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Recent developments in flame retardantsfor sustainable fire safety solutions
Presentation byMichael Kearns, Technical Business Support EMEA
Great Lakes Solutions, a Chemtura businessMay 22, 2013
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What are flame retardants?
How do they work?
3
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4
Flame Retardants Interrupt the Fire Cycle
Three ingredients of a fire:
A fuel source
An oxygen source
An ignition source
Flame retardants work by one ofthree mechanisms
Interruption of radical mechanismof combustion process in the gasphase
Reaction in the solid phase toform a carbonaceous char which
serves as a barrier between fueland the heat and oxygen source
Endothermic processes, such asrelease of water, to remove theheat from the reaction
Source: European Flame Retardants Association, www.cefic-efra.com
Take away one (or more) of
these and the fire can be
delayed/prevented
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5
Most Widely Used Flame Retardants Types
Mechanism Flame Retardants Types Uses & Limitations
Gas phase,Free radicalquenching
Halogenated FlameRetardants
Brominated FRs
Chlorinated FRs
Halogenated polymers
Antimony Synergists
Most versatile class of flame retardant Used widely used in thermoplastics,
epoxy thermosets for printed wiringboards, polyurethane foams, polyesters
Only option for many olefinic and styrenicpolymers uses
Often used with Antimony trioxide
synergist
Condensedphase, Charforming
Phosphorus and Nitrogencontaining flameretardants
Phosphates, Melaminephosphates
Ammonium
Polyphosphates Melamine Cyanurate
Typically effective in oxygen or nitrogencontaining polymers such aspolycarbonate, polyesters, polyamidesand epoxy resins
Often used with synergist to promote charformation, e.g. cyanurates
Phosphate esters used in PC/ABS Phosphates provide FR plasticizer for PVC
Endothermic
Metal Hydrates
Aluminum Trihydrate
Magnesium Hydroxide
Use at high loadings
Wire & cable, coatings, rubber,thermosets
Less use in engineered plastics
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6
Great Lakes Solutions
Polymeric and Reactive Flame Retardant Technologies
Polymer Technology Products
Polyamides PolybromostyreneFiremaster® CP44-HF
Firemaster® PBS64-HW, PDBS-80™
Polycarbonate, PBTBrominated Oligomer
Polybromostyrene
BC-52™, BC-58™, Firemaster® CP44-HF
Firemaster® PBS64-HW, PDBS-80™
Unsaturated Polyesters Reactive Intermediate PHT-4 ™, BA-59P™
Polyurethane Reactive IntermediatePHT-4 Diol™, PHT-4 Diol™ LV,
Firemaster® 520
Polyolefins, HDPE, PPProprietary Polymeric
Emerald Innovation™ 1000
Emerald Innovation™ 3000 Styrenics, PS, HIPS, ABS
Epoxy Reactive IntermediatesBA-59P™
Emerald Innovation™ 2000
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Flame Retardants Choices for Polyolefins
Polymertype
Bromine-based FRPhosphorus-based
FRSynergists,
Smoke Suppressants
Polyolefins
Firemaster® 2100REmerald Innovation™ 1000
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
TPOFiremaster® 2100REmerald Innovation™ 1000
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
EPDM
DP 45™
Firemaster® 2100REmerald Innovation™ 1000
Reofos® 95Reofos® RDP
Reofos® BAPP
Timonox® /TMS®Blue StarUltrafine® Blue Star
ZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
7
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Flame Retardants Choices for PVC & Polyurethane
Polymertype
Brominebased FR
Phosphorus based FR Synergists,Smoke Suppressants
PVCDP 45™ Firemaster® 2100REmerald Innovation™ 1000
Reofos® 35, 50, 65 95,Kronitex® CD, TCP
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
Rigid PU
PHT 4 Diol™
PHT 4 Diol LV™ Firemaster® 508
Reofos® 35, 50, 65, 95
FlexiblePU
DP 45™Firemaster® BZ 54Firemaster® 550Firemaster® 600
Reofos® 35, 50, 65, 95Kronitex® CDP, TCPEmerald Innovation™ NH-1
