GLS - 2013 Feiplast Brazil PDF

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
Agenda
How flame retardants work
Great Lakes Solutions products by application/polymer
Emerald InnovationTM
products for sustainable solutions

Emerald InnovationTM 1000
Emerald InnovationTM 3000 stabilization in XPS
Conclusions
What are flame retardants?

How do they work?
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
Take away one (or more) of

these and the fire can be
delayed/prevented
Source: European Flame Retardants Association, www.cefic-efra.com
4
Most Widely Used Flame Retardants Types

Mechanism
Gas phase,
Free radical
quenching
Condensed
phase, Char
forming
Endothermic
5
Flame Retardants Types
Uses & Limitations
Halogenated Flame
Retardants
Brominated FRs
Chlorinated FRs
Halogenated polymers
Antimony Synergists
Most versatile class of flame retardant

Used widely used in thermoplastics,
Phosphorus and Nitrogen

containing flame
retardants
Phosphates, Melamine
phosphates
Ammonium
Polyphosphates
Melamine Cyanurate
Typically effective in oxygen or nitrogen
Metal Hydrates
Aluminum Trihydrate
Magnesium Hydroxide
Use at high loadings

Wire & cable, coatings, rubber,
epoxy thermosets for printed wiring

boards, polyurethane foams, polyesters
Only option for many olefinic and styrenic
polymers uses
Often used with Antimony trioxide
synergist
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
thermosets
Less use in engineered plastics
Great Lakes Solutions

Polymeric and Reactive Flame Retardant Technologies
Polymer
Technology
Firemaster CP44-HF
Firemaster PBS64-HW, PDBS-80
Polyamides
Polybromostyrene
Polycarbonate, PBT
Brominated Oligomer
Polybromostyrene
BC-52, BC-58, Firemaster CP44-HF
Unsaturated Polyesters
Reactive Intermediate
PHT-4 , BA-59P
Polyurethane
Reactive Intermediate
PHT-4 Diol, PHT-4 Diol LV,

Firemaster 520
Proprietary Polymeric
Emerald Innovation 1000

Polyolefins, HDPE, PP
Styrenics, PS, HIPS, ABS
Epoxy
Products
Reactive Intermediates
Firemaster PBS64-HW, PDBS-80
BA-59P
Flame Retardants Choices for Polyolefins

Polymer
type
Polyolefins
TPO
EPDM
Bromine-based FR
Phosphorus-based
FR
Timonox /TMSBlue Star

Ultrafine Blue Star
ZB 223, ZB 467, Smokebloc
Ongard 2, LSFR
Theromoguard CPA
Firemaster 2100R

Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA
Firemaster 2100R
DP 45
Firemaster 2100R
Synergists,
Smoke Suppressants
Reofos 95
Reofos RDP
Reofos BAPP

Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA
Flame Retardants Choices for PVC & Polyurethane

Polymer
type
PVC
DP 45
Firemaster 2100R
Phosphorus based FR
Reofos 35, 50, 65 95,
Kronitex CD, TCP
Reofos 35, 50, 65, 95
Rigid PU
PHT 4 Diol
PHT 4 Diol LV
Firemaster 508
Flexible
PU
DP 45
Firemaster BZ 54
Firemaster 550
Firemaster 600
Reofos 35, 50, 65, 95

Kronitex CDP, TCP
Emerald Innovation NH-1
PDBS 80
DE-83R
Firemaster BZ 54
Firemaster 2100R
Reofos 35, 50, 65, 95

Reofos RDP
Reofos BAPP
TPU
Bromine
based FR
Synergists,
Smoke Suppressants
Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA

Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA
Flame Retardants Choices for Styrenic Resins

Polymer
type
Phosphorus
based FR
Synergists,
Smoke Suppressants
SP 75
Firemaster 2100R

Ultrafine Blue Star
ZB 223, ZB 467, Smokebloc Ongard 2,
LSFR Theromoguard CPA
ABS
BA-59P
BC-52, BC-58
Firemaster 2100R

Ultrafine Blue Star
Reofos RDP
Reofos BAPP
PC/ABS
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW
BC-52 , BC-58
Firemaster 2100R

Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA
PDBS 80
Reofos RDP,
Reofos BAPP

