Synthesis and Characterization of Farnesene-Based Polymers

Yoo, Taejun; Henning, Steven K.

doi:10.5254/rct.17.82683

Cited by 40 publications

(63 citation statements)

References 11 publications

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“…However, there is little exploitation of sesquiterpenes by the scientific community. 25,26 Among molecules defined as sesquiterpenes, caryophyllene and humulene stand out, since these molecules are made of interesting structural elements. These molecules are found in many essential oils such as rosemary, cannabis sativa, hops, and mostly clove oil.…”

Section: Introductionmentioning

confidence: 99%

Caryophyllene as a Precursor of Cross-Linked Materials

Medeiros

Coz

Grau

2020

ACS Sustainable Chem. Eng.

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This paper aims at the synthesis of a new type of elastomers from caryophyllene. The adopted strategy was to cross-link the polycaryophyllene, which was synthesized by ring-opening metathesis polymerization (ROMP). The polycaryophyllene obtained showed Mn = 2 x 10 4 g.mol-1 (Đ = 1.5) with a glass transition temperature (Tg) of-35 °C. On the first hand, thermal cross-linking was performed in the presence of organic peroxides or sulfur system. On the second hand, thiol-ene coupling initiated by UV-light at room temperature was also investigated as an alternative pathway to cross-link the polycaryophyllene. The materials obtained were analyzed by TGA, DSC, and DMA. The Tg of cross-linked polycaryophyllene could be easily modulated from-35 °C to a range between-25 and 10 °C by changing the type of cross-linking agent. The curing process led to the improvement of thermal stability ranging from 200 °C to around 340 °C. Finally, the network storage modulus varied from 1 to 100 MPa at room temperature.

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Section: Introductionmentioning

confidence: 99%

Caryophyllene as a Precursor of Cross-Linked Materials

Medeiros

Coz

Grau

2020

ACS Sustainable Chem. Eng.

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“…Myrcene has been copolymerized with monomers typically used for thermoplastics like α‐methyl‐ p ‐methylstyrene and poly(lactic acid) by anionic polymerization, and more recently copolymerized with GMA and styrene by NMP . Far has been homopolymerized by ionic polymerization, but polymerization by RDRP has not yet been reported. This study investigates NMP of bio‐based Far with incorporation of functional GMA.…”

Section: Introductionmentioning

confidence: 99%

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Luk

Marić

2019

Macro Reaction Engineering

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polymers with controlled architectures. [11,12] Styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) triblock copolymers have long been commercialized too, such as the Kraton family of thermoplastic elastomers, which are made by anionic polymerization. [13,14] While many industrial applications use free radical polymerization, CRP precisely controls the molecular architecture of polymer chains, therefore making homopolymers, diblock and triblock copolymers with narrow molecular weight distributions (MWDs) and low dispersity. [15] Ionic polymerization is a truly "living" method, but it is intolerant to functional monomers and impurities. [16] CRP, more properly defined as reversible deactivation radical polymerization (RDRP), is a newer, more versatile technique to control the polymerization of free radicals. It utilizes activationdeactivation equilibrium or reversible chain transfer to suppress irreversible termination such that the propagating radical is primarily in its dormant state. [17] Amongst the several types of RDRP, atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation transfer (RAFT) [21][22][23] can polymerize a wide variety of functional monomers like vinyl esters and (meth) acrylates. This study will focus on nitroxide-mediated polymerization (NMP) as it is particularly adept for polymerization of styrene-diene systems. [24][25][26] NMP is able to polymerize functionalized styrene and acrylate monomers successfully, [27] however it is limited in its ability to maintain active chain ends in the polymerization of methacrylates. [28,29] It was discovered that the rate of dissociation (k d ) is very large because of steric stabilization of the propagating methacrylate radical, and the rate of combination (k c ) is very low due to steric hindrance provided by the bulky SG1-nitroxide (N-tert-butyl-N-[1-diethylphosphono-(2,2dimethylpropyl)] nitroxide). Consequently, the activationdeactivation equilibrium (K eq = k d /k c ) is high, resulting in termination by disproportionation. [30] To overcome this, small amounts of controlling comonomer like styrene or acrylonitrile can be added to effectively lower K eq . [28,31] Furthermore, the SG1-based nitroxide, BlocBuilder, can be modified with an N-succinimidyl ester group (N-succinimidyl modified commercial BlocBuilder [NHS-BB]) to better control the polymerization of methacrylates, [32] and successful polymerization of Nitroxide-Mediated Polymerization Farnesene (Far) is a bio-based terpene monomer that is similar in structure to commercially used dienes like butadiene and isoprene. Nitroxide-mediated polymerization (NMP) is adept for the polymerization of dienes, but not particularly effective at controlling the polymerization of methacrylates using commercial nitroxides. In this study, Far is statistically copolymerized with a functional methacrylate, glycidyl methacrylate (GMA), by NMP using N-succinimidyl modified commercial BlocBuilder (NHS-BB) initiator. Reactivity ratios are determined to be r Far = ...

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“…In fact, since FDR is a by-product of the distillation of β-farnesene (PR 15), this polymer may arise during the process. Nevertheless, elsewhere, assays have successfully demonstrated the utilization of β-farnesene to produced biopolymers through anionic or cationic pathways [ 34 ] and involving redox reactions [ 35 ].…”

Section: Resultsmentioning

confidence: 99%

Phytosterols and Novel Triterpenes Recovered from Industrial Fermentation Coproducts Exert In Vitro Anti-Inflammatory Activity in Macrophages

et al. 2021

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The unstoppable growth of human population that occurs in parallel with all manufacturing activities leads to a relentless increase in the demand for resources, cultivation land, and energy. In response, currently, there is significant interest in developing strategies to optimize any available resources and their biowaste. While solutions initially focused on recovering biomolecules with applications in food, energy, or materials, the feasibility of synthetic biology in this field has been demonstrated in recent years. For instance, it is possible to genetically modify Saccharomyces cerevisiae to produce terpenes for commercial applications (i.e., against malaria or as biodiesel). But the production process, similar to any industrial activity, generates biowastes containing promising biomolecules (from fermentation) that if recovered may have applications in different areas. To test this hypothesis, in the present study, the lipid composition of by-products from the industrial production of β-farnesene by genetically modified Saccharomyces cerevisiae are studied to identify potentially bioactive compounds, their recovery, and finally, their stability and in vitro bioactivity. The assayed biowaste showed the presence of triterpenes, phytosterols, and 1-octacosanol which were recovered through molecular distillation into a single fraction. During the assayed stability test, compositional modifications were observed, mainly for the phytosterols and 1-octacosanol, probably due to oxidative reactions. However, such changes did not affect the in vitro bioactivity in macrophages, where it was found that the obtained fraction decreased the production of TNF-α and IL-6 in lipopolysaccharide (LPS)-induced inflammation.

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Synthesis and Characterization of Farnesene-Based Polymers

Cited by 40 publications

References 11 publications

Caryophyllene as a Precursor of Cross-Linked Materials

Caryophyllene as a Precursor of Cross-Linked Materials

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Phytosterols and Novel Triterpenes Recovered from Industrial Fermentation Coproducts Exert In Vitro Anti-Inflammatory Activity in Macrophages

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