Photoinitiated cationic polymerization of limonene 1,2‐oxide and α‐pinene oxide

Abstract

Limonene 1,2-oxide (LMO) and a-pinene oxide (a-PO) are two high reactivity biorenewable monomers that undergo facile photoinitiated cationic ring-opening polymerizations using both diaryliodonium salt and triarylsufonium salt photoinitiators. Comparative studies showed that a-PO is more reactive than LMO, and this is because it undergoes a simultaneous double ring-opening reaction involving both the epoxide group and the cyclobutane ring. It was also observed that a-PO also undergoes more undesirable side reactions than LMO. The greatest utility of these two monomers is projected to be as reactive diluents in crosslinking photocopolymerizations with multifunctional epoxide and oxetane monomers. Prototype copolymerization studies with several difunctional monomers showed that LMO and a-PO were effective in increasing the reaction rates and shortening the induction periods of photopolymerizations of these monomers.

Pinenes: Abundant and Renewable Building Blocks for a Variety of Sustainable Polymers

“…myrcene polymyrcene-PAMMS living anionic polymerization [83] pinene-lactamp olyamide cationic or anionic ROP [87,88] 4-isopropyl-caprolactone polyesterc oordination insertion ROP [90] a-pinene a-pinene poly-a-pinene cationic in IL [96,97] a-pinene oxide polyester tandem synthesis with dicarboxylic acids and anhydrides [94] pinocarvone pinene-based polyketone radical polymerization [98] Angewandte Chemie myrcene polymyrcene-PAMMS living anionic polymerization [83] pinene-lactamp olyamide cationic or anionic ROP [87,88] 4-isopropyl-caprolactone polyesterc oordination insertion ROP [90] a-pinene a-pinene poly-a-pinene cationic in IL [96,97] a-pinene oxide polyester tandem synthesis with dicarboxylic acids and anhydrides [94] pinocarvone pinene-based polyketone radical polymerization [98] Angewandte Chemie…”

“…[97] a-PO was shown to be more reactive then LO (also for side reactions), which was attributed to as imultaneous double ring-opening reaction involving both the epoxide ring and the cyclobutane ring. [97] a-PO was shown to be more reactive then LO (also for side reactions), which was attributed to as imultaneous double ring-opening reaction involving both the epoxide ring and the cyclobutane ring.…”

Catalytic isomerisation of α-pinene oxide in the presence of ETS-10 supported ferrocenium ions

“…Possibly, the chemical nature of the supported iron species changes and/or active sites are passivated by adsorption of reaction products. PinOx can undergo cationic ring-opening polymerisation to give ether polymers [48]. Table 1), suggesting that TFT is a more efficient solvent than hexane for the catalyst recovery.…”

Cationically UV-Cured Epoxy Composites

“…39 Research is being carried out to synthesize novel epoxies with different functionalities, not only to have diverse applications like thermally stable elastomers with improved chemical resistance, wetting agents, surfactants, and hydrophobic coatings, [40][41] but also to explore sustainable and renewable biomass-based raw materials. 42 Simultaneously, investigations are being carried out to develop photopolymerization process to address environmental concerns. [43][44][45] Epoxies are less photo-reactive than other commercial monomers like acrylates, but their charm is still due to their limited shrinkage (less than acrylics), which guarantees potential decrease in internal stress and appropriate adhesion property.…”