This communication describes recent developments in this laboratory directed towards the design of cationically polymerizable monomers from biorenewable sources. Three classes of ubiquitous biorenewable substrates were explored, namely: lipids, carbohydrates and terpenes. Considered in the synthesis and design were the cost and availability of the substrates, and the practicality and environmental acceptability of the chemical methodology. The polymerizations of the monomers were carried out using photoinitiated cationic polymerization.

SYNOPSISThe synthesis of 1,2,3-tris( 1-propen0xy)propane ( G T P E ) was carried out by the rearrangement of 1,2,3-tris( 2-propenoxy )propane (glycerol triallyl ether, GTAE) and the Z : E isomer composition of the GTPE was determined using gas chromatography and 'H-NMR. The photoinitiated cationic polymerization of the GTPE was studied using realtime infrared spectroscopy ( R T I R ) . Employing the data from these studies, rates of polymerization for the respective E and Z propenyl ether double bonds were calculated. The rate of incorporation of Z-double bonds of GTPE into the crosslinked polymer matrix is 1.6 times that of E-double bonds. The effects of oxygen and several other free radical polymerization inhibitors were investigated. An increase in the photogel time and decrease of the gel-content in the presence of these inhibitors implicates the involvement of free radicals in the process of the generation of propagating cationic centers when diaryliodonium salt cationic photoinitiators are used. 0 1994 John Wiley & Sons, Inc. Keywords: photopolymerization propenyl ethers cationic polymerization diaryliodonium salt triarylsulfonium salt free radicals inhibition 1,2,3-tris( 1-propen0xy)propane

SYNOPSISThe preparation of several novel mono-and dipropenyl and divinyl ethers derived from renewable starting materials is described using simple, straightforward synthetic methods. Utilizing real-time infrared spectroscopy, the reactivity of the monomers in photoinitiated cationic polymerization was studied employing diaryliodonium and triarylsulfonium salts as photoinitiators. The monomers were shown to undergo very rapid cationic photopolymerization.

SYNOPSISA series of aromatic monomers bearing cationically polymerizable propenyl groups were prepared and characterized using the readily available starting materials: isoeugenol and o-ally1 phenol. Monomers with both propenyl and vinyl ether functional groups were also synthesized by the reaction of these starting materials with chloroethyl vinyl ether. The reactivity of the resulting monomers in photoinitiated cationic polymerization was studied using differential scanning photocalorimetry and photogel point measurements. Their thermal properties were determined using thermogravimetric analysis. 0 1994 John Wiley & Sons, Inc.

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