1. 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,
Eliminates need for volatile diluents
Enables cheaper processing
Enables use near engine components, etc.
High temp epoxy performance at 1/10th cost

2. 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

3. 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.

4. 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.

5. 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

6. 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.

7. 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)

8. 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!

9. 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.