instances, it may be desirable or necessary to provide a separate attachment or other anchoring element 104 on the tooth 102 and a corresponding socket or aperture 106 in the appliance 100 so that the appliance can apply a selected force on the tooth. Exemplary instruments are described in various patents and patent applications assigned to Align Technology, inc (including Those used in systems), including, for example, U.S. Pat. nos. 6,450,807 and 5,975,893, and on the company's website, which is accessible on the world wide web (see, for example, the URL "invisalign. Com"). Examples of dental mounting attachments suitable for use with orthodontic appliances are also described in patents and patent applications assigned to AlignTechnology, inc, including, for example, U.S. patent nos. 6,309,215 and 6,830,450.

Fig. 1B illustrates a tooth repositioning system 110 that includes a plurality of appliances 112, 114, 116. Any of the appliances described herein may be designed and/or provided as part of a set of multiple appliances for use in a tooth repositioning system. Each appliance may be configured such that the tooth receiving cavity has a geometry corresponding to the intermediate or final tooth arrangement intended for the appliance. The patient's teeth may be gradually repositioned from the initial tooth arrangement to the target tooth arrangement by placing a series of incremental position adjustment appliances over the patient's teeth. For example, the tooth repositioning system 110 may include a first appliance 112 corresponding to an initial tooth arrangement, one or more intermediate appliances 114 corresponding to one or more intermediate arrangements, and a final appliance 116 corresponding to a target arrangement. The target tooth arrangement may be a planned final tooth arrangement selected for the patient's teeth at the end of all planned orthodontic treatments. Alternatively, the target arrangement may be one of some intermediate arrangements of the patient's teeth during orthodontic treatment, which may include a variety of different treatment scenarios including, but not limited to, sites where surgery is recommended, sites where adjacent face stripping (IPR) is appropriate, sites where progress checking is planned, sites where anchoring positions are optimal, sites where palate expansion is required, sites where dental restorations are involved (e.g., inlays, onlays, crowns, bridges, implants, veneers, etc.). Thus, it will be appreciated that the target tooth arrangement may be any planned resulting arrangement of the patient's teeth after one or more incremental repositioning phases. Likewise, the initial tooth arrangement may be any initial arrangement of the patient's teeth followed by one or more incremental repositioning stages.

Fig. 1C illustrates an orthodontic treatment method 150 using a plurality of appliances, according to an embodiment. Method 150 may be implemented using any of the appliances or sets of appliances described herein. In step 160, a first orthodontic appliance is applied to the teeth of the patient to reposition the teeth from the first tooth arrangement to the second tooth arrangement. In step 170, a second orthodontic appliance is applied to the teeth of the patient to reposition the teeth from the second tooth arrangement to the third tooth arrangement. Method 150 may be repeated as necessary using any suitable number and combination of successive appliances to incrementally reposition the patient's teeth from the initial arrangement to the target arrangement. The appliances may be produced all at the same stage, in groups or batches (e.g. at the beginning of a stage of treatment), or one at a time, the patient may wear each appliance until the pressure of each appliance against the teeth is no longer felt, or until the maximum tooth movement for a given stage of compression is reached. A plurality of different appliances (e.g., a set of appliances) may be designed and even manufactured before any of the plurality of appliances is worn by a patient. After wearing the appliances for an appropriate period of time, the patient may replace the current appliance with the next appliance in the series until no more appliances remain. The appliance is not typically fixed to the teeth and the patient can place and replace the appliance (e.g., a patient-removable appliance) at any time during the treatment. The last appliance or several appliances in the series may have a geometry or geometries selected to overcorrect the tooth arrangement. For example, the geometry of one or more appliances may (if fully realized) move individual teeth beyond the tooth arrangement selected as "final". Such overcorrection may be desirable in order to counteract potential recurrence after the repositioning method is terminated (e.g., to allow individual teeth to move back to their pre-corrected positions). Overcorrection may also help to increase the speed of correction (e.g., appliances having geometries beyond the desired intermediate or final position may move individual teeth toward that position at a greater rate). In this case, the use of the appliance may be terminated before the teeth reach the prescribed position of the appliance. In addition, to compensate for any inaccuracy or limitation of the appliance, an over correction may be deliberately made.

The various embodiments of orthodontic appliances presented herein may be manufactured in a variety of ways. In some embodiments, orthodontic appliances (or portions thereof) herein may 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 portion thereof) without using a physical template (e.g., a mold, mask, etc.) to define the geometry of the object. Additive manufacturing techniques may be categorized as follows: (1) Barrel photopolymerization (e.g., stereolithography), in which an object is composed of a barrel of liquid photopolymer resin layer by layer; (2) Material jetting, wherein the material is jetted onto a build platform using a continuous or Drop On Demand (DOD) method; (3) Adhesive jetting, in which alternating layers of build material (e.g., powder-based material) and bond material (e.g., liquid adhesive) are deposited by a printhead; (4) Fused Deposition Modeling (FDM), wherein a material is stretched through a nozzle, heated, and deposited layer by layer; (5) Powder bed melting including, but not limited to, direct Metal Laser Sintering (DMLS), electron Beam Melting (EBM), selective thermal sintering (SHS), selective Laser Melting (SLM), and Selective Laser Sintering (SLS); (6) Sheet lamination, including but not limited to layered solid fabrication (LOM) and ultrasonic additive fabrication (UAM); and (7) directed energy deposition including, but not limited to, laser near net shape (laser engineering net shaping), directed light fabrication, direct metal deposition, and 3D laser cladding. For example, stereolithography may be used to directly fabricate one or more of the devices herein. In some embodiments, stereolithography involves selectively polymerizing a photosensitive resin (e.g., a photopolymer) according to a desired cross-sectional shape using light (e.g., ultraviolet light). By sequentially aggregating a plurality of object cross sections, the object geometry can be built up in a layer-by-layer manner. As another example, the devices herein may be directly manufactured using selective laser sintering. In some embodiments, selective laser sintering involves selectively melting and fusing layers of powder material according to a desired cross-sectional shape using a laser beam in order to establish an object geometry. As yet another example, the appliance herein may be directly manufactured by fused deposition modeling. In some embodiments, fused deposition modeling involves fusing and selectively depositing filaments of thermoplastic polymer in a layer-by-layer fashion to form an object. In yet another example, material jetting may 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 a continuous layer of object geometry.

Alternatively or in combination, some embodiments of the appliances (or portions thereof) herein may be produced using indirect manufacturing techniques, for example by thermoforming on a male or female mold. Indirect fabrication of orthodontic appliances may involve producing a male or female mold of a patient's dentition in a target arrangement (e.g., by rapid prototyping, milling, etc.), and thermoforming one or more sheets of material over a mold to create an appliance shell.

In some embodiments, the direct fabrication methods provided herein build object geometry in a layer-by-layer fashion, forming continuous layers in discrete build steps. Alternatively or in combination, a direct fabrication method may be used that allows for continuous build of the object geometry, referred to herein as "continuous direct fabrication". Various types of continuous direct manufacturing processes may be used. As an example, in some embodiments, the devices herein are fabricated using "continuous liquid phase printing" in which an object is continuously built from a reservoir of photo-polymerizable resin 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 photopolymerization inhibitors (e.g., oxygen) into the dead zone to form a polymerization gradient. Continuous liquid phase-to-phase printing can achieve manufacturing speeds of about 25 to about 100 times faster than other direct manufacturing methods, and speeds of about 1000 times faster by incorporating a cooling system. Continuous liquid phase 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 entirety.

