Polybenzoxazines : New Chemistry

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Polybenzoxazines New Chemistry

• Roger Tietze
• Robert Kultzow
• Tim Truong

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Presentation

• Introduction
• Chemistry
• Material Properties
• Bisphenol A benzoxazine
• Conclusion
• Future Developments

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Introduction

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

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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.

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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

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Benzoxazine Synthesis
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XU3560 Benzoxazine Bisphenol A benzoxazine
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Benzoxazine Polymerization
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Benzoxazine/Epoxy Polymerization
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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

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Neat Resin Castings
Resin Type Cure
LZ8001 FR4 bis A epoxy 1 hour _at_ 177C
MY720/DDS High Tg epoxy 4 hour _at_ 200C
Arocy B40 Cyanate Ester 4 hours _at_ 218C
BMI/DABA Polyimide 4 hours _at_ 218C
Polybenzoxazine A Benzoxazine 2 hours _at_ 200C
Polybenzoxazine B Benzoxazine 2 hours _at_ 200C
Polybenzoxazine C Benzoxazine 2 hours _at_ 200C
Polybenzoxazine D Benzoxazine 2 hours _at_ 200C
Polybenzoxazine E Benzoxazine 2 hours _at_ 200C
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Neat Resin Castings
Resin Glass Transition Temperatures, C
LZ8001 epoxy / Dicy 130C 140C
MY720 / DDS ? 200C
Arocy B40 ? 240C
BMI Resin/DABA ? 240C
Polybenzoxazine A 160C
Polybenzoxazine B 155C
Polybenzoxazine C 250C
Polybenzoxazine D 170C
Polybenzoxazine E 200C

• TMA Analysis

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UL94 Testing Neat Resin
Resin 1st Burn 2ndBurn Length Rating
LZ8001 / Dicy 8.0 N/a Burn to clamp HB
MY720 / DDS 46.0 N/a Burn to clamp HB
Arocy B40 15.6 7.8 3.2 V1
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 V0
Polybenzoxazine D 5.9 3.9 2.0 V1
Polybenzoxazine E 2.9 2.4 1.1 V0
Note Longest burn time recorded
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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

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Benzoxazine Electrical Properties of Neat Resins
Neat Resin Sample DK Range Df Range
LZ8001 3.5 3.7 0.020 0.035
AER4100 3.5 3.7 0.020 0.035
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
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Neat Resin Results

• Benzoxazines more flame resistant than epoxies
• Good electrical properties
• High glass transition temperatures

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Typical Properties XU3560

• Visual appearance Yellow chunks
• Melting point, C 80-85
• Viscosity _at_ 125?C, cps 185
• Volatile, 2
• DSC uncured
• Initiation Temperature To, ?C 231
• Peak Temperature Tg, ?C 241
• ?H, J/g 238

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Mechanical Properties
48hrs boiling water
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Formulations for XU3560
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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 TgC,
  good thermal oxidation stability, low water
  pick-up, reduced shrinkage, good electrical, and
  are room temperature stable.

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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.

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• Thank You
• Questions