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

Polyurethanes & Specialties

Polybenzoxazines : New ChemistryPolybenzoxazines : New Chemistry

Roger TietzeRoger Tietze

Robert KultzowRobert Kultzow

Tim TruongTim Truong

Huntsman Advanced Materials

PresentationPresentation

• IntroductionIntroduction• ChemistryChemistry• Material PropertiesMaterial Properties• Bisphenol A benzoxazineBisphenol A benzoxazine• ConclusionConclusion• Future DevelopmentsFuture Developments


IntroductionIntroduction

Technology Origin:Technology Origin:

• Chemistry discovered in the 1930’sChemistry discovered in the 1930’s• Patent technology was acquired from a Swiss Patent technology was acquired from a Swiss

Research organization in the early 1990’sResearch organization in the early 1990’s• Huntsman has modified and enhanced the scope of Huntsman has modified and enhanced the scope of

benzoxazine technologybenzoxazine technology• Technology has been commercializedTechnology has been commercialized• Huntsman trade name : Azyrals Huntsman trade name : Azyrals


ChemistryChemistry

• Benzoxazines are a unique non-halogen thermoset Benzoxazines are a unique non-halogen thermoset resin chemistryresin chemistry

• These compounds can be synthesized from phenols, These compounds can be synthesized from phenols, formaldehyde, and amines.formaldehyde, and amines.

• No halogen based precursorsNo halogen based precursors• Benzoxazines can homopolymerize to form a Benzoxazines can homopolymerize to form a

polybenzoxazine thermoset networkspolybenzoxazine thermoset networks• Benzoxazines also co-cure with epoxiesBenzoxazines also co-cure with epoxies• Electronics PWB market has a need for a non-Electronics PWB market has a need for a non-

halogen resin chemistry.halogen resin chemistry.


Polybenzoxazine ChemistryPolybenzoxazine Chemistry

AdvantagesAdvantages• Potential low cost high performance thermosetPotential low cost high performance thermoset• High purity resin systemHigh purity resin system• High glass transition temperatureHigh glass transition temperature• Low shrinkageLow shrinkage• Low coefficient of thermal expansionLow coefficient of thermal expansion• Better moisture resistance.Better moisture resistance.• Better flammability resistance than epoxies and other Better flammability resistance than epoxies and other

thermosetsthermosets• Excellent electrical properties Excellent electrical properties


Benzoxazine Synthesis

O H R3

R2

R1

H H

O N H 2 R4

N

O

R4

R3

R2

R1

-2H 2 O

2 x + +


XU3560 Benzoxazine : XU3560 Benzoxazine : Bisphenol A benzoxazineBisphenol A benzoxazine

CH3

CH3

O O

NN


Benzoxazine PolymerizationBenzoxazine Polymerization

N

OO

N

O

O

H

H

R1

R1

O

O

H

H

N

O

O

H

H

N

N N

R1

R1

Heat


O

OR2

"O

O

N

OO

N

O

OO

R2"

O

O

OO

R2"

O

OH

R1

R1

O

O

H

N

OH

N

N N

R1

R1

OO

R2"

O

H H H

Catalyst

Heat

+

Epoxy

Benzoxazine/Epoxy PolymerizationBenzoxazine/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

ResinResin TypeType CureCure

LZ8001LZ8001 FR4 bis A epoxyFR4 bis A epoxy 1 hour @ 177°C1 hour @ 177°C

MY720/DDSMY720/DDS High Tg epoxyHigh Tg epoxy 4 hour @ 200°C4 hour @ 200°C

Arocy B40Arocy B40 Cyanate EsterCyanate Ester 4 hours @ 218°C4 hours @ 218°C

BMI/DABABMI/DABA PolyimidePolyimide 4 hours @ 218°C4 hours @ 218°C

Polybenzoxazine APolybenzoxazine A BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C

Polybenzoxazine BPolybenzoxazine B BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C

Polybenzoxazine CPolybenzoxazine C BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C

Polybenzoxazine DPolybenzoxazine D BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C

Polybenzoxazine EPolybenzoxazine E BenzoxazineBenzoxazine 2 hours @ 200°C2 hours @ 200°C