As another example, a continuous direct fabrication method may enable continuous build of an object geometry by continuous movement of a build platform (e.g., along a vertical or Z-direction) during a radiation phase such that the depth of hardening of the irradiated photopolymer is controlled by the speed of movement. Thus, a continuous polymerization of the material on the build surface can be achieved. Such a method is described in U.S. Pat. No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety.

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

In yet another example, a continuous direct fabrication method utilizes a "spiral lithography" method in which focused radiation is used to cure a liquid photopolymer while continuously rotating and raising a build platform. Thus, the object geometry can be continuously built along the spiral 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.

The direct fabrication methods provided herein are compatible with a variety of materials, including but not limited to one or more of the following: polyesters, copolyesters, polycarbonates, thermoplastic polyurethanes, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic, cyclic block copolymers, polyetheretherketones, polyamides, polyethylene terephthalates, polybutylene terephthalates, polyetherimides, polyethersulfones, polytrimethylene terephthalates, styrene Block Copolymers (SBC), silicone rubbers, elastomeric alloys, thermoplastic elastomers (TPE), thermoplastic vulcanizate (TPV) elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers, thermoplastic polyamide elastomers, thermosets, or combinations thereof. The material for direct fabrication may be provided in uncured form (e.g., liquid, resin, powder, etc.) and may be cured (e.g., by photopolymerization, photo-curing, gas curing, laser curing, cross-linking, etc.) to form the orthodontic appliance or a portion thereof. The properties of the material before curing may be different from the properties of the material after curing. Once cured, the materials herein may exhibit sufficient strength, rigidity, durability, biocompatibility, etc., for use in orthodontic appliances. The post-cure characteristics of the materials used may be selected according to the desired characteristics of the corresponding portion of the appliance.

In some embodiments, the relatively rigid portion of the orthodontic appliance may be formed by direct fabrication using one or more of the following materials: polyesters, copolyesters, polycarbonates, thermoplastic polyurethanes, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic acid, cyclic block copolymers, polyetheretherketones, polyamides, polyethylene terephthalates, polybutylene terephthalates, polyetherimides, polyethersulfones and/or polytrimethylene terephthalates.

In some embodiments, the relatively resilient portion of the orthodontic appliance may be formed by direct manufacture using one or more of the following materials: styrene Block Copolymers (SBC), silicone rubber, elastomer alloys, thermoplastic elastomers (TPE), thermoplastic vulcanizate (TPV) elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers and/or thermoplastic polyamide elastomers.

The machine parameters may include curing parameters. For Digital Light Processing (DLP) based curing systems, the curing parameters may include power, curing time, and/or grayscale of the complete image. For laser-based curing systems, the curing parameters may include power, speed, beam size, beam shape, and/or power distribution of the beam. For printing systems, curing parameters may include material drop size, viscosity, and/or curing power. These machine parameters may be monitored and adjusted periodically (e.g., some parameters per 1-x layer and some parameters after each build) as part of the process control of the manufacturing machine. Process control may be achieved by including sensors on the machine that measure power and other beam parameters per layer or per few seconds and automatically adjust them through a feedback loop. For DLP machines, depending on the stability of the system, the grey scale may be measured and calibrated before, during and/or at the end of each build and/or at predetermined time intervals (e.g., once per n builds, once per hour, once per day, once per week, etc.). In addition, material properties and/or photo features may be provided to the manufacturing machine, which may be used by the machine process control module to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variations in material properties. By implementing process control over the manufacturing machine, reduced variation in fixture accuracy and residual stress can be achieved.

Optionally, the direct fabrication methods described herein allow for fabrication of devices comprising multiple materials, referred to herein as "multi-material direct fabrication". In some embodiments, the multi-material direct fabrication method involves simultaneously forming objects from multiple materials in a single fabrication step. For example, a multi-tip extrusion device (multi-tip extrusion apparatus) can be used to selectively dispense multiple types of materials from different material supplies in order to manufacture objects from multiple different materials. Such a method is described in U.S. patent No. 6,749,414, the entire disclosure of which is incorporated herein by reference. Alternatively or in combination, the multi-material direct fabrication method may involve forming an object from multiple materials in multiple sequential fabrication steps. For example, a first portion of an object may be formed from a first material according to any direct manufacturing method herein, then a second portion of an object may be formed from a second material according to the methods herein, and so on until the entirety of the object has been formed.

Direct manufacturing may provide various advantages over other manufacturing methods. For example, direct manufacturing allows orthodontic appliances to be produced without using any mold or template to shape the appliance, thereby reducing the number of manufacturing steps involved and improving the resolution and accuracy of the final appliance geometry, as compared to indirect manufacturing. Furthermore, direct manufacturing allows for precise control of the three-dimensional geometry of the appliance, such as the appliance thickness. The complex structure and/or ancillary components may be integrally formed as one piece with the appliance housing in a single manufacturing step rather than added to the housing in a separate manufacturing step. In some embodiments, the devices used to produce the device geometries that are difficult to create using alternative manufacturing techniques are manufactured directly, such as devices with very small or fine features, complex geometries, undercuts, adjoining structures, shells with variable thickness, and/or internal structures (e.g., to increase strength by reducing weight and material usage). For example, in some embodiments, the direct fabrication methods herein allow for the fabrication of orthodontic appliances having feature sizes of 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.

The direct fabrication techniques described herein may be used to produce devices 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 for the production of orthodontic appliances having a strength that varies by no more than about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% in all directions. Furthermore, the direct fabrication methods herein may be used to produce orthodontic appliances at a faster rate than other fabrication techniques. In some embodiments, the direct manufacturing methods herein allow orthodontic appliances to be produced in a time interval of less than or equal to about 1 hour, about 30 minutes, about 25 minutes, about 20 minutes, about 15 minutes, about 10 minutes, about 5 minutes, about 4 minutes, about 3 minutes, about 2 minutes, about 1 minute, or about 30 seconds. Such manufacturing speeds allow for rapid "beside" production of custom appliances, for example during routine reservations or inspections.

In some embodiments, the direct manufacturing methods described herein enable process control over various machine parameters of a direct manufacturing system or apparatus to ensure that the resulting appliance is manufactured with high precision. Such precision can help ensure that the required force system is accurately transferred to the tooth, effectively causing tooth movement. Process control may be implemented to account for process variability caused by a variety of sources, such as material properties, machine parameters, environmental variables, and/or aftertreatment parameters.

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

The machine parameters may include curing parameters. For Digital Light Processing (DLP) based curing systems, the curing parameters may include power, curing time, and/or grayscale of the complete image. For laser-based curing systems, the curing parameters may include power, speed, beam size, beam shape, and/or power distribution of the beam. For printing systems, curing parameters may include material titer, viscosity, and/or curing power. These machine parameters may be monitored and adjusted periodically (e.g., some parameters per 1-x layer and some parameters after each build) as part of process control on the manufacturing machine. Process control may be achieved by including sensors on the machine that measure power and other beam parameters per layer or per few seconds and automatically adjust them through a feedback loop. For DLP machines, the grayscale can be measured and calibrated at the end of each build. In addition, material properties and/or photo features may be provided to the manufacturing machine, which may be used by the machine process control module to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variations in material properties. By implementing process control over the manufacturing machine, reduced variation in fixture accuracy and residual stress can be achieved.

In many embodiments, environmental variables (e.g., temperature, humidity, sunlight, or exposure to other energy/curing sources) are kept within narrow limits that reduce variability in appliance thickness and/or other properties. Optionally, machine parameters may be adjusted to compensate for environmental variables.

