a new sustainable polymeric fire safety solution for thermoplastics and elastomers
DESCRIPTION
A new generation of High Performance Polymeric flame-retardants has been developed at Albemarle Corporation. Designed for use in a broad range of plastics, these products are made via a break-through technology. The flexibility of this technology allows the products to be tailored to offer a unique set of physical and flame retardant properties in a “single-package” solution. Thanks to their non-bio accumulative, non-toxic and excellent recyclability these products are ideal for a polymer industry striving for more environmentally friendly and sustainable fire safety solutions.TRANSCRIPT
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A New Sustainable Polymeric Fire Safety Solution for Thermoplastics and Elastomers
21st Annual Conference on Recent Advances on Flame Retardancy of Polymeric Materials
May 24, 2010
Kumar G. Kumar, Arthur Mack, Douglas Luther, Vijay Kotian and Bo LiuAlbemarle Corporation
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Agenda
� Why a new Flame Retardant?� What is GreenArmor?� How well does GreenArmor perform in
� Styrenics� Polyolefins� Polyamides � Polyesters
� Registration status� Commercialization timeline� Sampling � Summary
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Why a New Flame Retardant?
�Environmentally friendly �Sustainable�Recyclable �Melt blendable (Efficiency !)�Better performing� Thermally stable (Aesthetics !)�Color stable
In a single In a single packagepackage
Growing need for efficient fire safety solutions that are…
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What is
� New Generation Polymeric Flame Retardant (MW > 1000)� High Bromine content � Better FR efficiency� Melt-blendable� Can be used in both thermoplastic and thermoset
polymers � Has excellent mechanical and electrical properties� Offers better thermal and color stability � Has excellent recyclability� Is offered in a low-color, non-dusting pellet form� Supports VECAP
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Typical Properties
Property GreenArmor
Specific Gravity 2.4Bromine Content ≥74 %Glass Transition Temperature (by DSC) 122°CTGA, (10 °C / min under N2) 1% weight loss 303°C 5% weight loss 355°C 10% weight loss 369°C
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in Styrenics
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Properties Comparison of in HIPS
In a General-Purpose Injection Molding HIPS resin:
FR GreenArmor TTBPT Saytex 8010 BEOBr % 10.0 10.0 10.0 10.0Antimony Trioxide % 4.0 4.0 4.0 4.0Properties UnitsUL-94, 1/8" UL-94 V-0 V-0 V-0 V-0t1 + t2 sec. 12 11 8 9MFI, 200oC/ 5kg ASTM D1238 g/10 min 14.7 18.1 9.7 25.8HDT ASTM D648 °C 70.6 70.1 71.4 66.5Vicat ASTM D1525 °C 97.2 94.8 96.8 90.1N-Izod Impact Strength ASTM D256 ft-lb/in 1.63 1.66 1.03 1.21Tensile Strength ASTM D638 psi x10^3 3.2 3.1 3.0 3.0Tensile Modulus ASTM D638 psi x10^5 2.9 2.8 3.1 2.9Elongation at yield ASTM D638 % 1.3 1.2 1.1 1.2Elongation at Break ASTM D638 % 19.3 28.2 7.8 18.6Flexural Strength ASTM D790 psi x10^3 6.8 6.6 5.7 6.4Flexural Modulus ASTM D790 psi x10^5 3.3 3.3 3.4 3.4
TTBPT: Tris-tribromophenoxy triazine
BEO: Brominated Epoxy Oligomer
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0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Tensile Strength Izod Impact
GreenArmor TTBPT Saytex 8010 BEO
0
20
40
60
80
100
Vicat Melt Flow Index
in HIPS Key Properties vs. other FR’s
psi x10³
ft-lb/in
Temp °C
g / 10 min
Best performance with GreenArmor !
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Capillary Melt Stability @ 250oC, 500 sec-1
60
70
80
90
100
110
120
130
140
5 10 15 20 25 30 35
Time, min
Vis
c P
a-s.