Neat Resin CastingsNeat Resin Castings

ResinResin Glass Transition Temperatures, °CGlass Transition Temperatures, °C

LZ8001 epoxy / DicyLZ8001 epoxy / Dicy 130°C – 140°C130°C – 140°C

MY720 / DDSMY720 / DDS 200°C200°C

Arocy B40Arocy B40 240°C240°C

BMI Resin/DABABMI Resin/DABA 240°C240°C

Polybenzoxazine APolybenzoxazine A 160°C160°C

Polybenzoxazine BPolybenzoxazine B 155°C155°C

Polybenzoxazine CPolybenzoxazine C 250°C250°C

Polybenzoxazine DPolybenzoxazine D 170°C170°C

Polybenzoxazine EPolybenzoxazine E 200°C200°C

• TMA Analysis


UL94 Testing : Neat ResinUL94 Testing : Neat Resin

ResinResin 11stst Burn Burn 22ndndBurnBurn LengthLength RatingRating

LZ8001 / DicyLZ8001 / Dicy 8.08.0 N/aN/a Burn to clampBurn to clamp HBHB

MY720 / DDSMY720 / DDS 46.046.0 N/aN/a Burn to clampBurn to clamp HBHB

Arocy B40Arocy B40 15.615.6 7.87.8 3.23.2 V1V1

BMI Resin/DABABMI Resin/DABA 51.051.0 N/aN/a Burn to clampBurn to clamp HBHB

Polybenzoxazine APolybenzoxazine A 31.031.0 19.219.2 4.24.2 HBHB

Polybenzoxazine BPolybenzoxazine B 28.028.0 7.27.2 2.82.8 HBHB

Polybenzoxazine CPolybenzoxazine C 4.94.9 2.02.0 0.30.3 V0V0

Polybenzoxazine DPolybenzoxazine D 5.95.9 3.93.9 2.02.0 V1V1

Polybenzoxazine EPolybenzoxazine E 2.92.9 2.42.4 1.11.1 V0V0

Note: Longest burn time recorded


Benzoxazine: Electrical TestingBenzoxazine: Electrical Testing

• Neat resin specimens : 0.5” x 0.5” Neat resin specimens : 0.5” x 0.5”

• Neat resin specimen thickness : 2.0 mm – 2.5 mmNeat resin specimen thickness : 2.0 mm – 2.5 mm

• HP4291A RF Impedance/Material AnalyzerHP4291A RF Impedance/Material Analyzer

• Linked to HP 16453A Dielectric Material Test Linked to HP 16453A Dielectric Material Test Fixture with a High Impedance Test HeadFixture with a High Impedance Test Head

• Calibration included the HP low loss capacitorCalibration included the HP low loss capacitor

• Frequency range : 1 MHz to 1.8 GHZFrequency range : 1 MHz to 1.8 GHZ

• Reported data range : 10 MHz – 1.5 GHZReported data range : 10 MHz – 1.5 GHZ


Benzoxazine: Electrical Properties of Benzoxazine: Electrical Properties of Neat ResinsNeat Resins

Neat Resin SampleNeat Resin Sample DK RangeDK Range Df RangeDf Range

LZ8001LZ8001 3.5 – 3.73.5 – 3.7 0.020 – 0.0350.020 – 0.035

AER4100AER4100 3.5 – 3.73.5 – 3.7 0.020 – 0.0350.020 – 0.035

Arocy B40Arocy B40 2.80 – 2.972.80 – 2.97 0.0050 – 0.00900.0050 – 0.0090

Polybenzoxazine APolybenzoxazine A 3.00 – 3.153.00 – 3.15 0.0060 – 0.01000.0060 – 0.0100

Polybenzoxazine BPolybenzoxazine B 3.15 – 3.303.15 – 3.30 0.0070 –0.01100.0070 –0.0110

Polybenzoxazine CPolybenzoxazine C 3.45 – 3.603.45 – 3.60 0.0070 – 0.00900.0070 – 0.0090

Polybenzoxazine DPolybenzoxazine D 3.40 – 3.453.40 – 3.45 0.0065 – 0.00850.0065 – 0.0085

