Polymerization of terpenes and terpenoids using metal catalysts

Palenzuela, Miguel; Sánchez-Roa, David; Damián, Jesús; Sessini, Valentina; Mosquera, Marta E.G.

doi:10.1016/bs.adomc.2021.01.004

Cited by 9 publications

(6 citation statements)

References 127 publications

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“…By no means these multifunctional molecules and are strong candidates to become platform chemicals. However [68,69], one area that has been less explored is their use as monomers [70] to create bio-based polymers and copolymers. This is surprising, as some polyterpenes have been known for a long time such as the case of natural rubber (cis-1,4-polyisoprene) which is a natural terpene-based polymer.…”

Section: Polymerization Of Terpenes and Terpenoidsmentioning

confidence: 99%

Terpenes and Terpenoids: Building Blocks to Produce Biopolymers

Mosquera

Jiménez

Tabernero

et al. 2021

Sustainable Chemistry

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Polymers are essential materials in our daily life. The synthesis of value-added polymers is mainly performed from fossil fuel-derived monomers. However, the adoption of the circular economy model based on the bioeconomy will reduce the dependence on fossil fuels. In this context, biorefineries have emerged to convert biomass into bioenergy and produce high value-added products, including molecules that can be further used as building blocks for the synthesis of biopolymers and bioplastics. The achievement of catalytic systems able to polymerize the natural monomer counterparts, such as terpenes or terpenoids, is still a challenge in the development of polymers with good mechanical, thermal, and chemical properties. This review describes the most common types of bioplastics and biopolymers and focuses specifically on the polymerization of terpenes and terpenoids, which represent a source of promising monomers to create bio-based polymers and copolymers.

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Section: Polymerization Of Terpenes and Terpenoidsmentioning

confidence: 99%

Terpenes and Terpenoids: Building Blocks to Produce Biopolymers

Mosquera

Jiménez

Tabernero

et al. 2021

Sustainable Chemistry

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“…(see e.g., Refs. [ 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 ] and references therein). Beyond doubt, β-pinene, which is the most abundant commercial terpene and is obtained from turpentine, belongs to a special class of natural olefins with a bicyclic substituent [ 25 , 26 ].…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Cationic Polymerization of β-Pinene, a Bio-Based, Renewable Olefin, with TiCl4 Catalyst from Cryogenic to Energy-Saving Room Temperature Conditions

Verebélyi

Szabó

Réti

et al. 2023

IJMS

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Polymers based on renewable monomers are projected to have a significant role in the sustainable economy, even in the near future. Undoubtedly, the cationically polymerizable β-pinene, available in considerable quantities, is one of the most promising bio-based monomers for such purposes. In the course of our systematic investigations related to the catalytic activity of TiCl4 on the cationic polymerization of this natural olefin, it was found that the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4/N,N,N′,N′-tetramethylethylenediamine (TMEDA) initiating system induced efficient polymerization in dichloromethane (DCM)/hexane (Hx) mixture at both −78 °C and room temperature. At −78 °C, 100% monomer conversion was observed within 40 min, resulting in poly(β-pinene) with relatively high Mn (5500 g/mol). The molecular weight distributions (MWD) were uniformly shifted towards higher molecular weights (MW) in these polymerizations as long as monomer was present in the reaction mixture. However, chain–chain coupling took place after reaching 100% conversion, i.e., under monomer-starved conditions, resulting in considerable molecular weight increase and MWD broadening at −78 °C. At room temperature, the polymerization rate was lower, but chain coupling did not occur. The addition of a second feed of monomer in the polymerization system led to increasing conversion and polymers with higher MWs at both temperatures. 1H NMR spectra of the formed polymers indicated high in-chain double-bond contents. To overcome the polarity decrease by raising the temperature, polymerizations were also carried out in pure DCM at room temperature and at −20 °C. In both cases, rapid polymerization occurred with nearly quantitative yields, leading to poly(β-pinene)s with Mns in the range of 2000 g/mol. Strikingly, polymerization by TiCl4 alone, i.e., without any additive, also occurred with near complete conversion at room temperature within a few minutes, attributed to initiation by adventitious protic impurities. These results convincingly prove that highly efficient carbocationic polymerization of the renewable β-pinene can be accomplished with TiCl4 as catalyst under both cryogenic conditions, applied widely for carbocationic polymerizations, and the environmentally benign, energy-saving room temperature, i.e., without any additive and cooling or heating. These findings enable TiCl4-catalyzed eco-friendly manufacturing of poly(β-pinene)s, which can be utilized in various applications, and in addition, subsequent derivatizations could result in a range of high-added-value products.

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“…Terpenes and terpenoids represent one of the largest families of natural products with a wide structural diversity that can be employed for many applications. 10 From a structural point of view, terpenes contain at least one double bond in their structure and can be considered derivatives of isoprene. These functionalized molecules can be easily derivatized to introduce new functional groups for use in polymerization and other reactions.…”

Section: Introductionmentioning

confidence: 99%