Transcript Benzoxazine Development Project

Polyurethanes & Specialties
Polybenzoxazines : New Chemistry
Roger Tietze
Robert Kultzow
Tim Truong
Presentation
Huntsman Advanced Materials
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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 other
thermosets
• Excellent electrical properties
Benzoxazine Synthesis
Huntsman Advanced Materials
OH
R3
O
+
2x
H
H
R2
R1
-2H2O
R3
O
N
R2
R1
R4
+
H 2N
R4
XU3560 Benzoxazine :
Bisphenol A benzoxazine
Huntsman Advanced Materials
CH3
O
N
O
CH3
N
Benzoxazine Polymerization
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O
O
N
N
Heat
O
H
R1
R1
O
O
O
N
N
N
N
H
R1
R1
O
H
H
H
O
H
Benzoxazine/Epoxy
Polymerization
Huntsman Advanced Materials
O
O
O
N
H
O
R1
H
O
N
N
N
N
H
R1
N
Catalyst
+
Heat
R1
O
O
O
R2
"
O
O
O
O
O
O
O
Epoxy
R1
H
O
O
H
O
R2
"
R2
"
R2
"
O
O
O
H
Benzoxazine: Neat Resin Sample Preparation
Huntsman Advanced Materials
To test the properties of benzoxazines and other
thermosets, neat resin samples were prepared by the
following procedure:
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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
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
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
LZ8001 epoxy / Dicy
130°C – 140°C
MY720 / DDS
 200°C
Arocy B40
 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
UL94 Testing : Neat Resin
Huntsman Advanced Materials
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
Huntsman Advanced Materials
• 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
Huntsman Advanced Materials
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
Huntsman Advanced Materials
• Benzoxazines more flame resistant than epoxies
• Good electrical properties
• High glass transition temperatures
Typical Properties XU3560
Huntsman Advanced Materials
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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
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)
Strength, ksi, (MPa)
Elongation, %
Compression Properties Dry @ RT
Modulus, ksi, (MPa)
Strength, ksi, (MPa)
Elongation, %
Toughness Properties Dry @ RT
KIc, lbin/in2, (MPam)
GIc, in-lb/in2, (J/m2)
*48hrs boiling water
XU3560
2hr/180C + 2hr/200C
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
Huntsman Advanced Materials
1
2
3
75
25
70
30
--3.50
1.05
70
30
10
3.50
1.05
2hr/180C +
2hr/200C
219
227
181
1hr/120C +
4hr/180C
204
198
164
1hr/120C +
4hr/180C
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)
Strength, ksi, (MPa)
Tensile Properties Dry @ RT
Modulus, ksi, (MPa)
Strength, ksi, (MPa)
Elongation, %
Toughness Properties Dry @ RT
KIc, lbin/in2, (MPam)
2
2
GIc, in-lb/in , (J/m )
Novel High Performance Systems
Huntsman Advanced Materials
Conclusions :
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We have developed unique benzoxazine resins with commercially
viable manufacturing processes.
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These resins afford wide formulation latitude and can be
formulated with epoxies, thermoplastics and catalysts to suit
various applications and fabrication processes.
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These resins are ideal for high performance composite, structural
adhesive and printing wiring board (PWB) applications.
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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