Polybenzoxazines : New Chemistry Roger Tietze Robert Kultzow Tim Truong

Presentation Introduction Chemistry Material Properties Bisphenol A benzoxazine Conclusion Future Developments

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

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.

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

Benzoxazine Synthesis

XU3560 Benzoxazine : Bisphenol A benzoxazine

Benzoxazine Polymerization

Benzoxazine/Epoxy Polymerization

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

Neat Resin Castings Resin Type Cure LZ8001 FR4 bis A epoxy 1 hour @ 177°C MY720/DDS High Tg epoxy 4 hour @ 200°C Arocy B40 Cyanate Ester 4 hours @ 218°C BMI/DABA Polyimide Polybenzoxazine A Benzoxazine 2 hours @ 200°C Polybenzoxazine B Polybenzoxazine C Polybenzoxazine D Polybenzoxazine E

Glass Transition Temperatures, °C Neat Resin Castings Resin Glass Transition Temperatures, °C LZ8001 epoxy / Dicy 130°C – 140°C MY720 / DDS  200°C Arocy B40  240°C BMI Resin/DABA Polybenzoxazine A 160°C Polybenzoxazine B 155°C Polybenzoxazine C 250°C Polybenzoxazine D 170°C Polybenzoxazine E 200°C TMA Analysis

UL94 Testing : Neat Resin Note: Longest burn time recorded Resin 2ndBurn Length Rating LZ8001 / Dicy 8.0 N/a Burn to clamp HB MY720 / DDS 46.0 Arocy B40 15.6 7.8 3.2 V1 BMI Resin/DABA 51.0 Polybenzoxazine A 31.0 19.2 4.2 Polybenzoxazine B 28.0 7.2 2.8 Polybenzoxazine C 4.9 2.0 0.3 V0 Polybenzoxazine D 5.9 3.9 Polybenzoxazine E 2.9 2.4 1.1 Note: Longest burn time recorded

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

Benzoxazine: Electrical Properties of Neat Resins Neat Resin Sample DK Range Df Range LZ8001 3.5 – 3.7 0.020 – 0.035 AER4100 Arocy B40 2.80 – 2.97 0.0050 – 0.0090 Polybenzoxazine A 3.00 – 3.15 0.0060 – 0.0100 Polybenzoxazine B 3.15 – 3.30 0.0070 –0.0110 Polybenzoxazine C 3.45 – 3.60 0.0070 – 0.0090 Polybenzoxazine D 3.40 – 3.45 0.0065 – 0.0085 Frequency = 10 MHZ – 1.5 GHz

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

Typical Properties XU3560 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

Mechanical Properties *48hrs boiling water

Formulations for XU3560

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.

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.

Thank You Questions