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Recent developments in flame retardants for sustainable fire safety solutions
Presentation by Michael Kearns, Technical Business Support EMEA Great Lakes Solutions, a Chemtura business May 22, 2013
2
Agenda
How flame retardants work
Great Lakes Solutions products by application/polymer
Emerald InnovationTM products for sustainable solutions
Emerald InnovationTM 1000
Emerald InnovationTM 3000
Emerald InnovationTM 3000 – stabilization in XPS
Conclusions
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What are flame retardants?
How do they work?
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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 of three mechanisms
Interruption of radical mechanism of combustion process in the gas phase
Reaction in the solid phase to form a carbonaceous char which serves as a barrier between fuel and the heat and oxygen source
Endothermic processes, such as release of water, to remove the heat 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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Most Widely Used Flame Retardants Types
Mechanism Flame Retardants Types Uses & Limitations
Gas phase, Free radical quenching
Halogenated Flame Retardants Brominated FRs Chlorinated FRs Halogenated polymers Antimony Synergists
Most versatile class of flame retardant Used widely used in thermoplastics,
epoxy thermosets for printed wiring boards, polyurethane foams, polyesters
Only option for many olefinic and styrenic polymers uses
Often used with Antimony trioxide synergist
Condensed phase, Char forming
Phosphorus and Nitrogen containing flame retardants Phosphates, Melamine phosphates Ammonium Polyphosphates Melamine Cyanurate
Typically effective in oxygen or nitrogen containing polymers such as polycarbonate, polyesters, polyamides and epoxy resins
Often used with synergist to promote char formation, 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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Great Lakes Solutions Polymeric and Reactive Flame Retardant Technologies
Polymer Technology Products
Polyamides Polybromostyrene Firemaster® CP44-HF Firemaster® PBS64-HW, PDBS-80™
Polycarbonate, PBT Brominated Oligomer
Polybromostyrene
BC-52™, BC-58™, Firemaster® CP44-HF
Firemaster® PBS64-HW, PDBS-80™
Unsaturated Polyesters Reactive Intermediate PHT-4 ™, BA-59P™
Polyurethane Reactive Intermediate PHT-4 Diol™, PHT-4 Diol™ LV, Firemaster® 520
Polyolefins, HDPE, PP Proprietary Polymeric
Emerald Innovation™ 1000 Emerald Innovation™ 3000 Styrenics, PS, HIPS, ABS
Epoxy Reactive Intermediates BA-59P™
Emerald Innovation™ 2000
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Flame Retardants Choices for Polyolefins
Polymer type
Bromine-based FR Phosphorus-based
FR Synergists,
Smoke Suppressants
Polyolefins
Firemaster® 2100R Emerald Innovation™ 1000
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
TPO
Firemaster® 2100R Emerald Innovation™ 1000
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
EPDM
DP 45™ Firemaster® 2100R Emerald Innovation™ 1000
Reofos® 95 Reofos® RDP Reofos® BAPP
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
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Flame Retardants Choices for PVC & Polyurethane
Polymer type
Bromine based FR
Phosphorus based FR Synergists, Smoke Suppressants
PVC
DP 45™ Firemaster® 2100R Emerald Innovation™ 1000
Reofos® 35, 50, 65 95, Kronitex® CD, TCP
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 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
Flexible PU
DP 45™ Firemaster® BZ 54 Firemaster® 550 Firemaster® 600
Reofos® 35, 50, 65, 95 Kronitex® CDP, TCP Emerald Innovation™ NH-1
TPU
PDBS 80™ DE-83R™ Firemaster® BZ 54 Firemaster® 2100R Emerald Innovation™ 1000
Reofos® 35, 50, 65, 95 Reofos® RDP Reofos® BAPP Emerald Innovation™ NH-1
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
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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® 2100R Emerald Innovation™ 1000
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
ABS
BA-59P™ BC-52™, BC-58™ Firemaster® 2100R Emerald Innovation™ 1000
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
PC/ABS
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW BC-52™ , BC-58™ Firemaster® 2100R Emerald Innovation™ 1000
Reofos® RDP Reofos® BAPP
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
PPE/HIPS
PDBS 80™ Emerald Innovation™ 1000
Reofos® RDP, Reofos® BAPP
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
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Flame Retardants Choices for Polystyrene Foams
Polymer type Bromine-based FR
EPS
Emerald Innovation™ 3000 CD 75P™
XPS
Emerald Innovation™ 3000 CD 75P™ SP 75™
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Flame Retardants Choices for Thermosets
