Terpene and Dextran Renewable Resources for the Synthesis of Amphiphilic Biopolymers

Abstract

The present work shows the synthesis of amphiphilic polymers based on the hydrophilic dextran and the hydrophobic terpenes as renewable resources. The first step concerns the synthesis of functional terpene molecules by thiol-ene addition chemistry involving amino or carboxylic acid thiols and dihydromyrcenol terpene. The terpene-modified polysaccharides were subsequently synthesized by coupling the functional terpenes with dextran. A reductive amination step produced terpene end-modified dextran with 94% of functionalization, while the esterification step produced three terpene-grafted dextrans with a number of terpene units per dextran of 1, 5, and 10. The amphiphilic renewable grafted polymers were tested as emulsifiers for the stabilization of liquid miniemulsion of terpene droplets dispersed in an aqueous phase. The average hydrodynamic diameter of the stable droplets was observed at about 330 nm.

Terpene- and terpenoid-based polymeric resins for stereolithography 3D printing

“…The thiol-ene 'click' reaction between limonene and various thiols has been discussed in a number of different publications previously. 31 In our hands, however, while the 1 H NMR spectroscopic analysis of the product of the reaction between PETMP and limonene confirmed the preferential addition of the thiol to the exocyclic alkene (in preference to the endocyc- lic alkene), in contrast to the observation of chemoselective addition to the exocyclic alkene observed by Firdaus et al, 30 our results indicate that about 27% of the endo-alkene moieties react with the thiol compared to 93% of the exo-alkene species (ESI Table 1 †). Extension of this study to other terpenes revealed that in linalool, the addition of thiols was more evenly distributed between the alkenes with 93% tri-substituted alkene and 80% di-substituted alkene consumed (ESI Table S2, Fig.…”

“…[19][20][21][22] This class of monomer is widely available, and may be found in essential oils, tree sap and materials, citrus fruit, and even as by-products from other manufacturing processes, such as the paper industry's Kraft process, or simply through the processing of citrus fruits and other renewable resources. [23][24][25][26] The inherent double bonds present in mono-, di-, tri-, and other polyterpenes make them excellent candidates for the creation of sustainably-sourced photo-crosslinkable resins, yet to date only a few studies have investigated their application beyond utilizing appended (meth)acrylate or epoxide functionalities for (controlled) radical polymerisation 27,[28][29][30] modified polysaccharides, 31 polycarbonates, 32 and even polysilanes, 33 with processing still being limited in such studies. Herein, we report our study of the application of five terpenes: limonene, terpinene, geraniol, nerol and linalool ( Fig.…”

Synthesis, characterization and properties of a bio-based elastomer: polymyrcene

“…4 On the other hand, terpenes or terpenoids refer to one of the largest families of naturally occurring compounds and are secondary metabolites synthesized mainly by plants, particularly conifers. 8 To make use of the chemical functionalities (unsaturation, functional groups) present in terpene molecules, various chemical strategies and a wide range of polymerisation techniques [9][10][11][12][13][14][15][16][17][18][19] had been studied. Thus, due to their abundance in nature, there has been great interest in producing polymers with terpenes as either functional entities or as the main constituent.…”

Thiol–Ene (Click) Reactions as Efficient Tools for Terpene Modification

“…45–97 %), and β‐pinene (ca. 0.5–28 %), are useful raw materials that are industrially converted into value‐added compounds through a variety of chemical modifications . Besides pinenes, limonene, a cyclic diene monoterpene, is also a valuable compound that is typically obtained from citrus peel .…”

“…Amphiphilic polymers have been prepared from the combination of two renewable starting materials, hydrophilic dextran and hydrophobic terpenes . The initial step involved a quantitative thiol–ene addition of cysteamine hydrochloride or 3‐mercaptopropionic acid to dihydromyrcenol ( 31 ) by using AIBN as a thermal initiator, thereby affording two kinds of terpenes that contain an amino group ( 32 ) or a carboxylic acid group ( 33 ; Scheme ).…”