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Development of Degradable Block Copolymers for Stereolithographic Printing Using Poly(propylene fumarate) and Lactones

Petersen, Shannon Rae
http://rave.ohiolink.edu/etdc/view?acc_num=akron1605017666239143

Abstract Details

2020, Doctor of Philosophy, University of Akron, Polymer Science.
Versatile Ring-Opening Copolymerization and Postprinting Functionalization of Lactone and Poly(propylene fumarate) Block Copolymers: Resorbable Building Blocks for Additive Manufacturing. Additive manufacturing has the potential to change medicine, but clinical applications are limited by a lack of resorbable, printable materials. Herein, we report the first synthesis of polylactone and poly(propylene fumarate) (PPF) block copolymers with well-defined molecular masses and molecular mass distributions using sequential, ring-opening polymerization and ring-opening copolymerization methods. These new copolymers represent a diverse platform of resorbable printable materials. Furthermore, these polymers open a previously unexplored range of accessible properties among stereolithographically printable materials, which we demonstrate by printing a polymer with a molecular mass nearly 4 times that of the largest PPF homopolymer previously printed. To further demonstrate the potential of these materials in regenerative medicine, we report the postprinting “click” functionalization of the material using a copper-mediated azide–alkyne cycloaddition. Degradable, Printable Poly(propylene fumarate) Based ABA Triblock Elastomers. Additive manufacturing is rapidly advancing tissue engineering, but the scope of its clinical translation is limited by a lack of materials designed to meet specific mechanical properties and resorption timelines. Materials that are printable via photochemical crosslinking, fully degradable, and elastomeric have proven particularly challenging to develop. Herein, we report the synthesis of a series of poly(propylene fumarate-b-γ-methyl-ε-caprolactone-b-propylene fumarate) ABA triblock polymers using a sequential ring-opening polymerization and ring-opening copolymerization. When crosslinked photochemically using a continuous liquid interface production digital light processing (DLP) Carbon M2 printer, these ABA type triblock copolymers are durable elastomers with tunable degradation and elastic properties. The polymers are shown to undergo slow, hydrolytic degradation in vitro with minimal loss of mechanical performance during degradation. The remarkable mechanical properties of elastomers found in nature are characterized by high elasticity and tensile strength that are difficult to mimic using synthetic methods. Sugar-based Thermoplastic Elastomers with Hydrogen Bond Induced Strain Hardening. Traditional strategies to synthetically recreate these properties primarily focus on the formation of chemically crosslinked networks or increasing the content of crystalline domains. While these provide materials that have found a myriad of uses, these strategies also have significant drawbacks including limited end-of-life options, reduced optical clarity, and a tradeoff between strength and extensibility. Herein, we report the synthesis of thermoplastic polyurethane elastomers containing renewably sourced 1,4:3,6-dianhydrohexitols that display exceptional strength and elongation at break, superior to both natural and synthetic commercial rubbers. The unique combination of the rigid ring structures adjacent to strong hydrogen bonding groups units are shown to impart unique material properties including strain rate dependent behavior, significant strain hardening, and high optical clarity that is retained throughout elongation. These phenomena are attributed to dynamic transitions between intra- and inter- molecular hydrogen bonding in the transient crosslinking network, as revealed by computational and experimental investigations. In addition to the renewably sourced feedstock, the self-assembled nature and high thermal stability of these materials enable facile reprocessing with minimal loss of mechanical performance, making them excellent candidates for sustainable alternatives to commodity elastomers.
Matthew Becker, PhD (Advisor)
Dobrynin Andrey, PhD (Committee Chair)
Wesdemiotis Chrys, PhD (Committee Member)
Cavicchi Kevin, PhD (Committee Member)
Willits Rebecca, PhD (Committee Member)
131 p.
Polymers
3D printing; stereolithography; cDLP; CLIP; degradable polymers; tissue engineering; elastomers; sustainable polymers; block copolymers

Recommended Citations

Citations

  • Petersen, S. R. (2020). Development of Degradable Block Copolymers for Stereolithographic Printing Using Poly(propylene fumarate) and Lactones [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1605017666239143

    APA Style (7th edition)

  • Petersen, Shannon. Development of Degradable Block Copolymers for Stereolithographic Printing Using Poly(propylene fumarate) and Lactones. 2020. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1605017666239143.

    MLA Style (8th edition)

  • Petersen, Shannon. "Development of Degradable Block Copolymers for Stereolithographic Printing Using Poly(propylene fumarate) and Lactones." Doctoral dissertation, University of Akron, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron1605017666239143

    Chicago Manual of Style (17th edition)

akron1605017666239143
177
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This open access ETD is published by University of Akron and OhioLINK.
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