Ultrafine Blue Star
HIPS
PPE/HIPS
Bromine
based FR
Flame Retardants Choices for Polystyrene Foams
Polymer type
10
Bromine-based FR
EPS

CD 75P
XPS

CD 75P
SP 75
Flame Retardants Choices for Thermosets

Polymer type
Bromine-based FR
UPES
(unsaturated
polyester)
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW *PHT 4
*BA-59P
Firemaster BZ-54
Firemaster 2100R
Epoxy
Phenolic
*BA-59P
Firemaster BZ-54
Firemaster 2100R
DP 45
Firemaster BZ-54
Firemaster 550
Firemaster 552
DE-83R
Firemaster 2100R
* Reactive FR
11
Phosphorusbased FR
Synergists,
Smoke Suppressants
Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA
Reofos 50, 65, 95

Kronitex CDP
Reofos RDP
Reofos BAPP

Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CPA
Ultrafine Blue Star
Ongard 2, LSFR
Theromoguard CP
Flame Retardants Choices for Polyamides
Polymer type
PA 6
PA 66
HTPA
12
Bromine-based FR
Synergists,
Smoke Suppressants
PDBS 80
Firemaster CP-44HF
Firemaster 2100R
Timonox/TMSBlue Star
Ultrafine Blue Star
ZB 467
PDBS 80
Firemaster CP-44HF

Ultrafine Blue Star
ZB 467
PDBS 80
Firemaster CP-44HF
Timonox/TMSBlue Star
Ultrafine Blue Star
ZB 467
Flame Retardants Choices for Engineering Thermoplastics
Polymer type
PBT
PET
PC
13
Bromine-based FR
Synergists,
Smoke Suppressants
PDBS 80
Firemaster CP-44HF
Firemaster PBS-64 HW BC-52
BC-58

Ultrafine Blue Star
ZB 467
PDBS 80
Firemaster CP-44HF

Ultrafine Blue Star
ZB 467
BC-52
BC-58
ZB 467
Developing Sustainable
Flame Retardant Solutions
Great Lakes Solutions

&
Emerald Innovation
series of flame retardants
14
Introducing Emerald Innovation, Our Next Generation

of Products
Sustainable, Versatile Polymeric Flame
Retardant
Combination Flame Retardant and Curing
Agent for Non-Halogen Epoxy Printed Circuit
Board Laminates
Sustainable, Innovative, High-Performance,
Brominated Polymeric Flame Retardant for
EPS and XPS Foam Insulation
Halogen-Free Flame Retardant for Flexible
Polyurethane Foam
Why Emerald Innovation?

Products are innovative, reliable and also minimize the impact on our
environment and human health while maintaining superior
performance and quality
15
A Sustainable, Versatile, Brominated Polymeric

Flame Retardant
16
EMERALD INNOVATIONTM 1000 TYPICAL PROPERTIES

Emerald InnovationTM 1000 IS A POLYMERIC BROMINATED FLAME RETARDANT
DESIGNED FOR USE IN A BROAD SPECTRUM OF APPLICATIONS
Property
Appearance
Off-white
powder
Bromine, %
78
Average particle size, (m)
5-6
5% wt loss, 0C
(Thermogravimetric Analysis (@ 10 0C/min under N2)
High bromine content with excellent thermal stability

17
Emerald
Innovation
1000
4100C
EMERALD INNOVATIONTM 1000

HIGH DENSITY POLYETHYLENE*
IN
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
Property
*LYONDELLBASELL PETROTHENE R590005 (0.8MFI)

ALL FORMULATIONS CONTAIN 6.3% ANTIMONY TRIOXIDE
Emerald Innovation 1000 offers an excellent balance of efficiency,

physical properties and flammability performance in HDPE formulations
18
LABEL
FR-1
FR-2
FR-3
FR-4
DESCRIPTION
DECABROMODIPHENYL OXIDE (DE-83R)
BIS (PENTABROMOPHENYL) ETHANE (2FIREMASTER 2100R)
POLY(PENTABROMOBENZYL) ACRYLATE (FR-1025)
ETHYLENEBIS(TETRABROMOPHTHALIMIDE) (SAYTEX BT-93)
COMPARISON OF MELT VISCOSITIES