Frequency = 10 MHZ – 1.5 GHz


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

Neat Resin ResultsNeat Resin Results


Typical PropertiesTypical Properties XU3560XU3560

• Visual appearanceVisual appearance Yellow chunks Yellow chunks • Melting point, °CMelting point, °C 80-8580-85• Viscosity @ 125Viscosity @ 125C, cps C, cps 185185• Volatile, %Volatile, % ~2~2

DSC uncuredDSC uncured• Initiation Temperature To, Initiation Temperature To, CC 231231• Peak Temperature Tg, Peak Temperature Tg, CC 241241 H, J/gH, J/g 238238


Mechanical PropertiesMechanical Properties

XU3560 Curing Cycle 2hr/180C + 2hr/200C Tg(C) DSC 171 Tg(C) DMA 163 Tg(C)DMA Wet* 150 Flex Properties Dry @ RT Modulus, ksi, (MPa) 667 (4602) Strength, ksi, (MPa) 19.1 (132) Tensile Properties Dry @ RT Modulus, ksi, (MPa) 773 (5334) Strength, ksi, (MPa) 4.5 (31) Elongation, % 1.2 Compression Properties Dry @ RT Modulus, ksi, (MPa) 508 (3505) Strength, ksi, (MPa) 33 (228) Elongation, % 8.3 Toughness Properties Dry @ RT KIc, lbin/in2, (MPam) 844 (0.94) GIc, in-lb/in2, (J/m2) 0.96 (168)

*48hrs boiling water


Formulations for XU3560Formulations for XU3560

1 2 3

97-191 75 70 70 CY 179 25 30 30 Hycar CTBN1300x13 --- 10 XB 6079 3.50 3.50 Benzopinacol 1.05 1.05 Curing Cycle 2hr/180C +

2hr/200C 1hr/120C + 4hr/180C

1hr/120C + 4hr/180C

Tg(C) DSC 219 204 NT Tg(C) DMA, E’ 227 198 200 Tg(C)DMA, E’ Wet* 181 164 158 Flex Properties Dry @ RT Modulus, ksi, (MPa) 642 742 527 Strength, ksi, (MPa) 16.7 19.3 19.2 Tensile Properties Dry @ RT Modulus, ksi, (MPa) 626 722 564 Strength, ksi, (MPa) 7.6 7.4 12.6 Elongation, % 1.6 1.0 2.8 Toughness Properties Dry @ RT KIc, lbin/in2, (MPam) 581 NT 850 GIc, in-lb/in2, (J/m2) 0.47 NT 1.23


Novel High Performance SystemsNovel High Performance Systems

Conclusions :Conclusions :

• We have developed unique benzoxazine resins with commercially We have developed unique benzoxazine resins with commercially

viable manufacturing processes. viable manufacturing processes.

• These resins afford wide formulation latitude and can be These resins afford wide formulation latitude and can be

formulated with epoxies, thermoplastics and catalysts to suit formulated with epoxies, thermoplastics and catalysts to suit

various applications and fabrication processes. various applications and fabrication processes.

• These resins are ideal for high performance composite, structural These resins are ideal for high performance composite, structural

adhesive and printing wiring board (PWB) applications. adhesive and printing wiring board (PWB) applications.

• The benzoxazine/epoxy systems have high TgThe benzoxazine/epoxy systems have high Tg°C°C, good thermal , good thermal

oxidation stability, low water pick-up, reduced shrinkage, good oxidation stability, low water pick-up, reduced shrinkage, good

electrical, and are room temperature stable. electrical, and are room temperature stable.


Benzoxazine TechnologyBenzoxazine Technology

Current StatusCurrent Status• Technology development work continuesTechnology development work continues• New candidate products have been introduced for New candidate products have been introduced for

– Aerospace composite marketsAerospace composite markets– High performance laminating marketsHigh performance laminating markets

• We have cooperative developments programs with Key We have cooperative developments programs with Key customerscustomers

• Qualifications in progress at major customers in both Electronic Qualifications in progress at major customers in both Electronic and Aerospace segmentsand Aerospace segments

• Industrial applications are being exploredIndustrial applications are being explored• Manufacturing in place in North America and Europe.Manufacturing in place in North America and Europe.• Process development work to install manufacturing capability in Process development work to install manufacturing capability in

Asia in the near future.Asia in the near future.


Thank YouThank You

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