TPU
PDBS 80™ DE-83R™Firemaster® BZ 54Firemaster® 2100REmerald Innovation™ 1000
Reofos® 35, 50, 65, 95Reofos® RDPReofos® BAPPEmerald Innovation™ NH-1
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
8
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Flame Retardants Choices for Styrenic Resins
Polymer
type
Bromine
based FR
Phosphorus
based FR
Synergists,
Smoke Suppressants
HIPS
SP 75™Firemaster® 2100REmerald Innovation™ 1000
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc® Ongard® 2,LSFR™ Theromoguard® CPA
ABS
BA-59P™BC-52™, BC-58™
Firemaster® 2100REmerald Innovation™ 1000
Timonox® /TMS®Blue StarUltrafine® Blue Star
ZB 223, ZB 467, Smokebloc® Ongard® 2,LSFR™ Theromoguard® CPA
PC/ABS
PDBS 80™Firemaster® CP-44HFFiremaster® PBS-64 HWBC-52™ , BC-58™ Firemaster® 2100REmerald Innovation™ 1000
Reofos® RDPReofos® BAPP
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
PPE/HIPS
PDBS 80™ Emerald Innovation™ 1000
Reofos® RDP,Reofos® BAPP
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc® Ongard® 2,LSFR™ Theromoguard® CPA
9
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Flame Retardants Choices for Polystyrene Foams
Polymer type Bromine-based FR
EPS Emerald Innovation™ 3000 CD 75P™
XPSEmerald Innovation™ 3000 CD 75P™ SP 75™
10
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Flame Retardants Choices for Thermosets
Polymer type Bromine-based FRPhosphorus-
based FRSynergists,
Smoke Suppressants
UPES(unsaturated polyester)
PDBS 80™Firemaster® CP-44HFFiremaster® PBS-64 HW *PHT 4™*BA-59P™Firemaster® BZ-54Firemaster® 2100REmerald Innovation™ 1000
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
Epoxy
*BA-59P™Firemaster® BZ-54Firemaster® 2100REmerald Innovation™ 1000
Reofos® 50, 65, 95Kronitex® CDPReofos® RDPReofos® BAPP
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CPA
Phenolic
DP 45™Firemaster® BZ-54Firemaster® 550Firemaster® 552DE-83R™ Firemaster® 2100REmerald Innovation™ 1000
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 223, ZB 467, Smokebloc®Ongard® 2, LSFR™Theromoguard® CP
* Reactive FR11
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Flame Retardants Choices for Polyamides
Polymer type Bromine-based FRSynergists,
Smoke Suppressants
PA 6
PDBS 80™Firemaster® CP-44HFFiremaster® PBS-64 HWFiremaster® 2100R
Timonox®/TMS®Blue StarUltrafine® Blue StarZB 467
PA 66
PDBS 80™Firemaster® CP-44HFFiremaster® PBS-64 HW
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 467
HTPA
PDBS 80™
Firemaster® CP-44HFFiremaster® PBS-64 HW
Timonox®/TMS®Blue Star
Ultrafine® Blue StarZB 467
12
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Flame Retardants Choices for Engineering Thermoplastics
Polymer type Bromine-based FRSynergists,
Smoke Suppressants
PBT
PDBS 80™Firemaster® CP-44HFFiremaster® PBS-64 HW BC-52™
BC-58™
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 467
PET
PDBS 80™ Firemaster® CP-44HFFiremaster® PBS-64 HW
Timonox® /TMS®Blue StarUltrafine® Blue StarZB 467
PC
Firemaster® PBS-64 HW
BC-52™BC-58™
ZB 467
13
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Developing Sustainable
Flame Retardant Solutions
Great Lakes Solutions
&
Emerald Innovation™
series of flame retardants
14
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Introducing Emerald Innovation™, Our Next Generation
of Products
Emerald Innovation™ 1000
Sustainable, Versatile Polymeric FlameRetardant
Emerald Innovation™ 2000
Combination Flame Retardant and Curing
Agent for Non-Halogen Epoxy Printed Circuit
Board Laminates
Emerald Innovation™ 3000
Sustainable, Innovative, High-Performance,
Brominated Polymeric Flame Retardant for
EPS and XPS Foam Insulation
Emerald Innovation™ NH-1
Halogen-Free Flame Retardant for FlexiblePolyurethane Foam
Emerald Innovation™ 1000 Emerald Innovation™ 2000
Emerald Innovation™ 3000 Emerald Innovation™ NH-1
15
Why Emerald Innovation™?
