A ‘greener’ one-pot synthesis of monoterpene-functionalised lactide oligomers

RAFT polymerisation of renewable terpene (meth)acrylates and the convergent synthesis of methacrylate–acrylate–methacrylate triblock copolymers

“…Some of these T g values are slightly higher than those reported by Sainz et al 18 This is because some of the polymers had higher molecular weights and additionally, the materials were analysed using dynamic mechanical analysis (DMA), which is known to slightly increase T g compared to DSC. 37 PαPMA and PβPMA are clear choices for a high T g hard block with values of 168 and 121°C respectively, while PLiA has the lowest T g at −3°C, so could be utilised as a soft block. PβPA exhibited a T g of 41°C at 27 000 g mol −1 , but it was reported in further work by Sainz, 38 that for a lower M n of 4200 g mol −1 , the T g was decreased to −8°C, 38 opening up the use of short lengths of PβPA as a soft block.…”

2‐Methyltetrahydrofuran (2‐MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP, FRP, and RAFT tandem polymerizations

“…[11] Previously we demonstrated the suitability of 2-MeTHF for ROP process producing a library of PDLLAbased oligomers initiated by terpene-alcohols, achieving a totally sustainable chemical process. [9] In the present work, we are interested to expand upon this and assess the ability of 2-MeTHF as a "multipolymerization" solvent, allowing multiple and tandem reactions in similar conditions to produce common polymeric products and make green synthesis more accessible. To further reduce the environmental burden related to the synthesis of these pharmaceutical-grade polymers, we also explored 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU) and Candida antarctica lipase B, also known as Nomozym 435 (lipase), as metal-free low-temperature catalysts for all the ROP reactions.…”

“…In addition, it exhibits a higher boiling point compared to DCM, THF, and other cyclic solvents, which can allow for reactions to be conducted at a higher temperature, giving access to thermally initiated radical processes under ambient pressure. A further advantage is that 2‐MeTHF shows a lower critical solution temperature with water, [ 9 ] minimizing the effects of hydrolytic initiation caused by contaminant water, a crucial limitation in ROP synthesis. At the laboratory scale, the cost of 2‐MeTHF is comparable to that of conventional solvents and can be expected to decrease with the economy of scale‐up.…”

Synthesis of novel carvone (meth)acrylate monomers for the production of hydrophilic polymers with high terpene content

“…When trans-sobrerol was used, the final nanoaggregates were more stable than those derived from limonene due to the presence of the free hydroxyl group. 16 In order to develop hydrophilic terpene-based polymers we focused on carvone as a primary feedstock. In fact, of all the terpene-based (meth)acrylate monomers previously proposed, 13 the carvones are the most promising because they possess two functionalisable double bonds offering the potential for introducing the maximum number of hydrophilic groups per molecule (Scheme 1) through epoxidation.…”

“…The resulting materials showed good ability to self‐assemble into micelles in water. When trans‐sobrerol was used, the final nanoaggregates were more stable than those derived from limonene due to the presence of the free hydroxyl group 16 …”