In many embodiments, the post-treatment of the appliance includes washing, post-curing, and/or support removal processes. Related post-treatment parameters may include purity of the detergent, wash pressure and/or temperature, wash time, post-cure energy and/or time, and/or consistency of the support removal process. These parameters may be measured and adjusted as part of a process control scheme. Furthermore, the physical properties of the appliance may be changed by modifying the post-processing parameters. Adjusting the aftertreatment machine parameters may provide another method to compensate for variability in material properties and/or machine properties.

The configuration of orthodontic appliances herein may be determined according to a treatment plan for a patient, for example, a treatment plan involving the sequential application of multiple appliances to incrementally reposition teeth. Computer-based treatment planning and/or appliance manufacturing methods may be used to facilitate the design and manufacture of appliances. For example, one or more of the appliance assemblies described herein may be digitally designed and manufactured by means of computer-controlled manufacturing equipment (e.g., computer Numerical Control (CNC) milling, computer controlled rapid prototyping, such as 3D printing, etc.). The computer-based methods presented herein may improve the accuracy, flexibility, and convenience of appliance manufacturing.

Fig. 2 illustrates a method 200 for designing an orthodontic appliance produced by direct manufacturing, according to an embodiment. The method 200 may be applied to any of the embodiments of orthodontic appliances described herein. Some or all of the steps of method 200 may be performed by any suitable data processing system or device, such as one or more processors configured with suitable instructions.

In step 210, a path of movement is determined for moving one or more teeth from an initial arrangement to a target arrangement. The initial alignment may be determined by molding or scanning of the patient's teeth or oral tissue, for example, using wax biting, direct contact scanning, x-ray imaging, tomographic imaging, ultrasound imaging, and other techniques, to obtain information about the position and structure of the teeth, jaw, gums, and other orthodontic related tissue. From the obtained data, a digital data set may be derived that represents an initial (e.g., pre-processed) arrangement of the patient's teeth and other tissue. Optionally, the initial digital data set is processed to segment the tissue elements from one another. For example, a data structure may be generated that digitally represents a single crown. Advantageously, a digital model of the entire tooth can be generated, including the measured or extrapolated hidden surface and root structure, as well as surrounding bone and soft tissue.

The target arrangement of teeth (e.g., desired and expected end result of orthodontic treatment) may be received from a clinician in the form of a prescription, may be calculated according to basic orthodontic principles, and/or may be computationally inferred from a clinical prescription. By way of illustration of the desired final position of the teeth and the digital representation of the teeth themselves, the final position and surface geometry of each tooth can be specified to form a complete model of the tooth arrangement at the end of the intended treatment.

Each tooth has an initial position and a target position, and a path of movement is defined for each tooth's movement. In some embodiments, the movement path is configured to move the tooth in the fastest manner with the least number of round trips to move the tooth from its initial position to its desired target position. The tooth path may optionally be segmented, and the segments may be calculated such that the motion of each tooth within one segment remains within the threshold limits of linear and rotational translation. In this way, the endpoints of each path segment may constitute a clinically viable repositioning, and the collection of segment endpoints may constitute a sequence of clinically viable tooth positions such that moving from one point to the next in the sequence does not result in tooth collision.

In step 220, a force system that produces movement of one or more teeth along a motion path is determined. The force system may include one or more forces and/or one or more torques. Different force systems may result in different types of tooth movement (e.g., tilting, translation, rotation, extrusion, intrusion, root movement, etc. biomechanical principles, modeling techniques, force calculation/measurement techniques, etc., including orthodontic knowledge and methods, may be used to determine the appropriate force system to apply to the tooth to accomplish the tooth movement. Sources may be considered in determining the force system to be applied, including literature, force systems determined through experimental or virtual modeling, computer-based modeling, clinical experience, minimizing unwanted forces, and the like.

The determination of the force system may include constraints on the allowable force, such as allowable direction and magnitude, and the desired movement caused by the applied force. For example, in the manufacture of a palatal expander, different patients may require different movement strategies. For example, the amount of force required to separate the palate may depend on the age of the patient, as very young patients may not have a fully developed bone suture. Thus, in adolescent patients and other patients without a fully occluded palate suture, palate expansion can be accomplished with a lower force level. Slower palate movements also contribute to bone growth to fill the expanded bone slot. For other patients, a faster expansion may be required, which may be achieved by applying a greater force. These requirements can be incorporated as desired to select the construction and materials of the appliance; for example, by selecting a palate expander that can apply a large force to break the palate suture and/or cause rapid expansion of the palate. Subsequent appliance stages may be designed to apply different amounts of force, such as first applying a greater force to fracture the bone slot and then applying a lesser force to keep the bone slot separate or gradually expand the palate and/or dental arch.

The determination of the force system may also include modeling of patient facial structures, such as skeletal structures of the jaw and palate. Scan data (e.g., X-ray data or 3D optical scan data) of the palate and dental arch, for example, can be used to determine parameters of the skeletal and muscular system of the patient's mouth, thereby determining a force sufficient to provide a desired expansion of the palate and/or dental arch. In some embodiments, the thickness and/or density of the bone slots in the palate can be measured or entered by a treatment professional. In other embodiments, the treatment professional may select an appropriate treatment based on the physiological characteristics of the patient. For example, the characteristics of the palate can also be assessed based on factors such as the age of the patient, e.g., young adolescent patients often require lower force to dilate the suture than older patients because the suture has not yet developed sufficiently.

In step 230, a dental arch or palate expander design of an orthodontic appliance configured to produce a force system is determined. The treatment or force modeling environment may be used to determine the design, appliance geometry, material composition, and/or performance of the dental arch or palate expander. The simulation environment may include, for example, a computer modeling system, a biomechanical system or device, and the like. Optionally, a digital model of the appliance and/or tooth may be produced, such as a finite element model. The finite element model may be created using various vendor-supplied computer program applications. For creating the solid geometry model, computer Aided Engineering (CAE) or Computer Aided Design (CAD) programs, such as those provided by Autodesk, inc. Of san-fei, california A software product. To create and model finite elementsThe analysis may be performed using program products from a number of suppliers including the finite element analysis software package of ANSYS, inc. Of kangsburg, pennsylvania, and the SIMULIA (Abaqus) software product of Dassault sysmes of waltham, ma.

Optionally, one or more dental arch or palate expander designs may be selected for testing or force modeling. As described above, the desired tooth movement can be identified, as well as the force system needed or desired to cause the desired tooth movement. Using the simulated environment, the candidate dental arch or palate expander designs can be analyzed or modeled to determine the actual force system generated using the candidate appliance. Optionally, one or more modifications may be made to the candidate instrument, and the force modeling may be further analyzed as described, for example, in order to iteratively determine an instrument design that yields a desired force system.

In step 240, a manufacturing specification for an orthodontic appliance incorporating the design of the dental arch or palate expander is generated. The instructions may be configured to control the manufacturing system or apparatus to produce an orthodontic appliance having a specified arch or palate expander design. In some embodiments, according to various methods provided herein, the instructions are configured to manufacture the orthodontic appliance using direct fabrication (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct fabrication, multi-material direct fabrication, etc.). In alternative embodiments, the instructions may be configured to indirectly fabricate the appliance, such as by thermoforming.

The method 200 may include the additional steps of: 1) Intraoral scanning of the patient's upper arch and palate to generate three-dimensional data of the palate and upper arch; 2) The three-dimensional shape of the implement is contoured to provide the clearance and tooth engaging structure as described herein.

While the above steps illustrate a method 200 of designing an orthodontic appliance according to some embodiments, one of ordinary skill in the art will recognize some variations based on the teachings described herein. Some steps may include sub-steps. Some of these steps may be repeated as desired. One or more steps of method 200 may be performed using any suitable manufacturing system or apparatus (e.g., embodiments described herein). Some steps may be optional and the order of the steps may be changed as desired.

