Biobased aliphatic polyesters from a spirocyclic dicarboxylate monomer derived from levulinic acid

Valsange, Nitin G.; González, María Nelly García; Warlin, Niklas; Mankar, Smita V.; Rehnberg, Nicola; Lundmark, Stefan; Zhang, Baozhong; Jannasch, Patric

doi:10.1039/d1gc00724f

Cited by 12 publications

(27 citation statements)

References 67 publications

(69 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The catalytic conversion of levulinic acid into 2-hydroxy-2-methylsuccinic acid (citramalic acid) was also reported [ 165 ], which is a high-value chemical that can replace succinic acid in polybutylene succinate, enhancing its properties. The synthesis of a cyclic diester via the ketalization of levulinic acid with pentaerythritol was described ( Figure 9 a), and the obtained monomer was polymerized by transesterification with 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol, yielding fully amorphous polyesters with glass transition temperatures ranging from 12 to 49 °C and thermal stability up to 300 °C [ 166 ]. An analogous approach took advantage of the aromatic character of vanillin to synthesize the allyl ether monomer 3,9-bis(4-(allyloxy)-3-methoxyphenyl)-2,4,8,10-tetraoxaspiro [5.5]undecane ( Figure 9 b), which was mixed with thiols with different functionalities and polymerized through thiol-ene click photopolymerization to form the corresponding networks with tunable properties [ 167 ].…”

Section: Broadening the Horizon: Bio-based Routes For Original Polymersmentioning

confidence: 99%

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

Gandini

Lacerda

2021

Molecules

View full text Add to dashboard Cite

A progressively increasing concern about the environmental impacts of the whole polymer industry has boosted the design of less aggressive technologies that allow for the maximum use of carbon atoms, and reduced dependence on the fossil platform. Progresses related to the former approach are mostly based on the concept of the circular economy, which aims at a thorough use of raw materials, from production to disposal. The latter, however, has been considered a priority nowadays, as short-term biological processes can efficiently provide a myriad of chemicals for the polymer industry. Polymers from renewable resources are widely established in research and technology facilities from all over the world, and a broader consolidation of such materials is expected in a near future. Herein, an up-to-date overview of the most recent and relevant contributions dedicated to the production of monomers and polymers from biomass is presented. We provide some basic issues related to the preparation of polymers from renewable resources to discuss ongoing strategies that can be used to achieve original polymers and systems thereof.

show abstract

Section: Broadening the Horizon: Bio-based Routes For Original Polymersmentioning

confidence: 99%

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

Gandini

Lacerda

2021

Molecules

View full text Add to dashboard Cite

show abstract

“…The thermal stability of the polyesters was evaluated by TGA, as shown in Figure and Table . All the synthesized polyesters showed two thermal decomposition maxima ( T d ) between ∼278 and 460 °C . The lower temperature maximum is likely connected to the decomposition of imine bonds.…”

Section: Resultsmentioning

confidence: 97%

“…All the synthesized polyesters showed two thermal decomposition maxima (T d ) between ∼278 and 460 °C. 77 The lower temperature maximum is likely connected to the decomposition of imine bonds. This is supported by this maximum being the dominant decomposition step for the monomers, while the higher temperature maximum was the main decomposition step for the polymers, with the exception of SBP5b.…”

Section: Synthesis Synthesis Of 4-(2-hydroxyethoxy)-2-methoxybenzalde...mentioning

confidence: 99%

Designed for Circularity: Chemically Recyclable and Enzymatically Degradable Biorenewable Schiff Base Polyester-Imines

Sathiyaraj

Najjarzadeh

Vanga

et al. 2023

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Bio-based plastics potentially have several positive impacts on the environment; however, in order to make a real difference, they need to have managed and sustainable end of life. This means they should from the start be designed for chemical, mechanical, and/or organic (biological) recycling. Development of energy-efficient and selective chemical recycling processes is a necessary part in reaching truly circular plastic flows. Polyesters are generally well suited for chemical recycling due to the presence of reversible ester bonds. Utilization of dynamic covalent chemistry to include a second, even more easily reversed bond, such as Schiff base (SB, imine bond), could further facilitate chemical recycling, enabling depolymerization back to monomeric products under mild conditions. Here, we present the synthesis of three vanillin-derived SB monomers SBM1, SBM2, and SBM3 and the corresponding polymers SBP3a–b, SBP4a–b, and SBP5a–b. Three different diamines and two potentially bio-sourced diesters were utilized to yield altogether six different polyester-imines with different aliphatic/aromatic contents. All the obtained SB-based polyesters were thermally stable at ∼290–330 °C and had a high char yield during the pyrolysis, which may indicate inherent flame resistance. All the polyesters were amorphous with glass transition temperatures from 36 to 76 °C. The chemical recyclability and hydrolytic degradation of the synthesized polyesters was evaluated by using real-time 1H NMR spectroscopy. Finally, the susceptibility of the synthesized polyester-imines to enzymatic degradation by PETase was demonstrated. The experimental results were further supported by induced-fit docking experiments to theoretically evaluate the potential productive binding of the produced polyester-imines and intermediates thereof to the active site of PETase.

show abstract

“…In recent years, the design and synthesis of bio-based hard monomers have been exploited to develop high performance polymeric materials for replacement of engineering plastics. Some bio-based hard monomers were used to obtain polymers with high glass transition temperatures, such as spirofuran-based monomers ( Figure 10 ) [ 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 ]. It is also found that the CO 2 emission for production of the bio-based rigid monomer 1 ( Figure 10 a,b) was much lower than that of fossil-based monomers, which gave rise to high performance polymers with a degradation temperature of up to 300 °C based on thermal gravimetric analysis (TGA) ( Figure 10 c) [ 86 ].…”

Section: Conclusion and Future Prospects Of Bio-based Polymersmentioning

confidence: 99%

Recent Advances in Lignocellulose-Based Monomers and Their Polymerization

Pei¹,

Liu²,

Zhu

et al. 2023

Polymers

View full text Add to dashboard Cite

Replacing fossil-based polymers with renewable bio-based polymers is one of the most promising ways to solve the environmental issues and climate change we human beings are facing. The production of new lignocellulose-based polymers involves five steps, including (1) fractionation of lignocellulose into cellulose, hemicellulose, and lignin; (2) depolymerization of the fractionated cellulose, hemicellulose, and lignin into carbohydrates and aromatic compounds; (3) catalytic or thermal conversion of the depolymerized carbohydrates and aromatic compounds to platform chemicals; (4) further conversion of the platform chemicals to the desired bio-based monomers; (5) polymerization of the above monomers to bio-based polymers by suitable polymerization methods. This review article will focus on the progress of bio-based monomers derived from lignocellulose, in particular the preparation of bio-based monomers from 5-hydroxymethylfurfural (5-HMF) and vanillin, and their polymerization methods. The latest research progress and application scenarios of related bio-based polymeric materials will be also discussed, as well as future trends in bio-based polymers.

show abstract

Biobased aliphatic polyesters from a spirocyclic dicarboxylate monomer derived from levulinic acid

Abstract: Levulinic acid derived from lignocellulose is an important biobased building block chemical. Here, we report on the synthesis and polymerization of a rigid spirocyclic diester monomer to produce polyesters and...

Cited by 12 publications

References 67 publications

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

Designed for Circularity: Chemically Recyclable and Enzymatically Degradable Biorenewable Schiff Base Polyester-Imines

Recent Advances in Lignocellulose-Based Monomers and Their Polymerization

Contact Info

Product

Resources

About