GreenArmor TTBPT Saytex 8010 BEO
in HIPS Melt Stability vs. other FR’s
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FR HIPS - Multi-Pass Recycle Results
5
10
15
20
25
30
35
0 2 4 6
Molding Cycle #
MF
I
80
85
90
95
100
0 2 4 6
Molding Cycle #
Vic
at
0.5
1.0
1.5
2.0
2.5
0 2 4 6
Molding Cycle #
Imp
act
NEAT GreenArmor TTBPT Saytex 8010 BEO
MFI VICAT
IzodBest performance with GreenArmor !
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FR HIPS - Humidity Aging Results
0
5
10
15
20
25
30
Neat GreenArmor TTBPT Saytex 8010 BEO
MFI
non-aged non-aged after 1st molding100% aged 30% aged/70% non-aged
86
88
90
92
94
96
98
Neat GreenArmor TTBPT Saytex 8010 BEO
Vic
at,
C
non-aged 100% aged 30% aged/70% non-aged
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Neat GreenArmor TTBPT Saytex 8010 BEO
Imp
ac
t
non-aged 100% aged 30% aged/70% non-aged
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GreenArmor Properties Comparison in ABS
In a General-Purpose Injection Molding ABS resin:
FR GreenArmor TTBPT TBBPA BEOBr % 12.0 12.0 12.0 12.0Antimony Trioxide % 4.5 4.5 4.5 4.5Properties UnitsUL-94, 1/8" UL-94 V-0 V-0 V-0 V0t1 + t2 sec. 8 8 7 8
MFI, 230oC/3.8kg ASTM D1238 g/10 min 9.1 13.8 25.4 20.9HDT ASTM D648 °C 74.0 74.0 66.3 72.5Vicat ASTM D1525 °C 103.1 100.8 90.1 97.3N-Izod Impact Strength ASTM D256 ft-lb/in 1.86 1.70 1.27 1.12Tensile Strength ASTM D638 psi x10^3 4.9 4.7 4.3 4.4Tensile Modulus ASTM D638 psi x10^5 3.1 3.1 3.3 3.3Flexural Strength ASTM D790 psi x10^3 9.2 9.0 7.9 9.0Flexural Modulus ASTM D790 psi x10^5 3.2 3.0 3.3 3.3
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Key Properties vs. other FR’s
0
1
2
3
4
5
6
Tensile Strength Izod Impact
GreenArmor TTBPT TBBPA BEO
0
20
40
60
80
100
120
Vicat Melt Flow
psi x10³ ft-lb/in Temp °C g / 10 min
Capillary Melt Stability @ 250oC, 500 sec-1
60
80
100
120
140
160
180
200
5 10 15 20 25 30 35Time, min
Vis
c.
GreenArmorTTBPTTBBPABEO
Best performance with GreenArmor !
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FR ABS -- Color Stability
ABS Extrudates from capillary rheometer @ 250°C for varying residence time
GreenArmor TTBPT TBBPA BEOTime, Min
Best Color retentionwith GreenArmor !