Fig. 3 illustrates a method 300 for digitally planning orthodontic treatment and/or designing or manufacturing appliances, according to an embodiment. The method 300 may be applied to any of the therapeutic procedures described herein and may be performed by any suitable data processing system.

In step 310, a digital representation of a patient's teeth is received. The digital representation may include surface topography data within the patient's mouth (including teeth, gingival tissue, etc.). The surface topography data may be generated by directly scanning the intraoral groove, a physical model of the intraoral groove (male or female), or an impression of the intraoral groove using a suitable scanning device (e.g., a handheld scanner, a desktop scanner, etc.).

In step 320, one or more treatment phases are generated based on the digital representation of the tooth. The treatment phase may be an incremental repositioning phase of an orthodontic treatment program designed to move one or more teeth of a patient from an initial tooth arrangement to a target arrangement. For example, the treatment phase may be generated by determining an initial tooth arrangement indicated by the digital representation, determining a target tooth arrangement, and determining a path of movement of one or more teeth in the initial arrangement required to achieve the target tooth arrangement. The movement path may be optimized based on minimizing the total distance moved, preventing interdental collisions, avoiding more difficult tooth movement, or any other suitable criteria.

In step 330, at least one orthodontic appliance is manufactured based on the generated treatment phase. For example, a set of appliances may be manufactured, each appliance being shaped according to a tooth arrangement specified for one treatment session, such that the appliances may be worn sequentially by a patient to incrementally reposition teeth from an initial arrangement to a target arrangement. The appliance set may include one or more orthodontic appliances described herein. Manufacturing of the appliance may involve creating a digital model of the appliance for use as input to a computer controlled manufacturing system. The appliance may be formed using direct manufacturing methods, indirect manufacturing methods, or a combination thereof, as desired.

In some instances, various arrangements or phasing of treatment phases may not be necessary for the design and/or manufacture of the appliance. As shown in dashed lines in fig. 3, the design and/or manufacture of an orthodontic appliance, and possibly a particular orthodontic treatment, may include using a representation of a patient's teeth (e.g., a digital representation of the received patient's teeth 310) followed by the design and/or manufacture of an orthodontic appliance based on the representation of the patient's teeth in the arrangement represented by the received representation.

Rail-mounted therapy

Also provided herein are methods of repositioning a patient's teeth using one or more orthodontic appliances comprising the polymeric materials described herein, e.g., as described in fig. 4 and in some cases referred to as "track-following treatment. In some cases, provided herein is a method of repositioning teeth of a patient, the method comprising: generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement; producing an orthodontic appliance comprising a polymeric material of the present disclosure; and using the orthodontic appliance to orbit at least one tooth of the patient toward an intermediate tooth arrangement or a final tooth arrangement. In various cases, the production of orthodontic appliances includes additive manufacturing.

The method of repositioning the patient's teeth may further include tracking 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 arrangement of the patient's teeth to the planned arrangement of the patient's teeth. In this case, greater than about 40%, 50%, 60%, or 70% of the patient's teeth may conform to the treatment plan after 1, 2, 3, 4, or more weeks of treatment. In some cases, more than 60% of the patient's teeth are in compliance with the treatment plan after 2 weeks of treatment. In some cases, the orthodontic appliance used in such a method has a retained repositioning force on at least one tooth of the patient after 2 days that is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the repositioning force originally provided to the at least one tooth of the patient.

Referring to fig. 4, a method 400 according to the present disclosure is shown. Various aspects of the method are discussed in further detail below. The process includes receiving information about an orthodontic condition of a patient (402), generating a case assessment (404), and generating a treatment plan for repositioning teeth of the patient (406). Briefly, patient/treatment information includes data comprising an initial arrangement of patient's teeth, including obtaining an impression or scan of the patient's teeth prior to initiating treatment, and may also include identification of one or more treatment targets selected by the practitioner and/or patient. A case estimate may be generated (404) to estimate the complexity or difficulty of moving a particular patient's teeth, generally or specifically corresponding to the identified treatment objective, and may also include practitioner experience and/or comfort of delivering the desired orthodontic treatment. However, in some cases, the assessment may include simply identifying particular treatment options of interest to the patient and/or practitioner (e.g., appointment planning, progress tracking, etc.). The information and/or corresponding treatment plan includes identifying a desired final or target arrangement of the patient's teeth, and a plurality of planned successive or intermediate tooth arrangements for moving the teeth along the treatment path from the initial arrangement to the selected final or target arrangement.

The method also includes generating a customized therapy guideline (408). The treatment plan may include a plurality of treatment phases and a set of customized treatment guidelines corresponding to one phase of the treatment plan is generated. The guidelines may include detailed information about the time and/or content (e.g., specific tasks) to be completed at a given treatment stage, and may guide practitioners in sufficient detail during the treatment stage, including less experienced practitioners or practitioners relatively unfamiliar with a particular orthodontic treatment procedure. The guideline is said to be customized because it is designed to correspond specifically to the treatment plan and is provided with respect to treatment information and/or well-defined activities in the generated treatment plan. The practitioner is then provided with customized treatment guidelines to help guide the practitioner how to provide a given treatment session. As described above, the appliance may be generated based on the planned schedule and may be provided to the practitioner and ultimately administered to the patient (410). The devices, e.g., 2, 3, 4, 5, 6, 7, 8, 9 or more devices, may be provided and/or applied in groups or batches, but are not limited to any particular application regimen. The appliance may be provided to the practitioner concurrently with a given set of guidelines, or the appliance and guidelines may be provided separately.

After treatment is initiated according to the plan, and after the appliance is applied to the patient, treatment progress tracking is performed, for example by tooth matching, to assess the current and actual arrangement of the patient's teeth as compared to the planned arrangement (412). If the patient's teeth are determined to be "in-orbit" and progress in accordance with the treatment plan, then the treatment will be planned and the treatment will proceed to the next treatment phase (414). If the patient's teeth substantially reach the final arrangement of the initial plan, then treatment will enter the final treatment phase (414). If it is determined that the patient's teeth are in track according to the treatment plan, but the final arrangement has not been reached, the next set of appliances may be administered to the patient.

Table 1 below gives the threshold difference between the planned and actual positions of the teeth, which is selected as an indication that the patient's teeth have progressed on track. If the patient's tooth progress reaches or is within a threshold, the progress is considered to be in track. If the patient's tooth progress exceeds a threshold, the progress is considered off-track.

Table 1 exemplary on-track therapy

By comparing the current position of the patient's teeth to their expected or planned positions, and by confirming that the teeth are within the parameter variance ranges disclosed in table 1, it is determined whether the patient's teeth are in track. If the patient's tooth development is determined to be in-orbit, the treatment may progress according to an existing or initial treatment plan. For example, according to a treatment plan, a patient determined to be on-track with progress may administer one or more subsequent appliances, e.g., a next set of appliances. The treatment may progress to the final stage and/or may reach a point in the treatment plan at which bite matching is repeated to determine whether the patient's teeth are evolving as planned or whether the teeth are off-track.

In some embodiments, as further disclosed herein, the present disclosure provides methods of treating a patient using a 3D printed orthodontic appliance. In certain embodiments, a method of repositioning a patient's teeth (or, in some embodiments, a single tooth) includes: generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement; producing a 3D printed orthodontic appliance comprising a polymeric material of the present disclosure; and using the orthodontic appliance to orbit at least one tooth of the patient toward an intermediate tooth arrangement or a final tooth arrangement. In a preferred embodiment, the method further comprises moving the patient's teeth in a track toward the intermediate arrangement or the final tooth arrangement. In some embodiments, the photocurable resins further disclosed herein are used to produce 3D printed orthodontic appliances. The on-track performance may be determined by, for example, table 1 above.