Polymer type Bromine-based FR Phosphorus-
based FR Synergists,
Smoke Suppressants
UPES (unsaturated
polyester)
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW *PHT 4™ *BA-59P™ Firemaster® BZ-54 Firemaster® 2100R Emerald Innovation™ 1000
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
Epoxy
*BA-59P™ Firemaster® BZ-54 Firemaster® 2100R Emerald Innovation™ 1000
Reofos® 50, 65, 95 Kronitex® CDP Reofos® RDP Reofos® BAPP
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CPA
Phenolic
DP 45™ Firemaster® BZ-54 Firemaster® 550 Firemaster® 552 DE-83R™ Firemaster® 2100R Emerald Innovation™ 1000
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 223, ZB 467, Smokebloc® Ongard® 2, LSFR™ Theromoguard® CP
* Reactive FR 11
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Flame Retardants Choices for Polyamides
Polymer type Bromine-based FR Synergists,
Smoke Suppressants
PA 6
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW Firemaster® 2100R
Timonox®/TMS®Blue Star Ultrafine® Blue Star ZB 467
PA 66
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 467
HTPA
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW
Timonox®/TMS®Blue Star Ultrafine® Blue Star ZB 467
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Flame Retardants Choices for Engineering Thermoplastics
Polymer type Bromine-based FR Synergists,
Smoke Suppressants
PBT
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW BC-52™ BC-58™
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 467
PET
PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW
Timonox® /TMS®Blue Star Ultrafine® Blue Star ZB 467
PC Firemaster® PBS-64 HW BC-52™ BC-58™
ZB 467
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Developing Sustainable Flame Retardant Solutions
Great Lakes Solutions &
Emerald Innovation™ series of flame retardants
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Introducing Emerald Innovation™, Our Next Generation of Products Emerald Innovation™ 1000 Sustainable, Versatile Polymeric Flame Retardant 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 Flexible Polyurethane Foam
Emerald Innovation™ 1000 Emerald Innovation™ 2000
Emerald Innovation™ 3000 Emerald Innovation™ NH-1
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Why Emerald Innovation™?
Products are innovative, reliable and also minimize the impact on our environment and human health while maintaining superior performance and quality
A Sustainable, Versatile, Brominated Polymeric Flame 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-white powder
Bromine, % 78
Average particle size, (µm) 5-6
5% wt loss, 0C (Thermogravimetric Analysis (@ 10 0C/min under N2)
4100C
EMERALD INNOVATIONTM 1000 TYPICAL PROPERTIES
High bromine content with excellent thermal stability
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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MULTI-AXIAL IMPACT OF HDPE WITH EMERALD INNOVATIONTM 1000 VS. FR-3
Superior compatibility of Emerald Innovation™ 1000 with HDPE results in significantly better toughness vs. FR-3 for demanding applications
FR-3 Emerald Innovation™ 1000
Brittle failure and delamination
Ductile yield
03/30/2012 V1.0 20
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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/10min 230oC/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)
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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
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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
No
tch
ed
Izo
d Im
pac
t St
ren
gth
, J
/m
% Kraton D1101
Emerald 1000
Firemaster 2100R
Emerald Innovation™ 1000
Firemaster 2100R
Impact Strength in Impact Modified HIPS
With 12% FR and 4% ATO
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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
She
ar V
isco
sity
, Pa-
sec
Shear Rate, 1/sec
CAPILLARY RHEOLOGY - HIPS
Emerald 1000
FR-1
FR-2
FR-3
Emerald Innovation™ 1000
24
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 2583
2777
Notched Izod Impact, J/m 107.3 55.0 83.8 41.1
MFI, g/10min, 230 ºC/10 kg
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 4 Emerald Innovation™ 1000
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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
LOW-ATO OR ATO-FREE SOLUTIONS
v.2.0 27
28
WHY THE NEED FOR ATO ALTERNATIVES
Antimony trioxide (ATO) is typically used as a synergist with aromatic 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 absolutely necessary 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 3.5
ZB 467 = Zn Borate Kemgard 981 = Zn phosphate Kemgard 911A = Ca/Zn molybdate Kemgard 911B = Zn molybdate
20% TALC FILLED POLYPROPYLENE (PROFAX 6323)
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Significant reduction in ATO content Potential cost reduction Reduced smoke emissions?