Products are innovative, reliable and also minimize the impact on our
environment and human health while maintaining superior
performance and quality
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A Sustainable, Versatile, Brominated PolymericFlame Retardant
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Emerald InnovationTM 1000 IS A POLYMERIC BROMINATED FLAME RETARDANT
DESIGNED FOR USE IN A BROAD SPECTRUM OF APPLICATIONS
Property Emerald
Innovation ™
1000
Appearance Off-whitepowder
Bromine, % 78
Average particle size, (µm) 5-6
5% wt loss, 0C
(Thermogravimetric Analysis (@ 100
C/min under N2)
4100C
EMERALD INNOVATIONTM 1000 TYPICAL PROPERTIES
High bromine content with excellent thermal stability
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EMERALD INNOVATIONTM 1000 IN
HIGH DENSITY POLYETHYLENE*
Emerald Innovation™ 1000 offers an excellent balance of efficiency,
physical properties and flammability performance in HDPE formulations
*LYONDELLBASELL PETROTHENE R590005 (0.8MFI)
ALL FORMULATIONS CONTAIN 6.3% ANTIMONY TRIOXIDE LABEL DESCRIPTION
FR-1 DECABROMODIPHENYL OXIDE (DE-83R)
FR-2 BIS (PENTABROMOPHENYL) ETHANE (2FIREMASTER® 2100R)
FR-3 POLY(PENTABROMOBENZYL) ACRYLATE (FR-1025)
FR-4 ETHYLENEBIS(TETRABROMOPHTHALIMIDE) (SAYTEX BT-93)
Property Emerald InnovationTM 1000 FR-1 FR-2 FR-3 FR-4
FR Load, % 19.0 19.0 19.0 21.0 22.3
UL-94, at 1.6 mm V-0 V-0 V-0 V-0 V-0
Gardner Impact, J 17.8 17.1 17.7 1.5 15.2
Elongation at Yield, % 8.5 10.1 8.7 5.6 6.9
Whiteness Index, CIE 49.7 55.8 49.5 61.3 46.6
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COMPARISON OF MELT VISCOSITIES CAPILLARY RHEOLOGY OF HDPE FORMULATION
CONTAINING EMERALD INNOVATIONTM 1000
Comparable viscosities in HDPE formulations indicate that Emerald
Innovation™ 1000 will process under similar conditions as current flame
retardant formulations
10
100
1000
10000
10 100 1000 10000
Viscosity, Pa-sec
Shear Rate, 1/sec
Emerald 1000
FR1
FR2
FR3
FR4
Emerald Innovation™ 1000
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EMERALD INNOVATIONTM 1000
PERFORMANCE IN TALC-FILLED POLYPROPYLENE, COPOLYMER
ALL FORMULATIONS CONTAIN 20% TALC AND 7% ANTIMONY TRIOXIDE
Emerald Innovation TM 1000 is an effective replacement for FR -1 and FR-2
in filled polypropylene formulations
Property Emerald InnovationTM 1000 FR-1 FR-2
FR Load, % 21.0 21.0 21.0
UL-94, 1.6 mm V-0 V-0 V-0
Melt flow index, g/10min230oC/2.16kg 11.4 12.8 11.9
Notched Izod Impact, J/m 33.6 35.8 41.1
Elongation at Yield, % 2.29 2.42 2.38
LABEL DESCRIPTION
FR-1 DECABROMODIPHENYL OXIDE (DE-83R)
FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTE® 2100R)
21
E I TM 1000
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Excellent impact performance
Efficiency at equal or lower load levels
Equivalent Vicat softening performance
Melt flow similar to DE-83R, superior to Firemaster 2100R
EMERALD INNOVATIONTM 1000
PERFORMANCE COMPARISON IN HIPS
All formulations contain 4.0% antimony trioxide
*afterglow
LABEL DESCRIPTION
FR-1 DECABROMODIPHENYL OXIDE (DE-83R)
FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER® 2100R)
FR-3 2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE
22
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REDUCED IMPACT MODIFIER LOADING
The higher impact strength achieved with Emerald Innovation™ 1000
provides an opportunity to reduce impact modifier loading, and thus
reduced formulation cost
Same impact strength
at over 40% lower
impact modifier load
80
90
100
110
120
130
140
150
160
170
0 1 3 5 N
o t c h e d I z o d I m p a c t S t r e n g t h , J / m
% Kraton D1101
Emerald 1000
Firemaster 2100R
EmeraldInnovation™ 1000
Firemaster 2100R
Impact Strength in Impact Modified HIPS
