Degradability, thermal stability, and high thermal properties in spiro polycycloacetals partially derived from lignin

Shen, Minjie; Vijjamarri, Srikanth; Cao, Hongda; Solís, Karla Fabiola Solís; Robertson, Megan L.

doi:10.1039/d1py01017d

Cited by 9 publications

(10 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Significant progress has been made in designing and synthesizing thermoplastic polyacetals (or linear polyacetals), and a more recent study by Coates et al demonstrated the reversible polymerization and depolymerization between polyacetal and a cyclic acetal (i.e., 1,3-dioxolane) monomer . The incorporation of acetal in polymer networks (or thermosets) have also been investigated, and reported efforts include exploring renewable/biobased raw materials, − designing degradable networks, ,, and developing reprocessable/recyclable networks. ,− However, most of the studies only focus on either the degradability or recyclability, and the closed-loop recycling of networks has barely been explored.…”

Section: Introductionmentioning

confidence: 99%

Recyclable, Degradable, and Fully Bio-Based Covalent Adaptable Polymer Networks Enabled by a Dynamic Diacetal Motif

Zhang

Gao

Chen

et al. 2023

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Covalent adaptable networks (CANs), which can reconfigure on-demand under photo- or thermal stimuli, have recently been pursued as an alternative to the traditional thermosetting polymers. While these materials have demonstrated excellent recyclability and reprocessability, the majority of them reported to date are based on non-renewable resources. Meanwhile, material recycling highly counts on the collection system, and any materials that inevitably escape from the collection system will eventually go to the environment, challenging nature’s ability to break down these materials. Therefore, CAN materials that possess both recyclability and degradability are highly desirable. In this work, we seek to simultaneously address the recyclability, renewability, and degradability of CAN materials. Spiro diacetal building blocks are derived from bio-based benzaldehyde and erythritol and then subjected to the curing process using bio-based epoxy soybean oil as crosslinkers, yielding fully biobased CAN materials. Owing to the dynamic and degradable features of acetal motifs, our CAN materials exhibit both good recyclability and acid degradability, and the degraded products are reusable for preparation of new CANs. In addition, by tuning the steric hindrance adjacent to the reactive phenol site, we are able to control the mechanical properties of CANs using different bio-based benzaldehydes (vanillin, ethyl vanillin, and syringaldehyde). The outcome of the current research provides a strategy for the design of recyclable and degradable bio-based CANs, which will extend the development of CANs.

show abstract

Section: Introductionmentioning

confidence: 99%

Recyclable, Degradable, and Fully Bio-Based Covalent Adaptable Polymer Networks Enabled by a Dynamic Diacetal Motif

Zhang

Gao

Chen

et al. 2023

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…The third stage of decomposition with a T peak at 230 °C and a mass loss of 15% occurs as a result of the decomposition of the glycosidic bonds in the polysaccharide structure [ 26 ]. According to the study by Shen et al, the decomposition of spiroacetal-type structures occurs in the range of 210–349 °C [ 27 ]. Therefore, stage IV with a T peak at 265 °C and a mass loss of ~11% corresponds to the degradation of the spiroacetal fragments in the PITAU copolymer structure.…”

Section: Resultsmentioning

confidence: 99%

Injectable Networks Based on a Hybrid Synthetic/Natural Polymer Gel and Self-Assembling Peptides Functioning as Reinforcing Fillers