In some embodiments, the method further comprises tracking the progression of the patient's teeth along the treatment path after the orthodontic appliance is applied. In some embodiments, tracking includes comparing the current arrangement of the patient's teeth to a planned arrangement of teeth. As one non-limiting example, after a period of time (e.g., two weeks) has elapsed after the first application of the orthodontic appliance, the current arrangement of the patient's teeth (i.e., two weeks of treatment) may be compared to the arrangement of the teeth of the treatment plan. In some embodiments, progress may also be tracked by comparing the current arrangement of the patient's teeth to the initial configuration of the patient's teeth. For example, the time period may 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 period of time may be from at least 3 days to at most 4 weeks, from at least 3 days to at most 3 weeks, from at least 3 days to at most 2 weeks, from at least 4 days to at most 4 weeks, from at least 4 days to at most 3 weeks, or from at least 4 days to at most 2 weeks. In certain embodiments, the time period may be restarted after the application of a new orthodontic appliance.

In some embodiments, after a period of use of the orthodontic appliance further disclosed herein, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of the patient's teeth conform to the treatment plan. In some 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.

In some embodiments of the methods disclosed above, the 3D printed orthodontic appliance has a retained repositioning force (i.e., a repositioning force after the orthodontic appliance has been applied to or worn by a patient for a period of time), and after the period of time, the retained repositioning force of the orthodontic appliance 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 of the at least one tooth originally provided to the patient (i.e., at the time of the original Shi Yingzheng orthodontic 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 more than 4 weeks.

In a preferred embodiment, the orthodontic appliance disclosed herein may move at least one tooth of a patient in a track. The track-wise movement is described further herein, as seen in table 1. In some embodiments, the orthodontic appliances disclosed herein may be used to effect orbital movement of at least one tooth of a patient toward an intermediate tooth arrangement. In some embodiments, the orthodontic appliances disclosed herein may be used to effect orbital movement of at least one tooth of a patient to a final tooth arrangement.

In some embodiments, the orthodontic appliance includes a first bending stress prior to the at least one tooth of the patient being orbitally moved toward the intermediate arrangement or the final tooth arrangement using the orthodontic appliance; and the orthodontic appliance includes a second bending stress after effecting the orbital movement of the at least one tooth of the patient toward the intermediate arrangement or the final tooth arrangement.

As provided herein, the disclosed methods may use orthodontic appliances as further disclosed herein. The orthodontic appliance may be directly manufactured using, for example, the resins disclosed herein. In certain embodiments, directly fabricating includes crosslinking the resin.

The appliances formed from the resins disclosed herein provide improved durability, strength, and flexibility, which in turn increases the rate of on-orbit progress of the treatment plan (rate of on-track progression). In some embodiments, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of patients treated with the orthodontic appliances (e.g., appliances) disclosed herein are classified as in-orbit 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 the teeth movements of a patient treated with an orthodontic appliance (e.g., appliance) 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 the teeth movements categorized as in-orbit movements.

Experimental method

In some embodiments, stress relaxation (stress relaxation) of a material or instrument can be measured by monitoring time-dependent stress resulting from stable strain. The degree of stress relaxation may also depend on temperature, relative humidity, and other applicable conditions (e.g., the presence of water). In an embodiment, the stress relaxation test conditions are at a temperature of 37±2 ℃ at 100% relative humidity or at a temperature of 37±2 ℃ in water.

The dynamic viscosity of the fluid indicates its resistance to shear flow. The SI unit of dynamic viscosity is Poisson's leaf (Pa.s). Dynamic viscosity is typically given in centipoise, where 1 centipoise (cP) equals 1mpa·s. Kinematic viscosity is the ratio of dynamic viscosity to fluid density; SI unit is m ² And/s. Devices for measuring viscosity include viscometers and rheometers.

Additive manufacturing or 3D printing methods for generating the appliances herein (e.g., orthodontic appliances) may be performed using a thermal lithographic device prototype from Cubicure (vienna, austria), which may be configured substantially as shown in fig. 5. In this case, the photocurable composition (e.g., resin) according to the present disclosure may be filled into a transparent material barrel of the device shown in fig. 5, which barrel may be heated to 90-110 ℃. The build platform can also be heated to 90-110 ℃ and lowered to establish full contact with the upper surface of the curable composition. By irradiating the composition with 375nm UV radiation using a diode laser from the Soliton, which may have an output power of 70mW, which may be controlled to track a predetermined prototype design and alternately raise the build platform, the composition may be cured layer by a photopolymerization process according to the present disclosure, resulting in a polymeric material according to the present disclosure.

VII Experimental methods

Unless otherwise indicated, all chemicals were purchased from commercial sources and used without further purification.

Recording on BRUKER AC-E-200FT-NMR spectrometer or BRUKER Avance DRX-400FT-NMR spectrometer ¹ HNMR and ¹³ CNMR spectroscopy. Chemical shifts are in ppm (s: singlet, d: doublet, t: triplet, q: quadruple, m: multiplet). The solvent used was deuterated chloroform (CDCl) ₃ 99.5% deuteration) and deuterated DMSO (d) ₆ DMSO,99.8% deuterated).

In some embodiments, stress relaxation of a material or device may be measured by monitoring time-dependent stress caused by a stable strain. The degree of stress relaxation may also depend on temperature, relative humidity, and other applicable conditions (e.g., the presence of water). In an embodiment, the test conditions for stress relaxation are a temperature of 37±2 ℃ at 100% relative humidity or a temperature of 37±2 ℃ in water.

The dynamic viscosity of the fluid indicates its resistance to shear flow. The SI unit of dynamic viscosity is Poisson's leaf (Pa.s). Dynamic viscosity is typically given in centipoise, where 1 centipoise (cP) equals 1mpa·s. Kinematic viscosity is the ratio of dynamic viscosity to fluid density; SI unit is m ² And/s. Devices for measuring viscosity include viscometers and rheometers. For example, a MCR301 rheometer from An Dongpa can be used for rheometry in rotary mode (PP-25, 50s-1, 50-115 ℃, 3 ℃ C./min).

Determining the moisture content at full saturation at the use temperature may include exposing the polymeric material to 100% humidity at the use temperature (e.g., 40 ℃) for a period of 24 hours, and then determining the moisture content by methods known in the art, such as by weight.

In some embodiments, the presence of crystalline and amorphous phases provides advantageous material properties for the polymeric material. For example, the property values of the cured polymeric material may be determined by using the following method:

flexural modulus, residual flexural stress and stress relaxation characteristics can be evaluated by three-point bending using a TA Instruments RSA-G2 instrument according to astm d 790; for example, stress relaxation can be measured at 30 ℃ and immersed in water and reported as residual load after 24 hours, expressed as a percentage (%) of initial load and/or in MPa;

storage modulus can be measured at 37 ℃ and reported in MPa;

t of cured polymeric material can be evaluated using Dynamic Mechanical Analysis (DMA) _g And provided herein as tan delta peaks;

tensile modulus, tensile strength, elongation at yield and elongation at break can be assessed according to ISO 527-25B; tensile strength at yield, elongation at break, tensile strength and young's modulus can be evaluated according to ASTM D1708;

molecular weight may be measured by size exclusion chromatography or gel permeation chromatography.