With 12% FR and 4% ATO
23
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COMPARISON OF MELT VISCOSITIES
220 0C
LABEL DESCRIPTION
FR-1 DECABROMODIPHENYL OXIDE (DE-83R)
FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER 2100R)
FR-3 2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE
Comparable viscosities in HIPS formulations indicate that Emerald
Innovation™ 1000 will process under same conditions as current flame
retardant formulations
10
100
1000
10000
10 100 1000 10000
S h e a r V i s c o s i t y , P a - s e c
Shear Rate, 1/sec
CAPILLARY RHEOLOGY - HIPS
Emerald 1000
FR-1FR-2
FR-3
Emerald
Innovation™ 1000
24
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Emerald
Innovation™
1000 FR 2 FR 3 FR 4
FR, % 13.0 13.0 16.2 21.7
UL-94 @ 1.6 mm V0 V0 V0 V0
Tensile strength, MPa 47.9 46.2 50.1 51.2
Strain at yield, % 3.02 2.66 2.86 2.53
Strain at break, % 15.3 15.1 7.1 3.02
Flexural strength, MPa 75.2 72.9 78.6 72.5
Flexural modulus, MPa 2437 2594 258
3
2777
Notched Izod Impact, J/m 107.3 55.0 83.8 41.1
MFI, g/10min, 230 ºC/10kg
29 21 43 73
HDT, ºC, , 1.8MPa 75.2 76.5 73.8 73.2
EMERALD INNOVATION™ 1000 IN INJECTION MOLDING GRADE ABS
* All formulations contain 5.0 % antimony trioxide and 0.3% PTFE
107
55
84
41
Joules/Meter
Notched Izod Impact Strength
Emerald 1000 FR 2 FR 3 FR 4Emerald
Innovation™
1000
25
High efficiency and excellent balance of properties
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EMERALD INNOVATIONTM 1000
YOUR SUSTAINABLE SOLUTION FOR POLYOLEFINS & STYRENICS
Performance comparisons for Emerald InnovationTM 1000 in
Polyolefins and Styrenics demonstrate comparable efficiency at
similar load levels over DE-83R and Firemaster® 2100R
The polymeric nature of Emerald InnovationTM 1000 makes it more
sustainable than other brominated flame retardants used in
Polyolefins & Styrenics, making Emerald InnovationTM 1000 the best
choice when developing a sustainable product portfolio
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LOW-ATO OR ATO-FREE SOLUTIONS
v.2.027
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WHY THE NEED FOR ATO ALTERNATIVES
Antimony trioxide (ATO) is typically used as a synergist witharomatic brominated flame retardants (BFR) in plastics
ATO functions via the formation of flame quenching antimony tri-
halides through a gas-phase mechanism. It is not absolutelynecessary but makes the system more cost effective
Alternatives to ATO are sought due to:
I. Cost volatility of antimony metal
II. Higher cost of ATO
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8,000
9,000
10,000
11,000
12,000
13,000
14,000
15,000
16,000
17,000
18,000
MONTHLY AVERAGE LMB PRICE OF SB METAL IN $/MT
COST VOLATILITY OF ANTIMONY METAL
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METAL SALTS
1 2 3 4 6
Emerald InnovationTM 1000, % 21 21 21 21 21
ATO TMS, % 7 2 2 2 2
Zn Borate, % - 7 3.5 3.5 3.5
Ca/Zn molybdate, % - - 3.5 - -
Zn molybdate, % - - - 3.5 -
Zn phosphate, % - - - - 3.5
UL-94 @ 1.6 mm V-0 V-0 V-0 V-0 V-0
Avg. Burn Time 2.9 3.0 3.4 2.6 3.5ZB 467 = Zn Borate
Kemgard 981 = Zn phosphate
Kemgard 911A = Ca/Zn molybdate
Kemgard 911B = Zn molybdate
20% TALC FILLED POLYPROPYLENE
(PROFAX 6323)
30
Significant reduction in ATO content
Potential cost reduction
Reduced smoke emissions?
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Emerald InnovationTM 1000, % 30 27 27 27 27
ATO, % 10 4.25 4.0 4.0 3.0
Modified clay* % - 4.25 4.0 4.5 4.5
Avg. Burn time, sec 4.2/1.8 4.2/1.8 1.8/3.0 3.4/4.2
Total Burn time, sec 39 30 30 24 38
UL-94 @1.6 mm V-0 V-0 V-0 V-0 V-0
MODIFIED CLAYS UNFILLED PP HOMOPOLYMER
PROFAX 6323
*Modified clay:
quaternary ammonium and siloxane treated
montmorillonite clay.
