Bio-Derived Isosorbide Methacrylate Has Excellent Properties Isosorbide methacrylate (IM) Lowest ever viscosity for methacrylate crosslinker IM has extremely low viscosity Low IM viscosity because of lack of H-bonding Highest ever Tg for a VE Resin! Sadler, J.M. et al. Journal of Materials Chemistry A, (2013) 1, 12579-12586 Eliminates need for volatile diluents Enables cheaper processing Enables use near engine components, etc. High temp epoxy performance at 1/10th cost

Pros and Cons of IM and Methacrylates IM has very high Tg IM has very low viscosity Cons All methacrylates require separations to remove unwanted by products This technology described herein eliminates the “Cons” of methacrylates

Typical Methacrylate Preparation + 4-DMAP + 40-60°C TEA, DCM + + HCl 0-25°C Separations step necessary to remove Solvent-aqueous liquid-liquid extraction generally required to extract HCl from methacrylate or to separate out methacrylic acid from methacrylate product. Separation process increases cost by factor of ~2.

Novel IM Methacrylate Preparation 4-DMAP + + 40-60°C AMC-2 or imidizole 70-95°C An epoxy is added to the IM/methacrylic acid mix. The epoxy and methacrylic acid react to form a mono-methacrylate reactive diluent. Method eliminates need for separation of methacrylic acid (or HCl) Reactive diluents are typically added to crosslinkers to help produce a well cured thermoset.

Use of other Alcohols Mono alcohols will produce reactive diluents + + 4-DMAP + 40-60°C + + AMC-2 or imidizole 70-95°C Mono alcohols will produce reactive diluents Diols will produce crosslinking agents Both will modify the resulting resin properties

Novel IM Methacrylate Preparation Mono epoxies produce reactive diluent Diepoxies react to produce dimethacrylate crosslinkers Use of mono- and di-epoxies allow tuning of the resin composition, crosslinker content, viscosity, and polymer properties.

IM + DGEBA and PGE Epoxy compound: Will consume methacrylic acid Will produce reactive diluents or crosslinkers that can copolymerize with IM Any epoxy compound can be used + Phenyl glycidyl ether (PGE) + + DGEBA or Epon AMC-2 or imidizole 70-95°C Vinyl ester of PGE (VE-PGE) + + Vinyl ester of DGEBA (VE)

Novel IM Preparation – Properties Baseline VE Method results in resins where low viscosities are achievable. Viscosities are tunable depending on the alcohols and epoxies used. IM + epoxy methacrylates made using new method Baseline IM IM + epoxy methacrylates made using new method Baseline IM Baseline VE Method results in polymers where high Tg is achievable. Tg is tunable depending on the alcohols and epoxies used. IM enables increased Tg with reduced viscosity!

Benefits and Applications Elimination of acid, tunable viscosity, and tunable polymer properties. Use of IM enables attainment of very high Tgs and low viscosities Reduces cost of the resins vs. that of pure IM or other methacrylate systems because method eliminates costly separation step. IM has low toxicity and is bio-derived Provides benefits for the following applications Composites – low viscosities allows resin flow through fibers. Higher Tg allows for higher temperature use. Adhesives – higher temperature applications. Additive manufacturing resins (stereolithography and ink jet printing) – IM is very beneficial in this application because it does not have phenolic rings that reduce rate and extent of cure during photo curing.