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
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Total FR loading can be reduced ATO loading significantly reduced Reduced smoke emissions possible?
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
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• Modified clay effectively replaces up to about 50% ATO • Cost saving potential • Minimum effect on flow
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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ATO FREE FORMULATIONS FOR IMPACT MODIFIED HIPS
20% PPE gives a V-0 rating in HIPS/Emerald 1000
This formulation is ATO free
Emerald InnovationTM 1000 FR2 FR3
FR, % 12.0 12.0 12.0 12.0 12.0 15.0
PPE, % 8.0 10.0 15.0 20.0 20.0 20.0
HIPS, % 74.8 72.8 67.8 62.8 62.7 59.7
Kraton D1101 5.0 5.0 5.0 5.0 5.0 5.0
Alkanox 240, % 0.2 0.2 0.2 0.2 0.2 0.2
UL-94 1/16” Fail Fail Fail V-0 Fail Fail
Average Burn time, secs >30 >30 >30 2.0 >30 >30
34
35
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-0 y = 0.75x2 - 10.39x + 37.88 R² = 0.9995
0
2
4
6
8
10
12
14
16
3 3.5 4 4.5 5 5.5 6 6.5
Bu
rn t
ime
, se
con
ds
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
Bu
rn t
ime
, se
con
ds
FR-1, wt %
PPE/HIPS (1:1) PPE/HIPS (1:3)
HIPS 5511, PPO640 35 35
36
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 57.1
Elongation 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
Ap
pa
ren
t S
hea
r V
isco
sit
y (
Pa
-s)
Apparent Shear Rate, 1/sec
36
37
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 15.0
PPE, % 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 0.2
PETS 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 triazine
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38
EMERALD INNOVATIONTM 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 8.38 38
39
EMERALD INNOVATIONTM 1000 VS. FR-2
Izod Impact Strength
Gardner Impact
HDT
Vicat softening temperature
Tensile Strength Elongation 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
39
40
0
2
4
6
8
10
12
14
16
18
20
190 200 210 220 230 240 250 260
MFI
, g/1
0m
ins
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
41
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
42
ATO FREE PC/ABS (80/20)
All formulations contain 0.1% Ultranox 626 & PETS wax
FR-6 formulation contains 0.1% PTFE
Emerald
Innovation™
1000
FR-5 FR-6 FR-7
FR % 8.0 10.5 8.6 13.0
UL-94, 1.6 mm V-0 V-2 V-2 V-0
Average Burn time, secs 1.7 1.6 2.6 0.6
Melt flow index, 260ºC/2.16kg; g/10mins 9.4 8.6 9.7 33.9
HDT ºC @ 1.8 MPa 111.8 115.2 112.5 81.7
Notched Izod Impact, 3.2 mm J/m 656.3 208.3 592.7 52.3
Tensile Strength, MPa 64.6 67.4 64.7 69.8
Elongation at Yield, % 5.3 5.6 5.5 4.4
Elongation at Break, % 40.3 31.7 38.0 23.1
Flexural Strength, MPa 104.7 108.7 106.6 113.0
Flexural Modulus, MPa 2675.9 2692.4 2691.0 3003.4
FR-5 = brominated carbonate oligomer
FR-6 = poly(pentabromobenzyl acrylate)
FR-7 = bisphenol-A bisdiphenyl phosphate 42
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FR-1 VS. FR-7
0
10
20
30
40
50
60
70
80
90
100
MFI
Izod Impact Strength
HDT, °C
Tensile Strength MPa
Elongation at Yield, %
Elongation at Break, %
Flexural Strength, MPa
Flexural Modulus, MPa
FR-1
FR-7
Emerald Innovation™ 1000 does not plasticize the resin unlike FR-7 Improved overall HDT, impact and mechanical properties
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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 16
40 18
30 22
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Emerald Innovation™ 1000 is very versatile in producing UL 94 VO over a wide range of different PC/ABS compositions
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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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Sustainable, Innovative, High-Performance, Brominated Polymeric Flame Retardant for Polystyrene Foams
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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 addressing the 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
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Emerald Innovation™ 3000