Charex 44PSS
Amcol/Nanocor
31
Total FR loading can be reduced
ATO loading significantly reduced
Reduced smoke emissions possible?
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Emerald InnovationTM 1000, % 26 26 26 26 26 26
ATO, % 8.7 7.7 6.7 5.7 4.7 3.7
Modified clay*, % - 1 2 3 3 4
Avg. Burn time, sec 0/1.5 1.8/0.6 1.4/2.2 0.8/1 2/0.8 2/5.2
Total Burn time, sec 15 12 18 9 18 36
UL-94 @ 1.6 mm V-0 V-0 V-0 V-0 V-0 V-0
MFI, g/10min 20.0 21.2 20.7 21.0 22.08 19.19
MODIFIED CLAYS UNFILLED PP COPOLYMER
SG702 18MFI
*Modified clay: quaternary ammonium and siloxane
treated montmorillonite clay.
Charex 44PSS
Amcol/Nanocor
32
• Modified clay effectively replaces up to about 50% ATO
• Cost saving potential
• Minimum effect on flow
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MECHANICAL PROPERTIES OF UNFILLED PP COPOLYMER
CONTAINING MODIFIED CLAY
Mechanical properties slightly better
0
10
20
30
40
50
60
70
80
90
100
Notched Izod
impact (J/m)
Tensile Strength,
MPa
Strain @ Yield,
%
Strain @ Break,
%
Modulus (MPa)
FR/ATO/Nanoclay
FR/ATO
FR, % 26 26
ATO , % 8.7 6.7
Modified clay, % 2
Izod Impact, J/m 118 135.2
Tensile strength, MPa 18.2 17.0
Strain at yield, % 2.5 2.5
Strain at break,% 4.8 6.1
Modulus, MPa 1588.0 1623.4
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PPE/HIPS
wt % FR-1 Flammability
time, seconds
UL94V
Rating
3 13.5 V-2
4 8.2 V-1
5 4.8 V-0
6 2.5 V-0
wt % FR-1 Flammability
time, seconds
UL94V
Rating
8 5.8 V-1
9 5.3 V-1
10 4.2 V-0
11 3.3 V-0
V-2
V-1
V-0
V-0y = 0.75x2 - 10.39x + 37.88R² = 0.9995
0
2
4
6
8
10
12
14
16
3 3.5 4 4.5 5 5.5 6 6.5
B u r n t i m e , s e c o n d s
FR-1, wt %
V-1
V-1
V-0
V-0
y = -0.1x2 + 1.04x + 3.92
R² = 0.9915
2
3
4
5
6
7
8 9 10 11 12
B u r n t i m e , s e c o n d s
FR-1, wt %
PPE/HIPS (1:1) PPE/HIPS (1:3)
HIPS 5511, PPO640 3535
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1:1 PPE/HIPS
1:1 HIPS/PPE exhibits a V-0 rating with 5% FR-1
Mechanical properties are comparable to the base resin
10
100
1000
10000
100 1000 10000
PPE/HIPS PPE/HIPS/Emerald 1000
Property No FR 5% FR-1
UL-94 Rating (1/16”) Fail V-0
Average burn time, seconds >30 4.6
Notched Izod Impact Strength, 1/8” J/m 141 118
Reverse Notched Izod Impact , 1/8”, J/m 710.8 885.4
HDT (ºC) @ 1.8 MPa 114.1 115.0
Tensile Strength , MPa 58.2 57.1Elongation at Yield, % 9.0 8.8
Elongation at Break, % 18.7 21.9
Flexural Strength, MPa 100.1 100.5
Flexural Modulus, MPa 2571.0 2659.3
Melt flow index, 280 ºC/5kg; g/10mins 16.2 20.0
Capillary Rheology
A p p a r e n t S h e a r V i s c o s i t y ( P a - s )
Apparent Shear Rate, 1/sec
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ATO FREE HIPS FORMULATION
Emerald InnovationTM 1000 demonstrates unique performance
Does not require ATO synergist unlike other BFRs
Emerald InnovationTM 1000 FR-2 FR-3 FR-4
FR, % 12.0 12.0 12.0 15.0PPE, % 20.0 20.0 20.0 20.0
HIPS, % 62.7 62.7 62.7 59.7
Kraton D1101, % 5.0 5.0 5.0 5.0
Alkanox 240, % 0.2 0.2 0.2 0.2PETS wax, % 0.1 0.1 0.1 0.1
UL-94 1/16” V-0 Fail Fail Fail
Average Burn time,
secs
2.6 >30 >30 >30
FR-1 = Emerald Innovation™ 1000
FR-2 = decabromodiphenyl ethane
FR-3 = decabromodiphenyl ether
FR-4 = 2,4,6-Tris(2,4,6-tribromophenoxy)-1,3,5 triazine37
EMERALD INNOVATIONTM 1000/PPE VS
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EMERALD INNOVATION 1000/PPE VS
FR-2/ATO FORMULATION Emerald
InnovationTM
1000
FR-2
FR % 12.0 12.0
PPE, % 20.0 -
ATO, % - 4.0
HIPS, % 62.7 78.7
Kraton D1101, % 5.0 5.0
