A Biosourced Epoxy Resin for Adhesive Thermoset Applications

Moreira, Vitor Bonamigo; Alemán, Carlos; Rintjema, Jeroen; Bravo, Fernando; Kleij, Arjan W.; Armelín, Elaine

doi:10.1002/cssc.202102624

Cited by 24 publications

(18 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Their ratio in the polymer product (m:n = 10:1) was controlled by the initial stoichiometry of both monomers, with LO in excess. 36 The synthesis of the resultant more-reactive hybrid polycarbonate oxide was facilitated by Al Me −PPNCl, showing the versatile nature of this type of binary catalyst. The thermal and physical properties of partially biobased thermosets obtained from a mixture of the hybrid polycarbonate and Jeffamine as the curing agent were scrutinized, exhibiting good film-forming properties at room temperature and under stoving conditions.…”

Section: Metallo-aminotriphenolatesmentioning

confidence: 99%

“…To increase the overall reactivity, a partial bioderived poly-epoxide was designed that combined the presence of both di- and monosubstituted epoxides (Scheme b). Their ratio in the polymer product ( m : n = 10:1) was controlled by the initial stoichiometry of both monomers, with LO in excess . The synthesis of the resultant more-reactive hybrid polycarbonate oxide was facilitated by Al Me –PPNCl, showing the versatile nature of this type of binary catalyst.…”

Section: Polycarbonate Synthesis Using Metallo-aminotriphenolatesmentioning

confidence: 99%

See 1 more Smart Citation

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Brandolese

Kleij

2022

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Conspectus The introduction of circular principles in chemical manufacturing will drastically change the way everyday plastics are produced, thereby affecting several aspects of the respective value chains in terms of raw feedstock, recyclability, and cost. The ultimate aim is to ensure a paradigm shift toward plastic-based (consumer) materials that overall can offer a more attractive and sustainable carbon footprint, which is an important requisite from a societal, political, and eventually economical point of view. To realize this important milestone, it is vitally important to control the polymerization processes associated with the creation of novel sustainable materials. In this respect, we realized that expanding the portfolio of biomass-derived monomers may indeed create an impetus for atom circularity; however, the often sterically congested nature of biomass-derived monomers minimizes the ability of previously developed catalysts to activate and transform these precursors. Our motivation was thus spurred by an apparent lack of catalysts suitable for addressing the conversion of such biomonomers, as we realized the potential that new catalytic processes could have to advance and contribute to the development of sustainable materials produced from polycarbonates and polyesters. These two classes of polymers represent crucial ingredients of important and large-scale consumer products and are therefore ideal fits for implementing new catalytic protocols that enable a gradual transition to plastic materials with an improved carbon footprint. When we started our research expedition, the field was dominated by metal catalysts that incorporated preferred, and in some cases even privileged, ligand backbones (such as salens) able to mediate both ring-opening and ring-opening copolymerization manifolds. One major drawback of these aforementioned catalysts is their rather rigid nature, a feature that reduces their ability to act as adaptive systems, especially in cases where bulky monomers are involved. While our initial focus was on the utilization of sustainable metal salen complexes (M = Zn, Fe) for the activation of small cyclic ethers, which are privileged monomers for polyester and polycarbonate production, we were rapidly confronted with severe limitations related to their inability to activate a wider range of complex epoxides and oxetanes, which was imparted by the planar coordination geometry of the salen ligand in most of its applied metal complexes. In our quest to find a catalytically more effective metal complex with the ability to electronically and sterically tune its substrate-binding and substrate-activation potential, we identified aminotriphenolates as structurally versatile, easily accessible, and scalable ligands for various earth-abundant metal cations. Moreover, the ligand backbone allows for switchable coordination environments around the metal centers, thus offering the necessary adaptation in substrate activation events. This Account describes how Al(III)- and Fe(III)-centered aminotriph...