Examples

The following examples are given to illustrate various embodiments of the invention and are not meant to limit the disclosure in any way. The present examples, as well as the methods described herein, are presently representative of certain embodiments, are exemplary, and are not intended as limitations on the scope of the invention. Variations therein and other uses within the spirit of the invention as defined by the scope of the claims will occur to those skilled in the art.

Example 1

Preparation of Poly (isobornyl acrylate) [2, HO-PIBOA-Br ]

This example describes the synthesis of polymer 2, which is a precursor to the photopolymerisable polymers described herein.

To a 100mL schlenk flask equipped with a magnetic stirring bar were added isobornyl acrylate (20.0 mL,94.9 mmol), ethyl acetate (20 mL), and Pentamethyldiethylenetriamine (PMDETA) (294 uL,1.42 mmol). The mixture was sparged with nitrogen for 1 hour. Copper (I) bromide (CuBr) (136 mg,0.949 mmol) was then added to the flask, and the mixture was heated at 75℃with stirring. A solution of 2-bromoisobutyric acid in 2-hydroxyethyl (275 uL,1.90 mmol) in ethyl acetate (1 mL) was injected into the flask to start the reaction. After 1 hour at 75 ℃, the reaction was quenched by cooling the flask in an ice water bath, opening the flask to atmosphere and adding dichloromethane. The mixture was passed through neutral alumina using methylene chloride to remove copper catalyst and precipitated in methanol to remove unreacted monomers to give poly (isobornyl acrylate) having terminal hydroxyl and bromo end groups, HO-PIBOA-Br (2).

Example 2

Preparation of Poly (isobornyl acrylate) [3, HO-PIBOA-OH ] having terminal hydroxyl groups

The previously synthesized polymer HO-PIBOA-Br (2) was stirred with TEA (6 equivalents per chain) and triethylamine (6 equivalents) in dimethylformamide/chloroform at 45℃for 3 days to give dihydroxy-terminated HO-PIBOA-OH (3).

An alternative route to HO-PIBOA-OH (3) involves first reacting HO-PIBOA-Br (2) with acrylic acid and 1, 8-diazabicyclo undec-7-ene to replace the bromine with an acrylate group; or coupling the atom transfer group HO-PIBOA-Br in the presence of styrene, thereby facilitating faster coupling. For the latter method, 1:1:2:4:1-5 [ HO-PIBOA-Br ] was used] ₀ :[CuBr] ₀ :-[PMDETA] ₀ :[Cu ⁰ ] ₀ [ styrene ]] ₀ Stirring in toluene at 70℃for several hours to achieve high (. Gtoreq.0.90) coupling efficiency.

Example 3

Preparation of diacrylamide-and di (meth) acryloyl-terminated poly (isobornyl acrylate) -photopolymerizable telechelic polymers (4, 5)

HO-PIBOA-OH (3) is then reacted with (meth) acrylic anhydride and 4-dimethylaminopyridine to give di (meth) acryl-terminated poly (isobornyl acrylate) (4), and acrylic anhydride is reacted with 4-dimethylaminopyridine to give telechelic polymer diacryl-terminated poly (isobornyl acrylate) (5).

Example 4

Forming polymeric materials from photocurable resins

This example describes the preparation of a photocurable resin comprising one or more telechelic polymers and/or telechelic block copolymers described herein, and the formation of polymeric materials from the photocurable resin. Exemplary material properties of the polymeric material are also described.

The photocurable resin is prepared by combining about 70wt% of the telechelic block copolymer (e.g., compound 5) with 30wt% of a reactive diluent comprising photoreactive end groups. The photoreactive end groups of the polymerizable component of the resin are acrylate or methacrylate moieties, which may contain various substituents described herein.

Example 5

Direct preparation of polymeric materials with photocurable resins

The polymeric material was prepared directly from the photocurable resin described in example 4.

The printing element was obtained using an Asiga Digital Light Projection (DLP) printer. The photocurable resin from example 4 was introduced into a DLP printer and a cured polymeric material of a specific shape was obtained. The photocurable low viscosity resin is compatible with the use of conventional 3D printers and the cured polymeric material has good mechanical properties.

Example 6

Treatment using orthodontic appliances

This embodiment describes the use of a direct 3D printed orthodontic appliance to move a patient's teeth according to a treatment plan. This embodiment also describes features that an orthodontic appliance may have after use, in contrast to features prior to use.

Patients who need or want therapeutic treatment to rearrange at least one tooth should evaluate their tooth arrangement. An orthodontic treatment plan is generated for the patient. Orthodontic treatment plans include a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial arrangement (e.g., an initially estimated arrangement) to a final arrangement. The treatment plan includes the use of orthodontic appliances that are manufactured using the photocurable resins and methods further disclosed herein to provide orthodontic appliances with low levels of hydrogen bonding units. In some embodiments, a plurality of orthodontic appliances are used, each of which may be made using the photocurable resins and methods further disclosed herein that comprise one or more polymerizable monomers.

Orthodontic appliances are provided and applied repeatedly to the patient's teeth to move the teeth through each intermediate tooth arrangement toward the final arrangement. The tooth movement of the patient is tracked. The actual tooth arrangement of the patient is compared to the planned intermediate arrangement. If it is determined that the patient's teeth are on track according to the treatment plan, but the final arrangement has not been reached, the next set of appliances may be administered to the patient. Table 1 above provides threshold differences in the planned and actual positions of the teeth, which are selected as an indication that the patient's teeth have progressed as planned. If the patient's tooth progress reaches or is within a threshold, the progress is considered as planned. Advantageously, use of the appliance disclosed herein increases the likelihood of planned tooth movement.

For example, an assessment and determination of whether the treatment is on-track may be made 1 week (7 days) after the first application of the orthodontic appliance. Additional parameters related to assessing the durability of the orthodontic appliance may also be performed after the application period. For example, the relative repositioning force (as compared to the force initially provided by the instrument), the residual bending stress, the relative bending modulus, and the relative elongation at break may be determined.

Furthermore, the terms and expressions which have been employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that while the present invention has been specifically disclosed by some embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the invention, and it will be apparent to those skilled in the art that the invention may be practiced with numerous variations of the instruments, instrument assemblies, method steps set forth in the present specification. As will be apparent to those of skill in the art, the methods and apparatus useful in the present methods may include a wide variety of optional components and processing elements and steps.

Claims

1. A telechelic polymer comprising a monomer, wherein the monomer comprises a reactive functional group and wherein two or more of the following conditions are satisfied:

(i) The monomer has a vapor pressure of at most 8000Pa at 60 ℃ in its monomeric state;

(ii) After heating at 90 ℃ for 2 hours, the mass loss rate of the monomer in its monomer state at 90 ℃ per hour is less than 0.25%;

(iii) The telechelic polymer has a molecular weight of no greater than 50kDa; and

(iv) The reactive functional group comprises a photopolymerizable moiety.

2. The telechelic polymer of claim 1, wherein three or more of conditions (i), (ii), (iii), and (iv) are satisfied.

3. The telechelic polymer of claim 1, wherein all conditions (i), (ii), (iii), and (iv) are satisfied.

4. A telechelic polymer, according to any of claims 1-3, wherein said monomer in its monomeric state has a vapor pressure of 2Pa to 10Pa at 60 ℃.

5. The telechelic polymer of any of claims 1-4, wherein the monomer in its monomeric state has a vapor pressure of 2Pa to 5Pa at 60 ℃.

6. The telechelic polymer of any of claims 1-5, wherein said monomer has a mass loss of 0.05% to 0.225% per hour at 90 ℃ in its monomer state after heating at 90 ℃ for 2 hours.