CAPILLARY RHEOLOGY OF HDPE FORMULATION
CONTAINING EMERALD INNOVATIONTM 1000
10000
Emerald1000
Innovation 1000
Emerald
FR1
FR2
FR3
1000
FR4
Viscosity, Pa-sec
100
10
10
100
1000
Shear Rate, 1/sec
Comparable viscosities in HDPE formulations indicate that Emerald

Innovation 1000 will process under similar conditions as current flame
retardant formulations
19
10000
MULTI-AXIAL IMPACT OF HDPE WITH

EMERALD INNOVATIONTM 1000 VS. FR-3
FR-3
Brittle failure and

delamination
Ductile yield
Superior compatibility of Emerald Innovation 1000 with HDPE results in

significantly better toughness vs. FR-3 for demanding applications
20
03/30/2012 V1.0

PERFORMANCE IN TALC-FILLED POLYPROPYLENE, COPOLYMER
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
2.29
2.42
2.38
Property
ALL FORMULATIONS CONTAIN 20% TALC AND 7% ANTIMONY TRIOXIDE

LABEL DESCRIPTION
FR-1 DECABROMODIPHENYL OXIDE (DE-83R)
FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTE 2100R)
Emerald Innovation TM 1000 is an effective replacement for FR -1 and FR-2

in filled polypropylene formulations
21

PERFORMANCE COMPARISON IN HIPS
All formulations contain 4.0% antimony trioxide

*afterglow
Excellent impact performance

Efficiency at equal or lower load levels
Equivalent Vicat softening performance
Melt flow similar to DE-83R, superior to Firemaster 2100R
22
LABEL DESCRIPTION
FR-1
FR-2
BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER 2100R)
FR-3
2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE
REDUCED IMPACT MODIFIER LOADING

Impact Strength in Impact Modified HIPS
With 12% FR and 4% ATO
Notched Izod Impact Strength, J/m
170
160
150
140
130
Emerald
Emerald
1000
Innovation
1000
120
Firemaster
Firemaster2100R
2100R
110
100
Same impact strength
at over 40% lower
impact modifier load
90
80
1
3
% Kraton D1101
The higher impact strength achieved with Emerald Innovation 1000

provides an opportunity to reduce impact modifier loading, and thus
reduced formulation cost
23
COMPARISON OF MELT VISCOSITIES

CAPILLARY RHEOLOGY - HIPS
10000
Shear Viscosity, Pa-sec
220 0C
1000
Emerald
Emerald
10001000
Innovation
FR-1
FR-2
100
FR-3
10
10
LABEL DESCRIPTION
FR-1
FR-2
BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER 2100R)
FR-3
2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE
100
1000
Shear Rate, 1/sec
Comparable viscosities in HIPS formulations indicate that Emerald

Innovation 1000 will process under same conditions as current flame
retardant formulations
24
10000
EMERALD INNOVATION 1000 IN INJECTION MOLDING GRADE ABS

Emerald
Innovation
1000
FR 2
FR 3
FR 4
13.0
13.0
16.2
21.7
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 C/10

kg
29
21
43
73
FR, %
UL-94 @ 1.6 mm
HDT, C, , 1.8MPa
75.2
Notched Izod Impact Strength
76.5
73.8
73.2
* All formulations contain 5.0 % antimony trioxide and 0.3% PTFE

High efficiency and excellent balance of properties
25
107
84
55
41
Joules/Meter
Emerald
Emerald
1000
Innovation
1000
FR 2
FR 3
FR 4

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
26
LOW-ATO OR ATO-FREE SOLUTIONS
27
v.2.0
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 trihalides through a gas-phase mechanism. It is not absolutely
necessary but makes the system more cost effective
Alternatives to ATO are sought due to:
28
I.
Cost volatility of antimony metal
II.
Higher cost of ATO
COST VOLATILITY OF ANTIMONY METAL

MONTHLY AVERAGE LMB PRICE OF SB METAL IN
$/MT
18,000
17,000
16,000
15,000
14,000
13,000
12,000
11,000
10,000
9,000
8,000
29
METAL SALTS
20% TALC FILLED POLYPROPYLENE