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in Styrenics - Summary
� GreenArmor is well suited for use in HIPS and ABS�Imparts high melt flow as it is melt-blendable �Imparts great impact strength �Provides great thermal resistance in HIPS and ABS �Provides great melt stability in HIPS and ABS�Has excellent mechanical properties in HIPS and ABS�Performs well in various HIPS and ABS grades�Exhibits excellent Recyclability
�HIPS containing GreenArmor retains its properties after six injection-molding cycles and after 168-hr humidity aging
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in Polyolefins
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FR XL-EVA -- Comparison
Ingredient Saytex 102E Saytex 8010 Saytex BT-93 GreenArmor
EVA 50 50 50 50Bright Sun HB ATO 7 7 7 7Surface modified Calcined Al Silicate 19 19 19 19FR Loading (wt%) 21 21 21 2140% Active Organic Peroxide 3 3 3 3Specific Gravity 1.41 1.41 1.39 1.37UL 94, 1/8 in V0 V0 V0 V0UL 94, T1+T2 time, sec 7.4 7.6 7.0 7.3Tensile Strength, psi 2090 2144 2109 2025Ultimate Elongation, % 205 199 173 200Dielectric Constant 2.98 2.89 3.07 2.89Dielectric Strength, V/mil 507 545 533 511Volume Resistivity, Ohm-cm, 10 1̂4 2.15 5.85 11.00 6.12
EVA
0
100
200
300
400
500
600
1 51 101 151 201 251 301time (s)
He
at
Re
lea
se
kW
/m2
GreenArmor Saytex 8010Saytex 8010ZDSaytex 102ESaytex BT-93
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FR PP Comparison
Ingredient Saytex 102E Saytex 8010 Saytex 8010ZD Saytex BT-93 GreenArmor
PP Copolymer 56.8 56.8 56.8 56.8 56.8FR Loading (wt%) 22.0 22.0 22.0 22.0 22.0Brightsun HB 7.0 7.0 7.0 7.0 7.0Talc 14.0 14.0 14.0 14.0 14.0Ethanox 310 0.1 0.1 0.1 0.1 0.1Ethaphos 368 0.1 0.1 0.1 0.1 0.1Mechanical PropertiesSpecif ic Gravity 1.27 1.27 1.26 1.26 1.25Tensile Strength psi X 10^3 2.5 2.3 3.5 2.8 2.7Tensile Modulus psi X 10^5 4.4 4.2 4.1 4.4 4.5Elongation @ Yield % 3.3 3.2 4.5 2.3 2.3Elongation @ Break % 30.6 25.5 42.1 8.7 7.5Flexural Strength psi X 10^3 6.3 6.2 5.9 6.6 6.6Flexural Modulus psi X 10^5 3.3 3.3 3.0 3.2 3.5Izod Impact ft-lb/in 0.52 0.51 0.75 0.38 0.42GLOSS 21.3 25.1 24.5 24.4 27.8Thermal PropertiesMelt Flow Index g/10 min 4.0 3.9 3.6 3.4 6.2HDT °C 119.5 120.8 114.7 118.7 115.3VICAT °C 154.2 154.3 152.1 153.9 148.2Electrical PropertiesDielectric Constant 2.51 2.49 2.50 2.55 2.49Dissipation Factor % 1.47 1.81 3.14 1.84 3.60Volume Resistivity 10^16 1.0 1.4 0.9 1.5 1.5Surface Resistivity 10^16 3.8 4.6 3.3 10.2 6.4Dielectric Strength v/mil 534 533 541 561 647
0100200300400500600700
1 51 101 151 201t (s)
He
at
Re
lea
se
kW
/m2
GreenArmor Saytex 8010Saytex 8010ZDSaytex 102ESaytex BT-93
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FR TPE -- Comparison
Ingredient Saytex 102E Saytex 8010 Saytex 8010ZD Saytex BT-93 GreenArmor
Polypropylene Copolymer 45.4 45.4 45.4 45.4 45.4
Polyolefin Elastomer (C2-C4) 11.4 11.4 11.4 11.4 11.4
FR Loading (wt%) 22.0 22.0 22.0 22.0 22.0Brightsun HB ATO 7.0 7.0 7.0 7.0 7.0Talc 14.0 14.0 14.0 14.0 14.0
Ethanox 310 0.1 0.1 0.1 0.1 0.1Ethaphos 368 0.1 0.1 0.1 0.1 0.1