UL-94 1/16” V-0 V-0
Average Burn time, secs 2.0 0.2
Notched Izod Impact Strength, 1/8” J/m 235.0 101.5
Gardner Impact, J 6.98 6.16
HDT, C @ 1.8 MPa 89.5 70.1
Vicat softening temperature, C 121.3 97.6
Tensile Strength, MPa 39.8 24.2
Elongation at Yield, % 2.43 1.49
Elongation at Break, % 27.8 36.0
Flexural Strength, MPa 69.5 37.5
Flexural Modulus, MPa 2310.3 2068.9
Melt flow index, 200 C/5kg; g/10mins 0.60 8.3838
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EMERALD INNOVATIONTM 1000 VS. FR-2
Izod Impact Strength
Gardner Impact
HDT
Vicat softening
temperature
Tensile StrengthElongation at Yield
Flexural Strength
Flexural Modulus
Melt flow index
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
FR-1
FR-2
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40
0
2
4
68
10
12
14
16
18
20
190 200 210 220 230 240 250 260
M F I ,
g / 1 0 m i n s
Temperature, C
PPO 640
PPO 630
8890C
FR2/ATO
MELT VISCOSITY AS A FUNCTION OF TEMPERATURE
MFI at 240 C for Emerald InnovationTM 1000/PPE is equivalent
to FR-2/ATO at 200 C
40
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PC/ABS (80/20)
% Emerald
InnovationTM 1000
Burn Time,
seconds
UL-94
14 0 V-0
12 0 V-0
10 0 V-0
9 0.9 V-0
8 2.1 V-0
7 3.3 V-0
41
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FR 1 S FR 7
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FR-1 VS. FR-7
0
10
20
30
40
50
60
7080
90
100
MFI
Izod ImpactStrength
HDT, C
Tensile Strength
MPa
Elongation at
Yield %
Elongation at
Break, %
Flexural Strength,MPa
Flexural Modulus,MPaFR-1
FR-7
Emerald Innovation™ 1000 does not plasticize the resin unlike FR-7
Improved overall HDT, impact and mechanical properties43
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V-0 PC/ABS BLENDS
5
7
9
11
13
15
17
19
21
23
10 30 50 70 90
% F R - 1
% PC in PC-ABS
FR-1 in PC-ABS
%PC % FR-1
80 8
70 10
60 12
50 14
45 1640 18
30 22
44
Emerald Innovation™ 1000 is very versatile in producing UL 94 VO
over a wide range of different PC/ABS compositions
CONCLUSIONS
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CONCLUSIONS
Performance comparisons for Emerald Innovation™ 1000 in polyolefins and
styrenics demonstrate comparable efficiency at similar load levels over DE-
83R™ and Firemaster® 2100R
Emerald Innovation™ 1000 provides higher multi-axial impact strength than
other polymeric brominated flame retardants tested
Evaluation of metal salts and modified clays show great potential to
significantly reduce the use of high cost ATO in polyolefins whilst maintaining
flammability performance
HIPS formulations containing Emerald Innovation™ 1000 & PPE exhibits V-0
performance without ATO
In PC/ABS blends Emerald Innovation™ 1000 exhibits V-0 without ATO over a
wide range
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Fire Safety of Polystyrene Foam Insulation
Polystyrene foam insulation provides many advantages
Lightweight, Rigid, Durable and Reusable
Excellent structural properties and moisture resistance
No mold growth, No microbiological degradation
Manufactured by two processes
Expanded Polystyrene foam (EPS – via styrene monomer)
Extruded Polystyrene foam (XPS – via polystyrene resin)
Must comply with stringent fire codes
EN ISO 11925-2
German DIN 4102 B2
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The polymeric structure of Emerald Innovation™ 3000
renders it not readily bioavailable*
, thus addressingthe environmental concerns that threaten the
sustainability of many current products.