show abstract

Section: Metallo-aminotriphenolatesmentioning

confidence: 99%

Section: Polycarbonate Synthesis Using Metallo-aminotriphenolatesmentioning

confidence: 99%

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Brandolese

Kleij

2022

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

show abstract

“…When combining limonene oxide 24b with vinyl cyclohexene oxide in a predetermined ratio during the polymerization and subsequently oxidizing the two sterically different double bond moieties, a partially bio‐based oxidized polycarbonate was obtained. [ 125 ] After curing with a diamine, it showed improved adhesion properties in comparison to petroleum‐based thermosets.…”

Section: Other Nitrogen‐containing Polymers Using Terpene Unitsmentioning

confidence: 99%

Nitrogen‐Containing Polymers Derived from Terpenes: Possibilities and Limitations

Scheelje

Destaso

Cramail

et al. 2022

Macro Chemistry & Physics

View full text Add to dashboard Cite

Nitrogen-containing polymers are widely applied materials, including polyamides, polyurethanes, and polyureas as well as epoxy thermosets. Their indispensability and the urgent need to replace fossil-based polymers considering more sustainable alternatives lead to significant efforts in exploring renewable feedstock as potential new building blocks. Being obtained from non-edible plant parts and often occurring as waste products, terpenes represent a promising group of renewable compounds that are of possible interest in the synthesis of nitrogen-containing polymers. The structural diversity of terpenes in combination with the mechanical properties that nitrogen-containing moieties bring into polymers can give rise to novel biobased materials that outstand mechanical and thermal properties of conventional fossil-based counterparts. In this review, an overview of the use of terpene compounds in the synthesis of nitrogen-containing polymers is given, covering different approaches to make use of terpenes as a valuable pool of renewable monomers.

show abstract

“…It is typically abundant in citrus peels and obtained via extraction as a major byproduct of citrus production; the annually recovered amount exceeds 70,000 tons. , Limonene contains two isomeric alkene groups from isoprene units with distinct reactivity, each of which experiences characteristic functionalization or polymerization reactions . Thus, owing to their availability and synthetic flexibility, researchers have devoted much effort to developing limonene-based polymers as a form of polycarbonates or polyesters. − Nonetheless, when processed into thermosets, limonene normally requires prior chemical modification such as epoxidation, and the resultant networks have been seldom endowed with a reversible nature so far; they are partially reusable or not. − Therefore, it is beneficial to develop an accessible design for reusable thermosets using natural limonene without the need for pretreatment, which is achievable by diversification of polymer structures and introduction of suitable reversible chemistry and further expands the adaptability of limonene for sustainable materials.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Renewable, Recyclable, Degradable Thermosets Endowed with Highly Branched Polymeric Structures and Reinforced with Carbon Fibers

Choi

Jeong

et al. 2023

Macromolecules

View full text Add to dashboard Cite

This paper demonstrates the molecular design of renewable polymer thermosets that are chemically recyclable yet degradable on demand. In this design, the thermosets comprise a limonene-based highly branched polymer, which has been synthesized via the regioselective thiol−ene reaction between natural limonene and multifunctional thiol, and a Meldrum's acid derivative for the click/declick reaction of thiol groups that are deliberately positioned on the outer surface of the branched polymer. Thus, the accessible thiols expedite the covalent bond exchange reaction and enable the formation of a network and bulk recycling of the entire network; the labile cross-linkers enable molecular degradation or repurposing of the materials under benign conditions. The thermosets can be also reinforced with the addition of carbon fibers. Thus, reversible deformation or self-lamination of the resultant carbon composites, which are degradable and recyclable, was achieved owing to the thermosets, which act as a matrix or binder. We envision that the renewable materials presented here would be advanced by introducing diverse biomolecules or reversible chemistry to develop disposable bio-based platforms that can be further upcycled at the end of their lifecycles.

show abstract

A Biosourced Epoxy Resin for Adhesive Thermoset Applications

Cited by 24 publications

References 30 publications

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates

Nitrogen‐Containing Polymers Derived from Terpenes: Possibilities and Limitations

Synthesis of Renewable, Recyclable, Degradable Thermosets Endowed with Highly Branched Polymeric Structures and Reinforced with Carbon Fibers

Contact Info

Product

Resources

About