Mechanical PropertiesSpecific Gravity 1.28 1.26 1.26 1.24 1.24Tensile Strength psi X 10^3 3.1 3.0 3.0 3.3 3.3Elongation @ Yield % 5.5 5.8 6.8 5.6 3.0Elongation @ Break % 113 360 362 14 67Flexural Strength psi X 10^3 5.5 5.7 5.3 5.8 5.9Flexural Modulus psi X 10^5 2.6 2.2 2.0 2.6 3.5Izod Impact ft-lb/in 0.61 0.74 1.03 0.52 0.54GLOSS 16.5 19.4 22.5 21.4 24.6Thermal Properties
Melt Flow Index g/10 min 3.7 3.7 4.1 3.2 6.7HDT °C 102.7 99.6 94.5 102.6 104.5VICAT °C 154.2 154.3 152.1 153.9 148.2Electrical Properties
Dielectric Constant 2.48 2.49 2.46 2.49 2.46Volume Resistivity 10^16 0.8 0.8 6.7 1.2 1.6Surface Resistivity 10^16 3.4 2.6 2.8 5.1 5.9Dielectric Strength v/mil 526 525 533 552 636
0
200
400
600
800
1000
1200
1 51 101 151time
Hea
t R
elea
se k
W/m
2
GreenArmor Saytex 8010Saytex 8010ZDSaytex 102ESaytex BT-93
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in Polyolefins --Summary
�GreenArmor is an excellent FR in Polyolefins and provides�Good physical properties �Comparable FR properties at lower Br content
�FR efficiency between Saytex 102E/8010 and Saytex BT-93�Lower Peak HRR vs. other FR’s
�Equivalent or better electrical properties�Improved processability
�Higher throughput
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in Polyamides
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FR - 30% GF Polyamide 6/6 -- Comparison
Ingredient GreenArmorSaytex HP 3010
Saytex HP 7010 BrPS-1 BrPS-2 BrPS-3 BrPS-4 BrPS-5 BrPS-6
Br % Units 74% 68% 68% 59% 64% 64% 64% 66% 66%FR Loading (Wt%) 19.0 20.7 20.7 23.6 22.9 22.9 22.9 21.5 21.5Brightsun HB Sb2O3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3PTFE Teflon 6C 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
FlammabilityLOI % Oxygen 36.8 36.4 36.1 35.4 36.5 37.5 37.3 36.7 38.1
Rating V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0sec 7 20 26 17 24 16 24 9 8
Physical PropertiesSpecif ic Gravity g/cm3 1.63 1.65 1.62 1.66 1.66 1.66 1.66 1.67 1.66
Gloss N/A 29.2 22.6 20.3 23.2 22.9 21.8 23.4 19.6 20.2Initial Color YI (D1925) 20.9 15.8 18.9 18.0 17.4 20.3 13.2 21.7 10.4
UL-94 1/32"
BrPS-1 thru BrPS-6: Competitive Brominated Polystyrene Products
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FR 30% GF Polyamide 6/6 –Comparison
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
Melt Flow Index
MFI (g
ms/10
min.
)
0
0.5
1
1.5
2
2.5
3
3.5
4
% E
long
atio
n
Gre
enAr
mor
HP 3
010
HP 7
010
PDBS
-80
PBS-
64
PBS-
64HW
CP-4
4HF
FR-8
03P
LMBS
-66
'@ Break
'@ Yield
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
Izod Impact
ft-lb
/in.
0
10
20
30
40
50
60
70
80
90
100
Gardner Impactin
. lb.
in.
GreenArmor BrPS-1 BrPS-4
Saytex HP-3010 BrPS-2 BrPS-5
Saytex HP-7010 BrPS-3 BrPS-6
Best performance with GreenArmor !
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FR 30% GF Polyamide 6,6Comparison of Rheology
Shear Sweep @ 280C
0
50
100
150
200
250
300
7297 4998 3004 997 499
Rate (1/s)
Vis
cosi
ty (P
a-s)
GreenArmor
Saytex HP 3010
Saytex HP 7010
BrPS-1
BrPS-2
BrPS-3
BrPS-4
BrPS-5
BrPS-6
Lowest Viscosity with GreenArmor !