Ghilan¹,

Croitoriu²,

Chiriac³

et al. 2023

Polymers

View full text Add to dashboard Cite

Double network (DN) hydrogels composed of self-assembling low-molecular-weight gelators and a hybrid polymer network are of particular interest for many emerging biomedical applications, such as tissue regeneration and drug delivery. The major benefits of these structures are their distinct mechanical properties as well as their ability to mimic the hierarchical features of the extracellular matrix. Herein, we describe a hybrid synthetic/natural polymer gel that acts as the initial network based on sodium alginate and a copolymer, namely poly(itaconic anhydride-co-3,9-divinyl-2,4,8,10-tetraoxaspiro (5,5) undecane). The addition of amino acids and peptide-derived hydrogelators, such as Fmoc-Lys-Fmoc-OH and Fmoc-Gly-Gly-Gly-OH, to the already-made network gives rise to DNs crosslinked via non-covalent interactions. Fourier transform infrared spectroscopy (FTIR) and thermal analysis confirmed the formation of the DN and highlighted the interactions between the two component networks. Swelling studies revealed that the materials have an excellent water absorption capacity and can be classified as superabsorbent gels. The rheological properties were systematically investigated in response to different variables and showed that the prepared materials present injectability and a self-healing ability. SEM analysis revealed a morphology consisting of a highly porous and interconnected fibrous network. Finally, the biocompatibility was evaluated using the MTT assay on dermal fibroblasts, and the results indicated that the new structures are non-toxic and potentially useful for biomedical applications.

show abstract

“…Other samples of PBT and PHT copolyesters exhibit T d values between 453 and 456 °C without notable differences to the homopolyester samples. The high thermal stabilities of Ct diesters can be attributed to the bicyclic ring structures of camphor and spiro-rings . DSC was used to examine the glass transition and melting behaviors of the homo- and copolyesters (Figure b,c).…”

Section: Resultsmentioning

confidence: 99%

“…The high thermal stabilities of Ct diesters can be attributed to the bicyclic ring structures 48 of camphor and spiro-rings. 49 DSC was used to examine the glass transition and melting behaviors of the homo-and copolyesters (Figure 3b,c).…”

Section: Thermal Properties Of the Dmt-based Homopolyesters And The C...mentioning

confidence: 99%

Thermally Stable Biodegradable Polyesters with Camphor and Tartaric Acid Coupled Cyclic Diester Monomers for Controlled Hydrolytic Degradations

Kang

Lee

et al. 2023

ACS Appl. Polym. Mater.

View full text Add to dashboard Cite

The development of biodegradable engineering plastics is challenging, because increases in biodegradability mostly degrade other material properties, such as mechanical and thermal properties of polymers. Here, we use bioderivatives of diester monomers, dimethyl (1S,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,2′-[1,3]dioxolane]-4′,5′-dicarboxylate (camphor dimethyl DL-tartrate, Ct diester), for the synthesis of phthalatebased copolyesters to enhance degradability without a notable loss of thermal stability. Ct diester synthesized by acetalization of tartaric acid and camphor contains a bridged type of rigid bicycling ring with high thermal stability and controlled degradation via hydrolysis of acetal groups within the spiro-ring structure. Various alkyl-length diols of ethylene, butylene, and hexylene are copolymerized with mixtures of dimethyl phthalate (DMT) and Ct diester in a 9:1 molar ratio. The glass transition temperature and degradation temperature of the copolyesters are comparable to those of DMT-based homopolyesters. Due to decreases in crystallinity, copolyesters exhibit slight decreases in melting temperature of 10 to 20 °C, which can be advantageous for reducing processing temperatures. Notably, the copolyesters demonstrate enhanced hydrolytic degradation of 9.3 to 26.2% in pH 2 environment for 18 days, as measured by the degree of molecular weight reductions. These values are between 1.7 and 3.5 times higher than the degradation rates of their control samples of DMT-based homopolyesters under the same degradation conditions.

show abstract

Degradability, thermal stability, and high thermal properties in spiro polycycloacetals partially derived from lignin

Abstract: Spiro polycycloacetals were synthesized from vanillin and syringaldehyde, along with high-performance co-monomers, exhibiting high glass transition temperatures and thermal stabilities, and rapid rates of hydrolysis in acidic solutions.

Cited by 9 publications

References 44 publications

Recyclable, Degradable, and Fully Bio-Based Covalent Adaptable Polymer Networks Enabled by a Dynamic Diacetal Motif

Recyclable, Degradable, and Fully Bio-Based Covalent Adaptable Polymer Networks Enabled by a Dynamic Diacetal Motif

Injectable Networks Based on a Hybrid Synthetic/Natural Polymer Gel and Self-Assembling Peptides Functioning as Reinforcing Fillers

Thermally Stable Biodegradable Polyesters with Camphor and Tartaric Acid Coupled Cyclic Diester Monomers for Controlled Hydrolytic Degradations

Contact Info

Product

Resources

About