Emerald Innovation™ 3000 is an efficient, sustainable
replacement for HBCD requiring minimal modification
to current formulations or production processes.
Applicable fire safety standards covering polystyrene
foam insulation can be achieved with Emerald
Innovation™ 3000.
Synergists commonly used for EPS and XPS production
are compatible with Emerald Innovation™ 3000.
Our strategy of greener innovation provides you with proven,
sustainable alternatives
The Value of Emerald Innovation™ 3000
* Per criteria described in US Federal Register notice 40 CFR 723
51
I i ™ 3000
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Emerald Innovation™ 3000
Property Emerald Innovation™ 3000
Appearance white powder
Bromine, % 64
Softening point,0
C 1205% wt loss, 0C(Thermogravimetric Analysis (@ 10 0C/min under N2)
2620C
52
Ph i l Ch i i E ld I i TM 3000 HBCD
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Physical Characteristics Emerald InnovationTM 3000 vs HBCD
Emerald InnovationTM 3000 is available in bags and Supersacks
Property Emerald Innovation
3000
HBCD
Appearance White powder White powder
Bromine Content % 64 75
Bulk Density Loose/Packed @
250 C, g/ml0.5/0.7 1.2/1.5
TGA 5% wt loss, 0C
(Thermogravimetric Analysis (@ 100C/min under N2)
262 238
Solubility in Styreneg/100g styrene @ 25o C
>20/100 2/100
Molecular Weight (AMU) 100,000 – 160,000 642
Emerald InnovationTM 3000 is a free-flowing, polymeric , brominated flame
retardant for use in EPS and XPS applications53
Emerald Innovation™ 3000 Flammability
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y
Performance Compared to HBCD
Emerald Innovation™ 3000 demonstrates comparable thermal stability
and fire retardant efficiency versus HBCD at similar bromine levels54
Flammability Performance
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Emerald Innovation™ 3000 demonstrates comparable fire safety
performance versus HBCD at similar bromine levels
Flammability Performance
55
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Emerald InnovationTM 3000
Stabilization in XPS
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i l h
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Experimental Approach
Several combinations of primary and secondary antioxidants in combination
with an epoxy novolac resin were evaluated.
All formulations were run on a single screw extruder for multi-pass evaluation in
Polystyrene Nova PS1600 @ 200ºC.
Pellets from extrusion pass 1, 3 & 5 were set aside for melt flow and color
determination on molded plaques.
The results show that a combination of AO1, P1 and E1 gives the best color andmolecular weight retention in XPS foam.
This optimized formulation is available from Chemtura as a non-dust blend (NDB1).
NDB® technology offers superior compositional control, better hydrolytic
stability and improved industrial hygiene
A01 Anox® 20P1 Ultranox® 626
E1 Epon 164 OR Equivalent
NDB1 Lowinox® XPS 162
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Excellent Color Stability
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Y e l l o w
n e s s I n d e x
Excellent Color Stability
Color stability superior to neat polystyrene resin
AO1/P1/E1
A01 Anox® 20
P1 Ultranox® 626
E1 Epon 164 OR Equivalent
EmeraldPS + Innovation™ 3000
+ AO1/P1/E1
EmeraldPS + Innovation™ 3000
EmeraldPS + Innovation™ 3000
+ alternative AO
60
Emerald InnovationTM 3000:
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Emerald InnovationTM 3000:
Stabilization in XPS Conclusions
Emerald InnovationTM 3000 is a highly efficient firesafety solution for XPS foam insulation.
An optimized stabilizer solution has been developed
for XPS containing Emerald InnovationTM 3000.
An optimized stabilizer formula is available fromAddivant as a non-dust blend
Non-dust blend technology combines multiple
additives into a single dust-free solution offering
improved productivity, industrial hygiene,
and shelf life.
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Acknowledgements and Thanks
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Acknowledgements and Thanks
Great Lakes Solutions Applications Research Laboratory
West Lafayette, Indiana
Dr. Subra Narayan
Harry Hodgen
Julie McKeown
Ken Bol