7. The telechelic polymer of any of claims 1-6, wherein said monomer has a mass loss rate of 0.025% to 0.125% at 90 ℃ in its monomer state after heating at 90 ℃ for 2 hours.

8. The telechelic polymer of any of claims 1-7, wherein the molecular weight of the telechelic polymer is from 5kDa to 40kDa.

9. The telechelic polymer of claim 8, wherein the molecular weight of the telechelic polymer is from 5kDa to 30kDa.

10. The telechelic polymer of claim 8, wherein the molecular weight of the telechelic polymer is from 5kDa to 20kDa.

11. The telechelic polymer of claim 8, wherein the molecular weight of the telechelic polymer is from 5kDa to 15kDa.

12. The telechelic polymer of claim 1, wherein the photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety.

13. The telechelic polymer of any of claims 1-12, wherein the photopolymerizable moiety comprises an acrylate or methacrylate moiety.

14. The telechelic polymer of claim 1, wherein the photopolymerizable moiety is capable of photo-induced diels-alder click reaction or photo-dimerization reaction.

15. The telechelic polymer of claim 1, wherein said monomer has a melting point of at least 25 ℃ in its monomeric state.

16. The telechelic polymer of any of claims 1-15, wherein the monomer is a compound according to formula (I):

wherein,

R ¹ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

17. A photocurable resin comprising the telechelic polymer of any of claims 1-16.

18. The photocurable resin of claim 17, wherein the photocurable resin is capable of polymerization-induced phase separation in one or more lateral directions during photocuring.

19. The photocurable resin of claim 18 wherein the photocurable resin, when polymerized, comprises one or more polymer phases.

20. According to claim 19The photocurable resin wherein at least one of the one or more polymer phases has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG _g )。

21. The photocurable resin of claim 20 wherein the polymerized form of the telechelic polymer is a component of said at least one polymer phase, T of said polymer phase _g At least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

22. The photocurable resin of any one of claims 18-21, wherein at least one of the one or more polymeric phases comprises a crystalline polymeric material.

23. The photocurable resin of claim 22, wherein the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

24. The photocurable resin of any one of claims 17-20, further comprising a second telechelic polymer comprising a second monomer, wherein the second monomer comprises a second reactive functional group and wherein one or more of the following conditions are satisfied:

(v) The second monomer has a vapor pressure of at most 8000Pa at 60 ℃ in its monomeric state;

(vi) After heating at 90 ℃ for 2 hours, the second monomer has a mass loss rate of less than 0.25% per hour at 90 ℃ in its monomer state;

(vii) The molecular weight of the second telechelic polymer is no greater than 50kDa; and

(viii) The second reactive functional group comprises a second photopolymerizable moiety.

25. The photocurable resin according to claim 24, which satisfies four or more of the conditions (i), (ii), (iii), (iv), (v), (vi), (vii) and (viii).

26. The photocurable resin according to any one of claims 24-25, which satisfies five or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii).

27. The photocurable resin according to any one of claims 24-26, which satisfies six or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii).

28. The photocurable resin according to any one of claims 24-27, which satisfies seven or more of conditions (i), (ii), (iii), (iv), (v), (vi), (vii), and (viii).

29. The photocurable resin according to any one of claims 24-28, which satisfies all of conditions (i), (ii), (iii), (iv), (v), (vi), (vii) and (viii).

30. The photocurable resin of claim 24, wherein the second monomer has a vapor pressure of 2Pa to 10Pa at 60 ℃ in its monomeric state.

31. The photocurable resin of claim 24, wherein the second monomer has a vapor pressure of 2Pa to 5Pa at 60 ℃ in its monomeric state.

32. The photocurable resin of claim 24, wherein the second monomer has a mass loss rate of 0.05% to 0.225% per hour at 90 ℃ in its monomer state after heating at 90 ℃ for 2 hours.

33. The photocurable resin of claim 24, wherein the second monomer has a mass loss rate of 0.025% to 0.125% at 90 ℃ in its monomer state after heating at 90 ℃ for 2 hours.

34. The photocurable resin of claim 24, wherein the second telechelic polymer has a molecular weight of 5kDa to 40kDa.

35. The photocurable resin of claim 34, wherein the second telechelic polymer has a molecular weight of 5kDa to 30kDa.

36. The photocurable resin of claim 34, wherein the second telechelic polymer has a molecular weight of 5kDa to 20kDa.

37. The photocurable resin of claim 34, wherein the second telechelic polymer has a molecular weight of 5kDa to 15kDa.

38. The photocurable resin of any one of claims 24-37, wherein the second photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silylene, alkynyl, alkenyl, vinyl ether, maleimide, fumarate, maleate, itaconate, or styryl moiety.

39. The photocurable resin of any one of claims 24-38, wherein the second photopolymerizable moiety comprises an acrylate or methacrylate moiety.

40. The photocurable resin of claim 24, wherein the second photopolymerizable moiety is capable of a photo-induced diels-alder click reaction or a photo-dimerization reaction.

41. The photocurable resin of claim 24 wherein the second monomer has a melting point of at least 25 ℃ in its monomer state.

42. The photocurable resin of any one of claims 24-41, wherein the second monomer is different from the monomer, and wherein the second monomer is a compound according to formula (II):

wherein,

R ³ is H, substituted or unsubstituted C _1-3 Alkyl or halogen; and

43. The photocurable resin of any one of claims 24-42, wherein the first telechelic polymer and the second telechelic polymer are part of a telechelic block copolymer.

44. The photocurable resin of claim 43, wherein said telechelic block copolymer has a block configuration of AB, wherein "A" is said telechelic polymer and "B" is said second telechelic polymer.

45. The photocurable resin of any one of claims 43-44, wherein the telechelic block copolymer is a compound according to formula (III):

wherein,

R ⁶ and R is ⁷ Independently for takingSubstituted 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 aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ring (C _3-8 ) Alkyl, or substituted or unsubstituted ring (C) _3-8 ) Heteroalkyl, and R ⁶ ≠R ⁷ The method comprises the steps of carrying out a first treatment on the surface of the And

n and m are independently positive integers from 1 to 100.

46. The photocurable resin of claim 43, wherein said telechelic block copolymer has the configuration of ABA or BAB, wherein "a" is said telechelic polymer and "B" is said second telechelic polymer.

47. The photocurable resin of claim 43, wherein said telechelic block copolymer further comprises a macroinitiator.

48. The photocurable resin of claim 47, wherein said macroinitiator is polycaprolactone, polytetrahydrofuran, hydrogenated polyethylene, hydroxyl-terminated polystyrene, polyester diol, polycarbonate diol, or polystyrene dihalide.

49. The photocurable resin of any one of claims 43-42, wherein the telechelic block copolymer has a polydispersity index (PDI) of from about 0.5 to about 3, or from about 1 to about 2.

50. The photocurable resin of any one of claims 17-49, wherein the photocurable resin is capable of 3D printing at a temperature of at least 25 ℃.

51. The photocurable resin of claim 50, wherein the photocurable resin is capable of 3D printing at a temperature of at least 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃, or 100 ℃.

52. The photocurable resin of any one of claims 17-51, further comprising a reactive diluent.

53. The photocurable resin of any one of claims 17-52, which has a viscosity of 30cP to 50,000cP at printing temperature.

54. The photocurable resin of claim 53, wherein the print temperature is from 20 ℃ to 150 ℃.

55. The photocurable resin of any one of claims 17-54, comprising less than 20wt% hydrogen bond units.

56. The photocurable resin of any one of claims 17-55, further comprising a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof.