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in Polyamides- Summary
�GreenArmor is an excellent FR in Polyamides and provides�Comparable or better mechanical properties�Low melt viscosity �Comparable FR properties at lower Br content
�Lower loadings than other BrPS products�Better Impact properties�Better Gloss�Equivalent or better electrical properties�Improved processability
�Higher throughput
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in Polyesters
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FR- 30% GF PBT -- Comparison
FR GASaytex
PBT-620Saytex
8010Saytex BT-93W BrPS-1 BrPS-2 BrPS-3 FR-1 FR-2
Saytex 120 FR-3
Br % 74% 54% 82% 67% 59% 64% 64% 58% 71% 82% 53%FR Loading (wt%) 11.0 15.0 10.0 12.0 13.6 12.8 12.8 14.1 11.5 10.0 15.4Brightsun HB Antimony Oxide 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0PTFE Teflon 6C 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Flammability Units GASaytex
PBT-620Saytex 8010
Saytex BT-93W BrPS-1 BrPS-2 BrPS-3 FR-1 FR-2
Saytex 120 FR-3
LOI % Oxygen 33.1 31.8 33.5 32.9 32.0 31.2 31.5 33.6 32.6 32.4 33.3Pass/Fail V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0seconds 7 8 8 8 8 9 8 8 10 9 9
Physical Properties Units GASaytex
PBT-620Saytex 8010
Saytex BT-93W BrPS-1 BrPS-2 BrPS-3 FR-1 FR-2
Saytex 120 FR-3
Specific Gravity g/cm3 1.68 1.67 1.70 1.73 1.70 1.69 1.69 1.72 1.67 1.72 1.67Gloss n/a 29.1 14.3 14.7 15.2 13.7 11.8 11.3 22.1 21.5 17 13.8Initial Color YI 14.80 11.40 13.37 21.35 14.27 14.92 16.10 12.95 13.08 13.66 13.34
UL-94 1/32"
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FR 30% GF PBT - Comparison
0
5
10
15
20
25
30
Glo
ss
Gloss
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
Mel
t Flo
w In
dex
(g/1
0 m
in.)
Melt Flow Index
0.0
30.0
60.0
90.0
120.0
150.0
180.0
210.0
240.0
Tem
pera
ture
(C)
HDT @ 120 C/hr.
-0.1
0.1
0.3
0.5
0.7
0.9
1.1
1.3
1.5
ft-lb
/in.
Izod Impact
GreenArmor BrPS-1 FR-2
Saytex PBT-620 BrPS-2 Saytex 120
Saytex 8010 BrPS-3 FR-3
Saytex BT-93W FR-1
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Fr 30% GF PBTComparison of Rheology
GreenArmor BrPS-1 FR-2
Saytex PBT-620 BrPS-2 Saytex 120
Saytex 8010 BrPS-3 FR-3
Saytex BT-93W FR-1
Capillary Rheology - Melt Stability - 250 C
0
100
200
300
400
500
600
700
6.2 12.5 18.5 24.5 31
Time (min.)
Visc
osity
(1/s
ec)
Lowest Viscosity with GreenArmor !