(PROFAX 6323)
1
Emerald InnovationTM 1000, %
21
21
21
21
21
ATO TMS, %
Zn Borate, %
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
Significant reduction in ATO content

Potential cost reduction
Reduced smoke emissions?
30
MODIFIED CLAYS
UNFILLED PP HOMOPOLYMER
PROFAX 6323
30
27
27
27
27
ATO, %
10
4.25
4.0
4.0
3.0
4.25
4.0
4.5
4.5
4.2/1.8
4.2/1.8
1.8/3.0
3.4/4.2
Modified clay* %
Avg. Burn time, sec
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 clay:
quaternary ammonium and siloxane treated
montmorillonite clay.
Charex 44PSS
Amcol/Nanocor
Total FR loading can be reduced

ATO loading significantly reduced
Reduced smoke emissions possible?
31
MODIFIED CLAYS
UNFILLED PP COPOLYMER
SG702 18MFI
26
26
26
26
26
26
ATO, %
8.7
7.7
6.7
5.7
4.7
3.7
0.8/1
2/0.8
2/5.2
Modified clay*, %
Avg. Burn time, sec
0/1.5 1.8/0.6 1.4/2.2
Total Burn time, sec
15
12
18
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 clay: quaternary ammonium and siloxane

treated montmorillonite clay.
Charex 44PSS
Modified clay effectively replaces up to about 50% ATO
Cost saving potential
Minimum effect on flow
32
Amcol/Nanocor
MECHANICAL PROPERTIES OF UNFILLED PP COPOLYMER

CONTAINING MODIFIED CLAY
Notched Izod
impact (J/m)
Modulus (MPa)
Strain @ Break,
%
100
90
80
70
60
50
40
30
20
10
0
FR/ATO/Nanoclay
FR/ATO
Tensile Strength,
MPa
Strain @ Yield,
%
Mechanical properties slightly better

33
FR, %
ATO , %
Modified clay, %
26
8.7
26
6.7
2
Izod Impact, J/m
118
135.2
18.2
2.5
4.8
1588.0
17.0
2.5
6.1
1623.4
Tensile strength, MPa

Strain at yield, %
Strain at break,%
Modulus, MPa
ATO FREE FORMULATIONS FOR IMPACT MODIFIED HIPS

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
20% PPE gives a V-0 rating in HIPS/Emerald 1000

This formulation is ATO free
34
PPE/HIPS
PPE/HIPS (1:1)
wt % FR-1
3
4
5
6
Flammability
time, seconds
13.5
8.2
4.8
2.5
PPE/HIPS (1:3)
UL94V
Rating
V-2
V-1
V-0
V-0
wt % FR-1
8
9
10
11
16
14
V-2
V-1
Burn time, seconds
Burn time, seconds
12
10
V-1
8
6
V-0
V-1
V-0
4
V-0
V-0
y = 0.75x2 - 10.39x + 37.88

R = 0.9995
y = -0.1x2 + 1.04x + 3.92

R = 0.9915
2
3
3.5
HIPS 5511, PPO640
35 35
Flammability UL94V
time, seconds Rating
5.8
V-1
5.3
V-1
4.2
V-0
3.3
V-0
4.5
FR-1, wt %
5.5
6.5
8
35
10
FR-1, wt %
11
12
1:1 PPE/HIPS
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
Capillary Rheology
10000
Apparent Shear Viscosity (Pa-s)
Property
1000
Reverse Notched Izod Impact , 1/8, J/m
710.8
885.4
HDT (C) @ 1.8 MPa
114.1
115.0
Tensile Strength , MPa
58.2
57.1
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
16.2
20.0
Melt flow index, 280 C/5kg; g/10mins
100
10
100
1:1 HIPS/PPE exhibits a V-0 rating with 5% FR-1

Mechanical properties are comparable to the base resin
36
1000
PPE/HIPS
PPE/HIPS/Emerald 1000
Apparent Shear Rate, 1/sec
10000
ATO FREE HIPS FORMULATION

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
Emerald InnovationTM 1000 demonstrates unique performance

Does not require ATO synergist unlike other BFRs
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
37
EMERALD INNOVATIONTM 1000/PPE VS