Property Emerald Innovation™ 3000
Appearance white powder
Bromine, % 64
Softening point, 0C 120
5% wt loss, 0C (Thermogravimetric Analysis (@ 10 0C/min under N2)
2620C
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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/ml
0.5/0.7 1.2/1.5
TGA 5% wt loss, 0C (Thermogravimetric Analysis (@ 10 0C/min under N2)
262 238
Solubility in Styrene g/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 applications
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Emerald Innovation™ 3000 Flammability Performance Compared to HBCD
Emerald Innovation™ 3000 demonstrates comparable thermal stability and fire retardant efficiency versus HBCD at similar bromine levels
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Emerald Innovation™ 3000 demonstrates comparable fire safety performance versus HBCD at similar bromine levels
Flammability Performance
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Emerald InnovationTM 3000
Stabilization in XPS
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Stabilization of Emerald InnovationTM 3000 for use in extruded polystyrene foam
Emerald InnovationTM 3000 is an efficient flame retardant for use in extruded polystyrene foam (XPS) and like HBCD will require stabilization during extrusion.
A stabilizer formula consisting of hindered phenol (AO1), a high performance phosphite (P1), and an epoxy novalac resin (E1) provides the most effective stabilization package for Emerald 3000 in XPS foam.
This stabilizer system provides an excellent balance of color and molecular weight
retention in XPS foam formulated with Emerald Innovation™ 3000.
Extensive Testing Conducted to Determine an Optimal Stabilizer Solution
A01 Anox® 20
P1 Ultranox® 626
E1 Epon 164 OR Equivalent
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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 and molecular 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® 20
P1 Ultranox® 626
E1 Epon 164 OR Equivalent
NDB1 Lowinox® XPS 162
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Molecular Weight Stability
Excellent retention of polystyrene molecular weight
Me
lt F
low
Ind
ex,
g/1
0m
ins
AO1/P1/E1
A01 Anox® 20
P1 Ultranox® 626
E1 Epon 164 OR Equivalent
Emerald PS + Innovation™ 3000 + AO1/P1/E1
Emerald PS + Innovation™ 3000
Emerald PS + Innovation™ 3000 + alternative AO
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60
Yello
wn
ess
Ind
ex
Excellent Color Stability
Color stability superior to neat polystyrene resin
AO1/P1/E1
A01 Anox® 20
P1 Ultranox® 626
E1 Epon 164 OR Equivalent
Emerald PS + Innovation™ 3000 + AO1/P1/E1
Emerald PS + Innovation™ 3000
Emerald PS + Innovation™ 3000 + alternative AO
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Emerald InnovationTM 3000: Stabilization in XPS Conclusions
Emerald InnovationTM 3000 is a highly efficient fire safety solution for XPS foam insulation.
An optimized stabilizer solution has been developed for XPS containing Emerald InnovationTM 3000.
An optimized stabilizer formula is available from Addivant 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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The polymeric nature of Emerald InnovationTM 3000 renders it more sustainable than other flame retardant alternatives.
Emerald InnovationTM 3000 is the best choice when developing a sustainable product portfolio.
In EPS and XPS, Emerald InnovationTM 3000 demonstrates comparable efficiency at similar bromine content to HBCD.
Unlike HBCD, Emerald InnovationTM 3000 does not interfere in polystyrene polymerization chemistry, providing improved control of molecular weight during EPS production.
The high solubility of Emerald InnovationTM 3000 in styrene monomer allows for easy introduction into EPS production processes.
Emerald InnovationTM 3000 can be easily incorporated into a masterbatch for use in XPS.
Emerald Innovation 3000TM: Your Sustainable FR Solution for EPS and XPS
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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
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