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KR-102962695-B1 - Method and composition comprising a chain transfer agent in an absorbable photopolymerizable formulation

KR102962695B1KR 102962695 B1KR102962695 B1KR 102962695B1KR-102962695-B1

Abstract

Compounds and compositions useful for additive printing, particularly additive printing technology such as stereolithography (SLA), are provided, wherein a composition of one or more photocurable compounds, such as a compound having a plurality of ethylene-based unsaturated groups and a compound having a plurality of thiol groups, is photopolymerized, optionally the polymerizable composition comprises two or more thermosetting compounds that are reactive with each other, optionally the polymerizable composition comprises one or more chain transfer agents, and optionally, is thermally polymerized to form a manufactured article in solid form.

Inventors

  • 본 마이클 아론
  • 스탠포드 매튜 머피
  • 부사리 하피즈
  • 틴달 데브라

Assignees

  • 폴리-메드, 인코포레이티드

Dates

Publication Date
20260507
Application Date
20220623
Priority Date
20210624

Claims (20)

  1. A composition comprising: a first organic compound (polyEU) having a plurality of ethylene-based unsaturated groups (EU); a second organic compound (polySH) having a plurality of thiol groups (SH) optionally; a photoinitiator; and at least one chain transfer agent comprising thiol groups. The above chain transfer agent is present in a molar ratio of chain transfer agent thiol groups to ethylene-based unsaturated groups of 0.03 to 0.80, and Among the above polyEUs, EU is acrylate, methacrylate, or norborneneyl, and Among the above polySH, a plurality of SHs are selected from 2, 3, and 4, and also A composition in which a plurality of the above polyEUs are selected from 2, 3, and 4.
  2. A composition according to claim 1, wherein at least one of the first organic compound, the optional second organic compound, the photoinitiator, or the chain transfer agent is bioabsorbable.
  3. A composition according to claim 1, further comprising one or more dyes, pigments, or UV absorbers that are biologically derived molecules of carotenoids, flavonoids, flavones, quinones, porphyrins, diketones, and beta-cyanidins.
  4. A composition according to claim 1, wherein the SH to EU equivalent ratio of X:Y is X:Y in the range of 25 to 75, Y is in the range of 75 to 25, and the sum of X and Y is 100.
  5. A composition according to claim 1, wherein the polySH is water-soluble or bioabsorbable.
  6. A composition according to claim 1, wherein the polySH is a macromer having a molecular weight of more than 1,000 g/mol.
  7. A composition according to claim 1, wherein the polyEU is water-soluble or bioabsorbable.
  8. A composition according to claim 1, wherein the polyEU is a macromer having a molecular weight of more than 1,000 g/mol.
  9. A composition according to claim 1, which is free of volatile materials having a boiling point of less than 110°C.
  10. A composition comprising a photochemically cured reaction product of the composition of claim 1, which, when decomposed, results in a decomposition product or a polymer backbone having a molecular weight of less than 20,000 Daltons.
  11. In item 10, a bioabsorbable composition.
  12. A composition that is solid at 50°C, according to item 10.
  13. As an additive manufacturing process, (a) a step of providing a vat for accommodating the first composition of claim 1; (b) a step of directing chemical radiation from a light source toward the first composition in the container, wherein the chemical radiation is effective in inducing polymerization of the components of the first composition to form a second composition; and (c) An additive manufacturing process comprising the step of forming a solid article comprising the second composition.
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Description

Method and composition comprising a chain transfer agent in an absorbable photopolymerizable formulation Reference to the priority application All applications for which a foreign or domestic priority claim is identified in the application data sheet submitted together with this application are incorporated herein by reference. Technical field of the present disclosure The present disclosure relates to the manufacture and use of curable compositions, such as photocurable and thermocurable compositions containing chain transfer agents, which are generally used to manufacture articles, e.g., bioabsorbable implants and degradation products thereof, by an additive manufacturing process. Stereolithography (SLA) is a relatively well-developed additive printing technology for manufacturing three-dimensional (3-D) objects. In the stereolithography method, light such as ultraviolet (UV) or visible light is used to photopolymerize liquid materials into designed structures, such as three-dimensional articles, with high accuracy and precision. Thin continuous layers are photopolymerized by UV or visible light, for example, under a sliced CAD (Computer-Aided Design) model. SLA generally uses a liquid photopolymerizable composition that can be referred to as a resin or ink formulation. The macroscopic properties and degradation profiles of articles produced by SLA depend in part on polymer chemistry and processing technology. After SLA polymerization of an absorbable macromer having ethylene-based unsaturated functional groups, the absorbable polymer segments may be degraded by hydrolysis or enzymatic degradation, leaving a non-absorbable polymer (i.e., a backbone) from the reacted ethylene-based unsaturated groups. To make such formulations in vivo or implantable in vivo, it is desirable that the non-absorbable polymer be water-soluble and have a molecular weight lower than approximately 20,000 Da so that these degradation products can be excreted by the kidneys. Ethylene-based unsaturated polyesters, which are degradation products such as the polymer backbone that degrade after free radical polymerization, are currently known to have molecular weights much greater than 20,000 Da. This may be the case for photopolymerization methods using biocompatible implantable resins with low concentrations of photoinitiators to reduce toxicity from photoinitiator compounds. The present disclosure provides compounds and compositions useful for chemical beam photoreactive 3-D printing processes, which include, but are not limited to, stereolithography (SLA) and digital light processing (DLP) methods for producing 3-D photoprinted articles having degradation products, particularly 3-D photoprinted articles desirable for implantable articles such as medical devices. The disclosed compounds and compositions have advantages over currently known compounds and compositions for this purpose. Not all topics discussed in the background section are necessarily prior art, and they should not be assumed to be prior art merely as a result of discussions in the background section. In this context, the recognition of problems in prior art discussed in the background section or related to such topics should not be treated as prior art unless explicitly stated to be so. Instead, discussions of any topic in the background section should be treated as part of the inventor's approach to a specific problem and may be creative in themselves. Briefly, in one aspect, the present disclosure provides compounds and compositions useful for reducing degradation products resulting from curing processes, such as photocuring processes or thermal curing processes used in conjunction with photocuring processes. Curing processes are useful for manufacturing articles such as medical devices and coatings. An exemplary curing process is stereolithography (SLA), an additive manufacturing process, wherein a curable composition according to the present disclosure, containing one or more photoreactive compounds including, for example, photoreactive macromers, is photopolymerized (photocured) during the process of forming an article. Another exemplary process is a coating process, wherein the compounds and/or compositions of the present disclosure are placed on a surface and then cured by exposure to heat (thermal curing) and/or exposure to chemical radiation (i.e., photopolymerization or photocuring) to provide a coating on the surface. These cured products, that is, products formed by curing compositions as disclosed herein, may generally be referred to herein as articles, coatings, films, materials, etc. Accordingly, it should be understood that when the present disclosure is illustrated by the manufacture of an article, a coating or other material may likewise be manufactured. In one aspect, the article, coating, etc. is biodegradable. In one aspect, the present disclosure provides a biodegradable polymer material formed by a curing process. Since the material may be used