Polybenzoxazines : New Chemistry

1. Polybenzoxazines : New Chemistry Roger Tietze Robert Kultzow Tim Truong

2. Presentation • Introduction • Chemistry • Material Properties • Bisphenol A benzoxazine • Conclusion • Future Developments

3. Introduction Technology Origin: • Chemistry discovered in the 1930’s • Patent technology was acquired from a Swiss Research organization in the early 1990’s • Huntsman has modified and enhanced the scope of benzoxazine technology • Technology has been commercialized • Huntsman trade name : Azyrals

4. Chemistry • Benzoxazines are a unique non-halogen thermoset resin chemistry • These compounds can be synthesized from phenols, formaldehyde, and amines. • No halogen based precursors • Benzoxazines can homopolymerize to form a polybenzoxazine thermoset networks • Benzoxazines also co-cure with epoxies • Electronics PWB market has a need for a non-halogen resin chemistry.

5. Polybenzoxazine Chemistry Advantages • Potential low cost high performance thermoset • High purity resin system • High glass transition temperature • Low shrinkage • Low coefficient of thermal expansion • Better moisture resistance. • Better flammability resistance than epoxies and other thermosets • Excellent electrical properties

6. Benzoxazine Synthesis

7. XU3560 Benzoxazine : Bisphenol A benzoxazine

8. Benzoxazine Polymerization

9. Benzoxazine/Epoxy Polymerization

10. Benzoxazine: Neat Resin Sample Preparation • To test the properties of benzoxazines and other thermosets, neat resin samples were prepared by the following procedure: • Resins and hardeners are melted • Degassed • Poured into a mold • Cured with the appropriate cure cycle

11. Neat Resin Castings

12. Neat Resin Castings • TMA Analysis

13. UL94 Testing : Neat Resin Note: Longest burn time recorded

14. Benzoxazine: Electrical Testing • Neat resin specimens : 0.5” x 0.5” • Neat resin specimen thickness : 2.0 mm – 2.5 mm • HP4291A RF Impedance/Material Analyzer • Linked to HP 16453A Dielectric Material Test Fixture with a High Impedance Test Head • Calibration included the HP low loss capacitor • Frequency range : 1 MHz to 1.8 GHZ • Reported data range : 10 MHz – 1.5 GHZ

15. Benzoxazine: Electrical Properties of Neat Resins Frequency = 10 MHZ – 1.5 GHz

16. Neat Resin Results • Benzoxazines more flame resistant than epoxies • Good electrical properties • High glass transition temperatures

17. Visual appearance Yellow chunks Melting point, °C 80-85 Viscosity @ 125C, cps 185 Volatile, % ~2 DSC uncured Initiation Temperature To, C 231 Peak Temperature Tg, C 241 H, J/g 238 Typical PropertiesXU3560

18. Mechanical Properties *48hrs boiling water

19. Formulations for XU3560

20. Novel High Performance Systems Conclusions : • We have developed unique benzoxazine resins with commercially viable manufacturing processes. • These resins afford wide formulation latitude and can be formulated with epoxies, thermoplastics and catalysts to suit various applications and fabrication processes. • These resins are ideal for high performance composite, structural adhesive and printing wiring board (PWB) applications. • The benzoxazine/epoxy systems have high Tg°C, good thermal oxidation stability, low water pick-up, reduced shrinkage, good electrical, and are room temperature stable.

21. Benzoxazine Technology Current Status • Technology development work continues • New candidate products have been introduced for • Aerospace composite markets • High performance laminating markets • We have cooperative developments programs with Key customers • Qualifications in progress at major customers in both Electronic and Aerospace segments • Industrial applications are being explored • Manufacturing in place in North America and Europe. • Process development work to install manufacturing capability in Asia in the near future.

22. Thank You Questions