FR-2/ATO FORMULATION
FR %
PPE, %
ATO, %
HIPS, %
Kraton D1101, %
UL-94 1/16
Notched Izod Impact Strength, 1/8 J/m
Gardner Impact, J
HDT, C @ 1.8 MPa
Vicat softening temperature, C
Tensile Strength, MPa
Melt flow index, 200 C/5kg; g/10mins
38
Emerald
InnovationTM
1000
12.0
20.0
62.7
5.0
V-0
2.0
235.0
6.98
89.5
121.3
39.8
2.43
27.8
69.5
2310.3
0.60
FR-2
12.0
4.0
78.7
5.0
V-0
0.2
101.5
6.16
70.1
97.6
24.2
1.49
36.0
37.5
2068.9
8.38
EMERALD INNOVATIONTM 1000 VS. FR-2

Melt flow index
Flexural Modulus
100.0 Izod Impact Strength

90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0.0
Gardner Impact
Elongation at Yield
FR-2
HDT
Vicat softening
temperature
Flexural Strength
39
FR-1
Tensile Strength
MFI, g/10mins
MELT VISCOSITY AS A FUNCTION OF TEMPERATURE

20
18
16
14
12
10
8
6
4
2
0
PPO 640
PPO 630
FR2/ATO
8890C
190
200
210
220
230
Temperature, C
240
250
260
MFI at 240 C for Emerald InnovationTM 1000/PPE is equivalent

to FR-2/ATO at 200 C
40
PC/ABS (80/20)
% Emerald
Burn Time,
InnovationTM 1000 seconds
14
0
12
0
10
0
9
0.9
8
2.1
7
3.3
41
UL-94
V-0
V-0
V-0
V-0
V-0
V-0
ATO FREE PC/ABS (80/20)

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
1.7
1.6
2.6
0.6
Melt flow index, 260C/2.16kg; g/10mins
9.4
8.6
9.7
33.9
HDT C @ 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
5.3
5.6
5.5
4.4
40.3
31.7
38.0
23.1
104.7
108.7
106.6
113.0
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
All formulations contain 0.1% Ultranox 626 & PETS wax

FR-6 formulation contains 0.1% PTFE
FR-1 VS. FR-7

MFI
Flexural Modulus,
MPa
Flexural Strength,
MPa
100
90
80
70
60
50
40
30
20
10
0
Elongation at
Break, %
Emerald Innovation 1000 does not plasticize the resin unlike FR-7
Improved overall HDT, impact and mechanical properties
FR-1
FR-7
HDT, C
Tensile Strength
MPa
Elongation at
Yield, %
43
Izod Impact
Strength
V-0 PC/ABS BLENDS

% FR-1
8
10
12
14
16
18
22
FR-1 in PC-ABS
% FR-1
%PC
80
70
60
50
45
40
30
23
21
19
17
15
13
11
9
7
5
10
30
Emerald Innovation 1000 is very versatile in producing UL 94 VO

over a wide range of different PC/ABS compositions
44
50
% PC in PC-ABS
70
90
CONCLUSIONS
Performance comparisons for Emerald Innovation 1000 in polyolefins and
styrenics demonstrate comparable efficiency at similar load levels over DE83R 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
45
Sustainable, Innovative, High-Performance,

Brominated Polymeric Flame Retardant for
Polystyrene Foams
46
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
47
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
The Value of Emerald Innovation 3000
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
51
Per criteria described in US Federal Register notice 40 CFR 723
Property
Appearance
white powder
Bromine, %
64
Softening point, 0C
120
5% wt loss, 0C
(Thermogravimetric Analysis (@ 10
52
0C/min
under N2)
2620C
Physical Characteristics Emerald InnovationTM 3000 vs HBCD

Property
Appearance
Bromine Content %
Bulk Density Loose/Packed @
250 C, g/ml
TGA 5% wt loss, 0C
(Thermogravimetric Analysis (@ 10
0C/min
Emerald Innovation
3000
HBCD
White powder
White powder
64
75
0.5/0.7
1.2/1.5
262
238
>20/100
2/100
100,000 160,000
642
under N2)
Solubility in Styrene
g/100g styrene @ 25o C
Molecular Weight (AMU)
Emerald InnovationTM 3000 is available in bags and Supersacks
Emerald InnovationTM 3000 is a free-flowing, polymeric , brominated flame

retardant for use in EPS and XPS applications
53
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
54
Flammability Performance
Emerald Innovation 3000 demonstrates comparable fire safety

performance versus HBCD at similar bromine levels
55

Stabilization in XPS
56
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.
A01
P1
E1
Extensive Testing Conducted to Determine an Optimal Stabilizer

