skip to main content


Title: Hydrolytically degradable poly(β-thioether ester ketal) thermosets via radical-mediated thiol–ene photopolymerization
Thiol–ene photopolymerization was exploited for the synthesis of poly(β-thioether ester ketal) networks capable of undergoing complete degradation under acid and/or basic conditions. Using the design of four novel bisalkene diketal monomers, we demonstrate the ability to tune degradation profiles under acidic conditions with timescales dictated by the structure of the diketal linker, while hydrolysis of the β-thioether ester functionality dominates the degradation profile under basic conditions irrespective of the diketal structure. All four poly(β-thioether ester ketal) networks exhibited degradation behavior characteristic of a surface erosion process. The networks showed mechanical (low modulus) and thermomechanical properties (low T g ) typical of thiol–ene thermosets with minimal influence from the structure of the diketal linkage. To highlight the advantages of endowing a step-growth network with ketal linker chemistry, we demonstrated the ability to recover diketone precursors from the thermoset degradation by-products and recycle these compounds into building blocks for additional thermoset materials.  more » « less
Award ID(s):
1710589 1449999
NSF-PAR ID:
10172681
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Polymer Chemistry
Volume:
10
Issue:
41
ISSN:
1759-9954
Page Range / eLocation ID:
5635 to 5644
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Hydrolytically degradable poly(β‐thioether ester ketal) thermosets are synthesized via radical‐mediated thiol‐ene photopolymerization using three novel dialkene acyclic ketal monomers and a mercaptopropionate based tetrafunctional thiol. For all thermoset compositions investigated, degradation behavior is highly tunable based on the structure of the incorporated ketal and pH. Complete degradation of the thermosets is observed upon exposure to acidic and neutral pH, and under high humidity conditions. Polymer networks composed of cross‐link junctions based on acyclic dimethyl ketals degrade the quickest, whereas networks containing acyclic cyclohexyl ketals undergo hydrolytic degradation on a longer timescale. Thermomechanical analysis reveals low glass transition temperatures and moduli typical of thioether‐based thermosets.

     
    more » « less
  2. null (Ed.)
    Photoinduced thiol-catalyzed hydrogen abstraction and β-scission of acyclic benzylidene acetals is demonstrated as a new route to “command-destruct” polymer thermosets. Using this approach, we show that poly(thioether acetal) networks synthesized via thiol–ene photopolymerization rapidly degrade to alkyl benzoate byproducts when triggered with light, transitioning from solid to liquid within seconds. The light-driven construction and destruction processes, accessible via distinct differences in kinetics, are readily amenable for photopatterning, additive/subtractive manufacturing and wavelength-selective applications. 
    more » « less
  3. null (Ed.)
    The development of tunable and degradable crosslinked-polyanhydride networks from renewably derived itaconic anhydrides and multifunctional thiols is presented. Itaconic acid was initially converted to ethyl itaconic anhydride and isoamyl itaconic anhydride via a two-step synthetic procedure on hundred-gram scale with minimal purification. Dinorbornene-functionalized derivatives were prepared via cycloaddition chemistry, and photoinitiated thiol–ene polymerization reactions were explored using commercially available tetra- and hexa-functional thiols, all using solvent-free syntheses. The thiol–ene reaction kinetics of different monomer compositions were characterized by real-time Fourier transform infrared (RT-FTIR) spectroscopy, with the norbornene functionalized derivatives exhibiting the highest reactivity towards thiol–ene photopolymerizations. The thermal and mechanical characteristics of the thermosets were analyzed and the viscoelastic behavior was investigated by dynamic mechanical analysis to understand the influence of the ester functionality and choice of crosslinker on the material properties. The anhydride backbone was found to be susceptible to controlled degradation under physiologically-(phosphate-buffered saline) and environmentally-relevant (artificial seawater) testing conditions over a period of 60 days at 50 °C. This work demonstrates that itaconic acid may be a useful feedstock in the generation of degradable polyanhydride networks via thiol–ene photopolymerization. 
    more » « less
  4. Abstract

    Thiol–norbornene (thiol–ene) photoclickable poly(ethylene glycol) (PEG) hydrogels are a versatile biomaterial for cell encapsulation, drug delivery, and regenerative medicine. Numerous in vitro studies with these 4‐arm ester‐linked PEG‐norbornene (PEG‐4eNB) hydrogels demonstrate robust cytocompatibility and ability to retain long‐term integrity with nondegradable crosslinkers. However, when transplanted in vivo into the subcutaneous or intraperitoneal space, these PEG‐4eNB hydrogels with nondegradable crosslinkers rapidly degrade within 24 h. This characteristic limits the usefulness of PEG‐4eNB hydrogels in biomedical applications. Replacing the ester linkage with an amide linkage (PEG‐4aNB) mitigates this rapid in vivo degradation, and the PEG‐4aNB hydrogels maintain long‐term in vivo stability for months. Furthermore, when compared to PEG‐4eNB, the PEG‐4aNB hydrogels demonstrate equivalent mechanical properties, crosslinking kinetics, and high cytocompatibility with rat islets and human mesenchymal stem cells. Thus, the PEG‐4aNB hydrogels may be a suitable replacement platform without necessitating critical design changes or sacrificing key properties relevant to the well‐established PEG‐4eNB hydrogels.

     
    more » « less
  5. Heterogeneous “linkers” are incorporated into polymers for a number of reasons, most commonly to facilitate the coupling of the targeted backbone segments. Due to their inclusion in the backbone, these linkers have the potential to affect the overall properties of the copolymer, even when present in relatively low weight percentages. To characterize the degree of impact of some common linkers, a set of polymers that incorporate both degradable sequenced segments and linkers were synthesized and systematically examined. Seven sequence-controlled olefin containing ester macrocycles were prepared, each with a unique central moiety, including a five-carbon alkyl chain, diethylene glycol, a urea, a thioether, a triazole, a bioaromatic, and an extension of the ester sequence. The macrocycles were polymerized via ED-ROMP to yield seven polymers that vary only in the the linker segment. The properties of all polymers were compared to determine the relative dominance of the different linker types. The properties tested in the study included thermal behavior, mechanical characteristics, hydrolytic degradation and film qualities. The thermal and mechanical properties proved to be dependent primarily on the ability of the linker to promote interchain interactions, as well as the weight fraction of the linker, whereas the hydrolytic degradation was dominated by the relative hydrophobicity of the linker groups. In all cases, the linker identity was a significant contributer to the behavior. 
    more » « less