Polyurethanes Specialties Polybenzoxazines New Chemistry Roger Tietze Robert

Polyurethanes & Specialties Polybenzoxazines : New Chemistry Roger Tietze Robert Kultzow Tim Truong

Presentation Huntsman Advanced Materials • • • Introduction Chemistry Material Properties Bisphenol A benzoxazine Conclusion Future Developments

Introduction Huntsman Advanced Materials 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 Huntsman Advanced Materials • 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 nonhalogen resin chemistry.

Polybenzoxazine Chemistry Huntsman Advanced Materials 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 othermosets • Excellent electrical properties

Benzoxazine Synthesis Huntsman Advanced Materials

XU 3560 Benzoxazine : Bisphenol A benzoxazine Huntsman Advanced Materials

Benzoxazine Polymerization Huntsman Advanced Materials

Benzoxazine/Epoxy Polymerization Huntsman Advanced Materials

Benzoxazine: Neat Resin Sample Preparation Huntsman Advanced Materials To test the properties of benzoxazines and othermosets, 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 Huntsman Advanced Materials Resin Type Cure LZ 8001 FR 4 bis A epoxy 1 hour @ 177°C MY 720/DDS High Tg epoxy 4 hour @ 200°C Arocy B 40 Cyanate Ester 4 hours @ 218°C BMI/DABA Polyimide 4 hours @ 218°C Polybenzoxazine A Benzoxazine 2 hours @ 200°C Polybenzoxazine B Benzoxazine 2 hours @ 200°C Polybenzoxazine C Benzoxazine 2 hours @ 200°C Polybenzoxazine D Benzoxazine 2 hours @ 200°C Polybenzoxazine E Benzoxazine 2 hours @ 200°C

Neat Resin Castings Huntsman Advanced Materials Resin Glass Transition Temperatures, °C LZ 8001 epoxy / Dicy 130°C – 140°C MY 720 / DDS 200°C Arocy B 40 240°C BMI Resin/DABA 240°C Polybenzoxazine A 160°C Polybenzoxazine B 155°C Polybenzoxazine C 250°C Polybenzoxazine D 170°C Polybenzoxazine E 200°C • TMA Analysis

UL 94 Testing : Neat Resin Huntsman Advanced Materials Resin 1 st Burn 2 nd. Burn Length Rating LZ 8001 / Dicy 8. 0 N/a Burn to clamp HB MY 720 / DDS 46. 0 N/a Burn to clamp HB Arocy B 40 15. 6 7. 8 3. 2 V 1 BMI Resin/DABA 51. 0 N/a Burn to clamp HB Polybenzoxazine A 31. 0 19. 2 4. 2 HB Polybenzoxazine B 28. 0 7. 2 2. 8 HB Polybenzoxazine C 4. 9 2. 0 0. 3 V 0 Polybenzoxazine D 5. 9 3. 9 2. 0 V 1 Polybenzoxazine E 2. 9 2. 4 1. 1 V 0 Note: Longest burn time recorded

Benzoxazine: Electrical Testing Huntsman Advanced Materials • Neat resin specimens : 0. 5” x 0. 5” • Neat resin specimen thickness : 2. 0 mm – 2. 5 mm • HP 4291 A RF Impedance/Material Analyzer • Linked to HP 16453 A 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 Huntsman Advanced Materials Neat Resin Sample DK Range Df Range LZ 8001 3. 5 – 3. 7 0. 020 – 0. 035 AER 4100 3. 5 – 3. 7 0. 020 – 0. 035 Arocy B 40 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 Huntsman Advanced Materials • • • Benzoxazines more flame resistant than epoxies Good electrical properties High glass transition temperatures

Typical Properties XU 3560 Huntsman Advanced Materials • • Visual appearance Melting point, °C Viscosity @ 125 C, cps Volatile, % DSC uncured • Initiation Temperature To, C • Peak Temperature Tg, C • H, J/g Yellow chunks 80 -85 185 ~2 231 241 238

Mechanical Properties Huntsman Advanced Materials *48 hrs boiling water

Formulations for XU 3560 Huntsman Advanced Materials

Novel High Performance Systems Huntsman Advanced Materials 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 Huntsman Advanced Materials 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.

Huntsman Advanced Materials Thank You Questions