57. The photocurable resin of any one of claims 17-56, wherein the photocurable resin comprises 0.5-99.5wt%, 1-99wt%, 10-95wt%, 20-90wt%, 25-60wt%, or 35-50wt% of a telechelic polymer, a second telechelic polymer, a telechelic block copolymer, or a combination thereof.

58. A polymeric material formed from the photocurable resin of any one of claims 17-57.

59. The polymeric material of claim 58, wherein the polymeric material has one or more of the following characteristics:

(A) A tensile modulus greater than or equal to 200MPa;

(B) A flexural stress and/or flexural modulus greater than or equal to 1.5MPa after 24 hours in a humid environment at 37 ℃;

(C) Elongation at break greater than or equal to 5%;

(D) The water absorption measured after 24 hours in a humid environment at 37 ℃ is lower than 25wt%;

(E) At least 30% of the visible light is transmitted through the polymeric material after 24 hours in a humid environment at 37 ℃; and

(F) Comprising a plurality of polymer phases, wherein at least one of the one or more polymer phases has a T of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 DEG C _g 。

60. The polymeric material of claim 59, wherein the polymeric material has at least two of the characteristics of (a), (B), (C), (D), (E), and (F).

61. The polymeric material of any of claims 59-60, wherein the polymeric material has at least three of the characteristics of (a), (B), (C), (D), (E), and (F).

62. The polymeric material of any of claims 59-61, wherein the polymeric material has at least four of the characteristics of (a), (B), (C), (D), (E), and (F).

63. The polymeric material of any of claims 59-62, wherein the polymeric material has at least five of the characteristics of (a), (B), (C), (D), (E), and (F).

64. The polymeric material of any of claims 59-63, wherein the polymeric material has all of properties (a), (B), (C), (D), (E), and (F).

65. The polymeric material of claim 59, wherein the polymeric material is characterized by a water absorption of less than 20wt%, less than 15wt%, less than 10wt%, less than 5wt%, less than 4wt%, less than 3wt%, less than 2wt%, less than 1wt%, less than 0.5wt%, less than 0.25wt%, or less than 0.1wt%, when measured after 24 hours in a humid environment at 37 ℃.

66. The polymeric material of any of claims 58-65, wherein the polymeric material has a conversion of double bonds to single bonds of greater than 60% as measured by FTIR compared to the photocurable resin.

67. The polymeric material of any one of claims 58-66, wherein the polymeric material has an ultimate tensile strength of 10MPa to 100MPa, 15MPa to 80MPa, 20MPa to 60MPa, 10MPa to 50MPa, 10MPa to 45MPa, 25MPa to 40MPa, 30MPa to 45MPa, or 30MPa to 40MPa after 24 hours in a humid environment at 37 ℃.

68. The polymeric material of any of claims 58-67, wherein the polymeric material is characterized by an elongation at break greater than 10%, an elongation at break greater than 20%, an elongation at break greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break of between 40% to 250% after 24 hours in a humid environment at 37 ℃.

69. The polymeric material of any of claims 58-68, wherein the polymeric material is characterized by a storage modulus of 0.1MPa to 4000MPa, a storage modulus of 300MPa to 3000MPa, or a storage modulus of 750MPa to 3000MPa after 24 hours in a humid environment at 37 ℃.

70. The polymeric material of any one of claims 58-69, wherein the polymeric material retains a flexural stress and/or flexural modulus of 100MPa or greater, 80MPa or greater, 70MPa or greater, 60MPa or greater, or 50MPa or greater after 24 hours in a humid environment at 37 ℃.

71. The polymeric material of any one of claims 58-70, wherein at least 40%, 50%, 60%, or 70% of visible light passes through the polymeric material after 24 hours in a humid environment at 37 ℃.

72. The polymeric material of any of claims 58-71, wherein the polymeric material is biocompatible, bioinert, or a combination thereof.

73. The polymeric material of any of claims 58-72, wherein the polymeric material is capable of being 3D printed.

74. A polymeric film comprising the polymeric material of any one of claims 58-73.

75. The polymer film of claim 74, wherein the film has a thickness of at least 100 μιη and no greater than 3 mm.

76. An instrument comprising the polymeric material of any one of claims 58-73 or the polymeric film of any one of claims 74-75.

77. A medical device comprising the polymeric material of any one of claims 58-73 or the polymeric film of any one of claims 74-75.

78. The medical device of claim 77, wherein the medical device is an orthodontic appliance.

79. The medical device of claim 78, wherein the orthodontic appliance is a dental appliance, a dental expander, or a dental spacer.

80. The medical instrument of any one of claims 77-79, wherein the medical instrument is producible by 3D printing.

81. A method of synthesizing a telechelic block copolymer comprising

Coupling the telechelic polymer (A) with a second telechelic polymer (B) to produce a telechelic block copolymer,

wherein the telechelic block copolymer comprises a photopolymerizable end group at its end and

wherein the telechelic block copolymer has a number average molecular weight of up to about 50 kDa.

82. The method of claim 81, wherein the telechelic polymer and the second telechelic polymer are prepared by Atom Transfer Radical Polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), and/or anionic polymerization.

83. A method of forming a polymeric material, the method comprising:

providing a photocurable resin of any one of claims 17-57;

exposing the photocurable resin to a light source; and

the photocurable resin is cured to form a polymeric material.

84. The method of claim 83, further comprising inducing phase separation in the formed polymeric material in one or more lateral directions during photocuring.

85. The method of claim 84, wherein the polymeric material comprises one or more polymeric phases.

86. The method of claim 85, wherein at least one polymer phase of the one or more polymer phases has a glass transition temperature (T) of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃ _g )。

87. The method of claim 86, wherein the polymerized form of the telechelic polymer is a component of the at least one polymer phase having a Tg of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

88. The method of any one of claims 84-87 wherein at least one of the one or more polymer phases comprises a crystalline polymer material.

89. The method of claim 88, wherein the crystalline polymeric material has a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

90. The method of any one of claims 84-89 wherein the polymeric material comprises one or more T _g An amorphous phase of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃, and one or more crystalline phases comprising a crystalline polymeric material having a melting point of at least 60 ℃, 80 ℃, 90 ℃, 100 ℃, or at least 110 ℃.

91. The method of any of claims 83-90, wherein the polymeric material is characterized by one or more of:

a tensile modulus greater than or equal to 200MPa;

a flexural stress and/or flexural modulus greater than or equal to 1.5MPa after 24 hours in a humid environment at 37 ℃; and

the elongation at break is greater than or equal to 5%.

92. The method of any of claims 83-91, further comprising manufacturing a medical device from the polymeric material.

93. The method of claim 92, wherein the medical device is an orthodontic appliance.

94. The method of claim 93, wherein the orthodontic appliance is a dental appliance, a dental expander, or a dental spacer.

95. A method of repositioning teeth of a patient, the method comprising:

generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving the teeth along a treatment path from an initial tooth arrangement to a final tooth arrangement;

producing an orthodontic appliance according to any one of claims 55 to 70; and

at least one tooth of the patient is moved in track toward an intermediate or final tooth arrangement using the orthodontic appliance.

96. The method of claim 95, wherein producing the orthodontic appliance comprises 3D printing the orthodontic appliance.

97. The method of any of claims 95-96, further comprising tracking progress of the patient's teeth along the treatment path after administering an orthodontic appliance to the patient, the tracking comprising comparing a current arrangement of the patient's teeth to a planned arrangement of the patient's teeth.

98. The method of any one of claims 95-97, wherein more than 60% of the patient's teeth conform to the treatment plan after 2 weeks of treatment.

99. The method of any of claims 95-98, wherein 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 originally provided to the at least one tooth of the patient.