A series of renewable bis(cyanate) esters have been prepared from bisphenols synthesized by condensation of 2-methoxy-4-methylphenol (creosol) with formaldehyde, acetaldehyde, and propionaldehyde. The cyanate esters have been fully characterized by infrared spectroscopy, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. These compounds melt from 88 to 143 °C, while cured resins have glass transition temperatures from 219 to 248 °C, water uptake (96 h, 85 °C immersion) in the range of 2.05-3.21%, and wet glass transition temperatures from 174 to 193 °C. These properties suggest that creosol-derived cyanate esters may be useful for a wide variety of military and commercial applications. The cure chemistry of the cyanate esters has been studied with FTIR spectroscopy and differential scanning calorimetry. The results show that cyanate esters with more sterically demanding bridging groups cure more slowly, but also more completely than those with a bridging methylene group. In addition to the structural differences, the purity of the cyanate esters has a significant effect on both the cure chemistry and final Tg of the materials. In some cases, post-cure of the resins at 350 °C resulted in significant decomposition and off-gassing, but cure protocols that terminated at 250-300 °C generated void-free resin pucks without degradation. Thermogravimetric analysis revealed that cured resins were stable up to 400 °C and then rapidly degraded. TGA/FTIR and mass spectrometry results showed that the resins decomposed to phenols, isocyanic acid, and secondary decomposition products, including CO2. Char yields of cured resins under N2 ranged from 27 to 35%, while char yields in air ranged from 8 to 11%. These data suggest that resins of this type may potentially be recycled to parent phenols, creosol, and other alkylated creosols by pyrolysis in the presence of excess water vapor. The ability to synthesize these high temperature resins from a phenol (creosol) that can be derived from lignin, coupled with the potential to recycle the composites, provides a possible route to the production of sustainable, high-performance, thermosetting resins with reduced environmental impact.

Renewable phenols derived from biomass sources often contain methoxy groups that alter the properties of derivative polymers. To evaluate the impact of o-methoxy groups on the performance characteristics of cyanate ester resins, three bisphenols derived from the renewable phenol creosol were deoxygenated by conversion to ditriflates followed by palladium-catalyzed elimination and hydrolysis of the methoxy groups. The deoxygenated bisphenols were then converted to the following cyanate ester resins: bis(4-cyanato-2-methylphenyl)methane (16), 4,4′-(ethane-1,1′-diyl)bis(1-cyanato-3-methylbenzene) (17), and 4,4′-(propane-1,1′-diyl)bis-(1-cyanato-3-methylbenzene) (18). The physical properties, cure chemistry, and thermal stability of these resins were evaluated and compared to those of cyanate esters derived from the oxygenated bisphenols. 16 and 18 had melting points 37 and >95°C lower, respectively, than the oxygenated versions, while 17 had a melting point 14°C higher. The T g 's of thermosets generated from the deoxygenated resins ranged from 267 to 283°C, up to 30°C higher than the oxygenated resins, while the onset of thermal degradation was 50−80°C higher. The deoxygenated resins also exhibited water uptakes up to 43% lower and wet T g s up to 37°C higher than the oxygenated resins. TGA-FTIR of thermoset networks derived from 16−18 revealed a different decomposition mechanism compared to the oxygenated resins. Instead of a low-temperature pathway that resulted in the evolution of phenolic compounds, 16−18 had significantly higher char yields and decomposed via evolution of small molecules including isocyanic acid, CH 4 , CO 2 , and NH 3 .

A renewable bisphenol, 4,4'-(butane-1,4-diyl)bis(2-methoxyphenol), was synthesized on a preparative scale by a solvent-free, Ru-catalyzed olefin metathesis coupling reaction of eugenol followed by hydrogenation. After purification, the bisphenol was converted to a new bis(cyanate) ester by standard techniques. The bisphenol and cyanate ester were characterized rigorously by NMR spectroscopy and single-crystal X-ray diffraction studies. After complete cure, the cyanate ester exhibited thermal stability in excess of 350 °C and a glass transition temperature (Tg ) of 186 °C. As a result of the four-carbon chain between the aromatic rings, the thermoset displayed a water uptake of only 1.8% after a four day immersion in 85 °C water. The wet Tg of the material (167 °C) was only 19 °C lower than the dry Tg , and the material showed no significant degradation as a result of the water treatment. These results suggest that this resin is well suited for maritime environments and provide further evidence that full-performance resins can be generated from sustainable feedstocks.

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Studies of the physical properties of the cocured networks formed from three similar dicyanate ester monomers revealed a number of unexpected variations from simple linear mixing rules. These variations shed light on important synergistic effects in cocured thermosetting networks and their possible causes. The monomers utilized were the dicyanate esters of Bisphenol A (BADCy) and Bisphenol E (LECy) and the silicon-containing analogue of Bisphenol A (SiMCy). The most important of the synergistic effects was a decrease of ∼25% in moisture uptake seen only in conetworks of LECy and SiMCy. For all other systems, a clear relationship between moisture uptake and the number density of cyanurate rings was observed. This relationship generally applies to many types of cyanate esters and gives an indication of the importance of specific sites (as opposed to free volume alone) in moisture uptake. Numerous additional examples of nonlinear mixing relations were observed in the glass transition temperature, density, and thermochemical stability of fully cured networks. Interestingly, the most widespread deviations from linear behavior were observed for conetworks of SiMCy and LECy, suggesting that factors such as the mismatch in network segment size may be more important than differences in flexibility or symmetry in driving significant physical interactions among conetwork components.