Solution
57
Anox 20
Ultranox 626
Epon 164 OR Equivalent
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 @ 200C.
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).
A01
P1
E1
NDB1
Anox 20
Ultranox 626
Lowinox XPS 162
NDB technology offers superior compositional control, better hydrolytic

stability and improved industrial hygiene
58
Melt Flow Index, g/10mins
Molecular Weight Stability
Emerald
Emerald
PS + Innovation 3000 PS + Innovation 3000
AO1/P1/E1
+ AO1/P1/E1
A01
P1
E1
Anox 20
Ultranox 626
Excellent retention of polystyrene molecular weight

59
Emerald
PS + Innovation 3000
+ alternative AO
Yellowness Index
Excellent Color Stability
Emerald
Emerald
PS + Innovation 3000 PS + Innovation 3000
AO1/P1/E1
+ AO1/P1/E1
A01
P1
E1
Anox 20
Ultranox 626
Color stability superior to neat polystyrene resin

60
Emerald
PS + Innovation 3000
+ alternative AO
Emerald InnovationTM 3000:

Stabilization in XPS Conclusions
61
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.
Emerald Innovation 3000TM:

Your Sustainable FR Solution for EPS and XPS
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.
62
Acknowledgements and Thanks

Great Lakes Solutions Applications Research Laboratory
West Lafayette, Indiana
Dr. Subra Narayan
Harry Hodgen
Julie McKeown
Ken Bol
63

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Recent developments in flame retardants

for sustainable fire safety solutions

products for sustainable solutions

What are flame retardants?

Flame Retardants Interrupt the Fire Cycle

Flame retardants work by one of

Take away one (or more) of

Most Widely Used Flame Retardants Types

Flame Retardants Types

Uses & Limitations

Most versatile class of flame retardant

Phosphorus and Nitrogen

Typically effective in oxygen or nitrogen

Use at high loadings

epoxy thermosets for printed wiring

Great Lakes Solutions

BC-52, BC-58, Firemaster CP44-HF

PHT-4 Diol, PHT-4 Diol LV,

Emerald Innovation 1000

Firemaster PBS64-HW, PDBS-80

Emerald Innovation 2000

Flame Retardants Choices for Polyolefins

Timonox /TMSBlue Star

Timonox /TMSBlue Star

Timonox /TMSBlue Star

Flame Retardants Choices for PVC & Polyurethane

Reofos 35, 50, 65, 95

Reofos 35, 50, 65, 95

Reofos 35, 50, 65, 95

Timonox /TMSBlue Star

Flame Retardants Choices for Styrenic Resins

Timonox /TMSBlue Star

Timonox /TMSBlue Star

Timonox /TMSBlue Star

Timonox /TMSBlue Star

Flame Retardants Choices for Polystyrene Foams

Emerald Innovation 3000

Emerald Innovation 3000

Flame Retardants Choices for Thermosets

Reofos 50, 65, 95

Timonox /TMSBlue Star

Flame Retardants Choices for Polyamides

Timonox /TMSBlue Star

Flame Retardants Choices for Engineering Thermoplastics

Timonox /TMSBlue Star

Timonox /TMSBlue Star

Great Lakes Solutions

Introducing Emerald Innovation, Our Next Generation

Emerald Innovation 1000

Emerald Innovation 3000

Why Emerald Innovation?

Emerald Innovation 2000

Emerald Innovation NH-1

A Sustainable, Versatile, Brominated Polymeric

EMERALD INNOVATIONTM 1000 TYPICAL PROPERTIES

Average particle size, (m)

High bromine content with excellent thermal stability

EMERALD INNOVATIONTM 1000

Emerald InnovationTM 1000

Whiteness Index, CIE

*LYONDELLBASELL PETROTHENE R590005 (0.8MFI)

Emerald Innovation 1000 offers an excellent balance of efficiency,