Tietze Huntsman Presentation

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
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
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 nonhalogen 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
OH
R3
O
2x
R2
R1
-2H2O
R3
O
N
R2
R1
R4
H 2N
R4
XU3560 Benzoxazine :
Bisphenol A benzoxazineHuntsman Advanced Materials
CH3
O
N
O
CH3
Benzoxazine Polymerization
Heat
R1
R1
O
N
O
H
R1
R1
O
Benzoxazine/Epoxy
Polymerization
R1
H
R1
Catalyst
Heat
R1
O
R2
"
O
O
O
O
Epoxy
R1
O
H
O
H
R2
"
R2
"
R2
"
O
H
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 @ 177C
MY720/DDS
High Tg epoxy
4 hour @ 200C
Arocy B40
Cyanate Ester
4 hours @ 218C
BMI/DABA
Polyimide
4 hours @ 218C
Polybenzoxazine A
Benzoxazine
2 hours @ 200C
Polybenzoxazine B
Benzoxazine
2 hours @ 200C
Polybenzoxazine C
Benzoxazine
2 hours @ 200C
Polybenzoxazine D
Benzoxazine
2 hours @ 200C
Polybenzoxazine E
Benzoxazine
2 hours @ 200C
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
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
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
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
Neat Resin Results

Benzoxazines more flame resistant than epoxies

Good electrical properties
High glass transition temperatures
Typical Properties XU3560

Visual appearance
Melting point, C
Viscosity @ 125C, 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
Curing Cycle
Tg(C) DSC
Tg(C) DMA
Tg(C)DMA Wet*
Flex Properties Dry @ RT
Modulus, ksi, (MPa)
Strength, ksi, (MPa)
Tensile Properties Dry @ RT
Modulus, ksi, (MPa)
Elongation, %
Compression Properties Dry @ RT
Modulus, ksi, (MPa)
Elongation, %
Toughness Properties Dry @ RT
KIc, lbin/in2, (MPam)
GIc, in-lb/in2, (J/m2)
*48hrs boiling water
XU3560
2hr/180C + 2hr/200C
171
163
150
667 (4602)
19.1 (132)
773 (5334)
4.5 (31)
1.2
508 (3505)
33 (228)
8.3
844 (0.94)
0.96 (168)
Formulations for XU3560

1
75
25
70
30
--3.50
1.05
70
30
10
3.50
1.05
2hr/180C +
2hr/200C
219
227
181
1hr/120C +
4hr/180C
204
198
164
1hr/120C +
4hr/180C
NT
200
158
642
16.7
742
19.3
527
19.2
626
7.6
1.6
722
7.4
1.0
564
12.6
2.8
581
0.47
NT
NT
850
1.23
97-191
CY 179
Hycar CTBN1300x13
XB 6079
Benzopinacol
Curing Cycle
Tg(C) DSC
Tg(C) DMA, E
Tg(C)DMA, E Wet*
Flex Properties Dry @ RT

Modulus, ksi, (MPa)
Tensile Properties Dry @ RT
Modulus, ksi, (MPa)
Elongation, %
Toughness Properties Dry @ RT
2
KIc, lbin/in , (MPam)
GIc, in-lb/in2, (J/m2)
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.
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
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Polyurethanes & Specialties

Polybenzoxazines : New Chemistry

Benzoxazines are a unique non-halogen thermoset

Huntsman Advanced Materials

Benzoxazine: Neat Resin Sample

Huntsman Advanced Materials

To test the properties of benzoxazines and other

Resins and hardeners are melted

Neat Resin Castings

FR4 bis A epoxy

Neat Resin Castings

Glass Transition Temperatures, C

LZ8001 epoxy / Dicy

UL94 Testing : Neat Resin

1st Burn 2ndBurn

Note: Longest burn time recorded

Benzoxazine: Electrical Testing

Huntsman Advanced Materials

Neat resin specimens : 0.5 x 0.5

Benzoxazine: Electrical Properties

Huntsman Advanced Materials

Neat Resin Sample

Frequency = 10 MHZ 1.5 GHz

Neat Resin Results

Benzoxazines more flame resistant than epoxies

Typical Properties XU3560

Formulations for XU3560

Flex Properties Dry @ RT

Novel High Performance

Huntsman Advanced Materials

We have developed unique benzoxazine resins with commercially

These resins afford wide formulation latitude and can be

These resins are ideal for high performance composite, structural

The benzoxazine/epoxy systems have high TgC, good thermal

We have cooperative developments programs with Key

Huntsman Advanced Materials

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