Biobased Plastics and Elastomers from Renewable Rosin via “Living” Ring-Opening Metathesis Polymerization

Abstract

Utilization of biomass for commodity polymers has gained tremendous interest. We report a method to prepare high molecular weight renewable homopolymers and block copolymers derived from natural rosin. Monomers with high renewable content (70 wt %) were prepared via a simple esterification reaction between dehydroabietic alcohol and 5exo-norbornenecarboxylic acid. Living and controlled polymerization of these monomers were achieved by ring-opening metathesis polymerization to obtain polymers with molecular weight up to ∼500 kg/mol. These homopolymers exhibit structure-dependent glass transition temperatures, excellent thermal stabilities, and thermoplastic properties. Chain entanglement molecular weight was determined via rheological assessments for such polymers with bulky side moieties. Using the living ROMP, dehydroabietic-based homopolymer was chainextended with a soybean oil-derived norbornene monomer to yield triblock copolymers, which showed behaviors of thermoplastic elastomers.

Sustainable rubbers and rubber additives

“…Ganewatta et al . prepared thermoplastic elastomers from natural rosin and modified vegetable oil, and discussed other sustainable elastomers from renewable biomass . Plant based phenolic acids with varying functionalities were utilized to prepare thiol‐ene elastomers using a photoinitiator …”

Impact of supramolecular interactions on swelling and release behavior of UPy functionalized HEMA‐based hydrogels

“…They showed that TPEs with high elastic recovery could be developed by using these novel monomers. 18 Similarly, supramolecular TPEs owe their bulk properties to the, so called, microphase separation between the hard and the soft domains in the structure, where hard domains are usually formed by inclusion of H-bonding modules (as an example of supramolecular interactions) within the polymer backbones. Therefore, polymer properties can be tailored with aptly selection of hydrogen bonding motifs such as ureidopyrimidinone (UPy, a quadruple H-bonding motif), which is easily introduced into polymer chains either as end-groups or as pending groups (K dim = 6 × 10 7 M −1 in chloroform) with strong tendency to form H-bonds through a quadruple array of H-bonding donors and acceptors (DDAA).…”

“…Next these high‐Tg polymers were used to design TPEs with a soft middle block derived from soybean oil. They showed that TPEs with high elastic recovery could be developed by using these novel monomers . Similarly, supramolecular TPEs owe their bulk properties to the, so called, microphase separation between the hard and the soft domains in the structure, where hard domains are usually formed by inclusion of H‐bonding modules (as an example of supramolecular interactions) within the polymer backbones.…”

Reduction of liquid terminated-carboxyl fluoroelastomers using NaBH4/SmCl3

“…[9][10][11][12] Because in contrast to ketones, 13 aldehydes 14 and esters, 15 which easily engage in reactions with reductive agents, carboxylic acids are generally unreactive. 16 On the other hand, although lithium aluminium hydride was widely used as a strong reductant in carboxyl reduction, 17 its poor chemical selectivity, ammability and explosive nature are unfavorable for large-scale production. Kamochi and Kudo reported the reduction of aryl carboxylic acid derivatives and some aliphatic carboxylic acids using SmI 2 , 18,19 however this strategy was low yielding and limited in scope for aliphatic carboxylic acids.…”