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FR 30% GF- PET -- Comparison
IngredientSaytex HP-3010G/PST
Saytex HP-7010G
Saytex BT-93W Saytex 120 BrPS-1 BrPS-2 FR-1 GreenArmor
PET (45% Glass-filled) 34 34 34 31 37 36 34 33PET (30% Glass-filled) 48.6 48.6 48.6 53.6 43.8 45.8 49.1 50.6FR Loading (w t%) 12 12 12 10 13.8 12.8 11.5 11Sodium Antimonate 5 5 5 5 5 5 5 5PTFE 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4LOI % Oxygen 27.5 27.5 31.7 31 29.3 29.6 30.1 30.6UL-94 Pass/Fail V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0t1+t2 seconds 14 11 11 13 34 13 8 11
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FR 30% GF PET -- Comparison
0.0
2.0
4.0
6.0
8.0
10.0
12.0
MFI
(g/1
0 m
in)
Melt Flow Index
Saytex HP-3010G/PST Saytex HP-7010G Saytex BT-93W
Saytex 120 BrPS-1 BrPS-2
FR-1 GreenArmor
0.00
0.50
1.00
1.50
ft-l
b/in
Notched IZOD
Saytex HP-3010G/PST Saytex HP-7010G Saytex BT-93W
Saytex 120 BrPS-1 BrPS-2FR-1 GreenArmor
050
100150200250300
6.1 12.4 18.5 24.6 30.7
Time (min)
Vis
cosi
ty (
1/se
c)
Saytex HP-3010G/PST Saytex HP-7010G Saytex BT-93WSaytex 120 BrPS-1 BrPS-2FR-1 GreenArmor
0
50
100
150
200
250
300
7300 4500 2000 1000 500
Rate (1/sec)
Vis
cosi
ty (
Pa-
s)
Saytex HP-3010G/PST Saytex HP-7010G Saytex BT-93WSaytex 120 BrPS-1 BrPS-2FR-1 GreenArmor
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FR 30% GF PETElectrical Properties
IngredientSaytex HP-3010G/PST
Saytex HP-7010G
Saytex BT-93W Saytex 120 BrPS-1 BrPS-2 FR-1 GreenArmor
PET (45% Glass-f illed) 34 34 34 31 37 36 34 33PET (30% Glass-f illed) 48.6 48.6 48.6 53.6 43.8 45.8 49.1 50.6FR Loading (w t%) 12 12 12 10 13.8 12.8 11.5 11Sodium Antimonate 5 5 5 5 5 5 5 5PTFE 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4Dielectric Strength kV/mm 19.49 20.08 18.40 17.67 19.50 19.29 17.77 16.07Dielectric Constant N/A 3.649 3.757 3.846 3.787 3.727 3.728 3.780 3.780Comparative Tracking Index Volts 225 200 200 200 200 200 175 200Volume Resistivity ohm-cm 1.00x10E15 1.02x10E15 7.84x10E14 8.62x10E14 1.32x10E15 1.12x10E15 1.01x10E15 1.18x10E15Surface Resistivity ohm-cm 1.19x10E16 2.52x10E15 4.24x10E15 1.07x10E16 1.65x10E16 1.19x10E16 3.89x10E15 6.15x10E15Dissipation Factor N/A 0.0126 0.0181 0.0057 0.0032 0.0055 0.0067 0.0161 0.0176
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in GF Polyesters - Summary
�GreenArmor is an excellent FR in PBT and PET and provides�Comparable or better mechanical properties�Low melt viscosity �Comparable FR properties at lower Br content
�Lower loadings than other BrPS products�Equivalent or better electrical properties�Better Gloss�Improved processability
�Higher throughput
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www.albemarle.comRegistration & Environmental Profile
�Registration�Testing under way�Global registration targeted to finalize by mid 2010�Japan by end-2010
�Mammalian toxicology�Low concern due to polymeric nature of GreenArmor
�Bioaccumulation�Not expected to bio-accumulate given its polymeric nature (based on model
evaluation)
�Ecotoxicity�Expected to be non-toxic to aquatic organisms (based on model evaluation)
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www.albemarle.comCommercialization Timeline & Sampling
�Completed applications testing�Commercial production Scope defined�Completed patent filings�Global Product Registration nearing completion�Product introduction underway�Commercial Production start-up 4Q2010�Samples requests - please contact your Albemarle Sales
Representative�Limited sample quantities until 4Q10 when large scale samples will be available
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www.albemarle.comSummaryGreenArmor is a high performing polymeric fire safety
solutions that is …
�Environmentally friendly �Sustainable�Recyclable �Melt blendable (Efficiency !)�Better performing�Thermally stable
(Aesthetics!)�Color stable