Renewable Polyethylene Mimics Derived from Castor Oil

Abstract

An increasing number of reports on the syntheses of carbohydrate- and plant oil-based polymers has been published in ongoing efforts to produce plastic materials from renewable resources. Although many of these polymers are biodegradable and this is a desirable property for certain applications, in some cases non-degradable polymers are needed for long-term use purposes. Polyolefins are one of the most important classes of materials that have already taken their places in our daily life. On the other hand, their production relies on fossil resources. Therefore, within this contribution, we discuss synthetic routes toward a number of polyethylene mimics derived from fatty acids via thiol-ene and ADMET polymerization reactions in order to establish more sustainable routes toward this important class of polymers. Two different diene monomers were thus prepared from castor oil derived platform chemicals, their polymerization via the two mentioned routes was optimized and compared to each other, and their thermal properties were investigated.

Chemo-enzymatic Synthesis, Derivatizations, and Polymerizations of Renewable Phenolic Monomers Derived from Ferulic Acid and Biobased Polyols: An Access to Sustainable Copolyesters, Poly(ester-urethane)s, and Poly(ester-alkenamer)s

“…Even though extensive research has been performed to develop commercial ferulic acid derived renewable polymers (22-35, 49, 59), only one example has been reported on ADMET polymerization involving ferulic acid derivatives as diene substrates. Indeed, Meier and co-workers reported on the use of a bisallylated ferulic acid derivative (2) as α,ω-diene monomer for the synthesis of renewable poly(ester-alkenamer)s (120). In their study, homopolymerization and copolymerization of 2 with oleic and erucic-derived α,ω-dienes resulted in polymers with molecular weights of 2-3 kDa and 9 kDa, respectively.…”

“…Thanks to the ease of handling and high functional group tolerance of the Ru-based catalysts used in acyclic diene metathesis (ADMET), this method is a very useful approach for the construction of defined polymer architectures (115) and allowed the synthesis of renewable polymers, such as polyesters, polyethers, polyamides and many others, very promising for commercial applications (41,(115)(116)(117)(118)(119)(120)(121)(122)(123)(124). Even though extensive research has been performed to develop commercial ferulic acid derived renewable polymers (22-35, 49, 59), only one example has been reported on ADMET polymerization involving ferulic acid derivatives as diene substrates.…”

Renewable sulfur-containing thermoplastics via AB-type thiol-ene polyaddition

“…reported the condensation of bifunctional thiols with bifunctional enes to prepare polyethylene mimicking polymers [25]. The molar masses of the reported AA/BB-type polymers were relatively limited.…”

Fatty Acid–Derived Aliphatic Long Chain Polyethers by a Combination of Catalytic Ester Reduction and ADMET or Thiol‐Ene Polymerization

“…Many examples of thiol‐ene polymerizations of long‐chain α,ω‐unsaturated monomers are described already . Typically, two different types of initiation are differentiated: thermal or UV‐initiation.…”

“…Here, we expand the concept of catalytic ester reduction for polymer synthesis to a set of six different ω,ω′ ‐unsaturated ether monomers, which were obtained from fatty acid–derived raw materials. In comparison to previous publications on ADMET and thiol‐ene polymerizations of fatty acid–derived substrates, of which only very few discuss ether monomers, here we describe a broader spectrum of monomers. Moreover, methyl‐THF is introduced for the first time in thiol‐ene polymerizations as more sustainable solvent and polarclean, which was shown by H. Cramail et al.…”