2013 SKZ China

Recent developments in flame retardants for sustainable fire safety solutions

Dr. Grace Han 4th International Conference on Flame Retardants

Chinese and International Markets

Requirements, Challenges and Innovations

19-20 May 2013

Agenda

Great Lakes Solutions Overview

Greener Innovation Strategies

Emerald InnovationTM 1000 – polymeric Flame Retardant

Solutions for Antimony Trioxide Reduction

Emerald InnovationTM 3000 – polymeric Flame Retardant

Global specialty chemical company listed on the New York Stock Exchange (“CHMT”)

Major markets served are energy & electronics, transportation, and agriculture

Committed to global sustainability and engineering chemical solutions that meet our customers’ evolving needs

More than 4,300 employees worldwide

Manufactures in 31 countries and sells products in over 100 countries

Global headquarters in Philadelphia, Pennsylvania

Regional headquarters and shared service centers in Sao Paulo, Brazil; Shanghai, China; Middlebury, Connecticut; and Manchester, United Kingdom

Great Lakes Solutions, an Industry Leader

Electrical & Electronics

Insulation & Furniture

Automotive

Fumigation Energy: Oilfield & Mercury Control

Fine Chemical/ Pharmaceutical

Biocides Automotive Tires Fumigation

Biocides

Other

Insulation &

Furniture

Electrical & Electronics

Auto

Fine Chem/ Pharma

Energy

Flame Retardants

Brominated Performance

Products

KE

Y B

US

INE

SS

ES

INDUSTRIES SERVED

Mercury control

Greener innovation

Rapid growth in electronics

Flame retarded energy efficient thermal insulation

Increased global fire safety standards KE

Y G

RO

WT

H

DR

IVE

RS

The Sustainability Challenge for Flame Retardants

In today’s society, products are expected to be “green”

But, what is green?

Ideally, this includes:

− Total Carbon Footprint

− Recyclability

− Green Chemistry & Engineering Principles

− Chemical Hazard Classification and Risk Assessment

5

Factors Affecting Flame Retardant Selection

Environment & Human Health

Functional Requirements

End-of-Life Aspects

Economic Feasibility

Meet Fire Safety Standard

6

How Do We Move Towards Environmentally Friendly, Sustainable FR Solutions?

Chemtura is applying a “Greener is Better” philosophy...

Greener Innovation

“Greener is Better” FR Design Strategy

Greener Alternatives That Achieve targeted fire safety standards

Meet or exceed baseline performance and manufacturability

Are cost effective based on total system cost

Minimize transition costs

Strive for zero environmental release VECAP to prevent release from manufacture to fabrication

Durable & recyclable to allow low-risk rework and recycling

Structures that are inherently Not migratory

Not bioavailable

Not toxic

Conclusions of USEPA Decabromodiphenyl ether alternatives assessment2

- “Large polymers (greater than 1,000 daltons) had generally low concerns because they cannot be absorbed or easily metabolized.”

- “Large discrete chemicals and large polymers (both halogenated and non-halogenated) had generally low ecotoxicity hazards. The larger chemicals and compounds with high Kow are not expected to be bioavailable in the water column. Most hazard designations based on SAR predicted ‘no effects at saturation’.

2. Lavoie, E.. USEPA , Conference Procedings, Fire Retardants in Plastics 2012, June 2012

9

DRAFT Assessments – “Classical” BFRs

4/19/2013 10

DRAFT Assessments – Polymeric BFRs

4/19/2013 11

DRAFT Assessments – Phosphorus and Nitrogen FRs

4/19/2013 12

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

13

Introducing Emerald Innovation™ Our Next Generation of Flame Retardant Products

Why Emerald Innovation™? Products are innovative, reliable and also minimize the impact on our environment and human health while maintaining superior performance and quality

EMERALD INNOVATION™ 1000 VERSATILE, EFFICIENT, SUSTAINABLE FLAME RETARDANT SOLUTION FOR IGNITION RESISTANT POLYMERS

Polymeric structure, not readily bioavailable1, offers sustainability replacement solutions for decabromodiphenyl oxide (DE-83R™) and decabromodiphenyl ethane (Firemaster® 2100R)

High bromine content, more efficient than other alternatives to DE-83R™ and Firemaster® 2100R

Offers an excellent balance of physical properties, flammability performance and process ability

Cost-effectively provides UL-94 V-0 performance in Polyolefin and Styrenic based formulations and other resins

1 49 Federal Register 46066 (Nov. 11, 1984), 40 CFR 723.250

Emerald Innovation™ 1000

EMERALD INNOVATION™ 1000 IS A POLYMERIC BROMINATED FLAME RETARDANT DESIGNED FOR USE IN A BROAD SPECTRUM OF

APPLICATIONS

Emerald Innovation™ 1000 Typical Properties

High content with excellent thermal stability

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 Innovation™ 1000 in HDPE*

*LYONDELLBASELL PETROTHENE R590005 (0.8MFI)

LABEL DESCRIPTION

FR-1 DECABROMODIPHENYL OXIDE (DE-83R™)

FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER ® 2100R)

FR-4 POLY(PENTABROMOBENZYL) ACRYLATE

FR-5 ETHYLENEBIS(TETRABROMOPHTHALIMIDE)

Property Emerald

Innovation™ 1000

FR-1 FR-2 FR-4 FR-5

FR Load, % 19.0 19.0 19.0 21.0 22.3

ATO % 6.3 6.3 6.3 6.3 6.3

UL-94, at 1.6 mm V-0 V-0 V-0 V-0 V-0

Gardner Multi-Axial 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

Emerald Innovation™ 1000 offers an excellent balance of efficiency, physical properties and flammability performance in HDPE formulations

Comparison of Melt Viscosities Capillary Rheology of HDPE Formulation Containing Emerald Innovation™ 1000

10

100

1000

10000

10 100 1000 10000

Vis

cosi

ty, P

a-se

c

Shear Rate, 1/sec

Emerald Innovation 1000

FR1

FR2

FR3

FR4 FR5

FR4

FR2

FR1


Comparable viscosities in HDPE formulations indicate that Emerald Innovation™ 1000 will process under similar conditions as current flame retardant formulations

Gardener Multi-Axial Impact of HDPE* with Emerald Innovation™ 1000 vs. FR-4

FR-4 Emerald Innovation™ 1000

Brittle failure and delamination

Ductile yield

* Tested at room temperature

Superior compatibility of Emerald Innovation™ 1000 with HDPE results in significantly better toughness vs. FR-4 for demanding applications

*LYONDELLBASELL PETROTHENE R590005 (0.8MFI)

Emerald Innovation™ 1000 Performance in Talc-Filled PP*


FR 1 FR 2

Flame retardant % 21 21 21

ATO % 7 7 7

Talc % 20 20 20

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 (FIREMASTER ® 2100R)

Emerald Innovation™ 1000 is an effective replacement for FR 1 or FR 2 for talc-filled PP

Excellent performance also demonstrated in PP homopolymer and copolymer

*Profax SG702 copolymer16 MFI 30.0% +

Profax 6323 homopolymer 12 MFI 21.0%

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 Innovation™ 1000 Performance 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

SOLUTIONS FOR ANTIMONY TRIOXIDE REDUCTION

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: Cost volatility of antimony metal Higher cost of ATO

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

Metal Salts

1 2 3 4 6

Emerald Innovation 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

20% Talc filled Polypropylene*

Significant reduction in ATO content Potential cost reduction Reduced smoke emissions?

ZB 467 = Zn Borate Kemgard 981 = Zn phosphate Kemgard 911A = Ca/Zn molybdate Kemgard 911B = Zn molybdate

*Profax 6323 homopolymer 12 MFI Kemgard is marketed by J.M.Huber Inc.,

Emerald Innovation 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*

*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?

*Profax 6323 homopolymer 12 MFI

Emerald Innovation 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*

*Modified clay: quaternary ammonium and siloxane treated montmorillonite clay. Charex 44PSS Amcol/Nanocor

Modified clay effectively replaces up to about 50% ATO Cost saving potential Minimum effect on flow

*Profax SG702 copolymer 18MFI

Mechanical Properties of Unfilled PP Copolymer Containing Modified Clay

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

Mechanical properties slightly better

PPE/HIPS Blends Antimony Oxide free

wt % FR-1 Flammability

time, seconds

UL94

Rating

1.6 mm

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

UL94

Rating

1.6mm

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

Mechanical properties for FR-1 are similar to base resin unlike FR-7

1:1 PPE/HIPS Control FR-1 FR-7

FR Load level, % 0 5 13.5

Notched Izod Impact Strength, 1/8” J/m 141 118 60.9

HDT (ºC) @ 1.8 MPa 114.1 115.0 79

Tensile Strength , MPa 58.2 57.1 49.6

Elongation at Yield, % 9.0 8.8 22

Elongation at Break, % 18.7 21.9 36.5

Flexural Strength, MPa 100.1 100.5 84.2

Flexural Modulus, MPa 2571.0 2659.3 2528

Melt flow index, 280 ºC/5kg; g/10mins 16.2 20.0 63.5

FR-7 = bisphenol-A bisdiphenyl phosphate

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

MFI g/10min

Notched Izod Impact J/m

Tensile Strength, Mpa

Strain @ Yield (%)

Strain @ Break (%)

Flexural Strength, Mpa

Flexural Modulus, Mpa

HDT, C

PPE/HIPS

Emerald innovation 1000

BAPP

Emerald Innovation 1000 does not detract properties of PPE/HIPS

ATO Free HIPS based Formulations

FR-1 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 @1.6 mm 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

Emerald Innovation 1000 demonstrates unique performance Does not require ATO synergist unlike other BFRs

FR-1/PPE vs FR-2/ATO Formulation

FR-1 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 @1.6 mm V-0 V-0

Average Burn time, secs 2.0 0.2

Notched Izod Impact Strength, 3.2 mm J/m 235.0 101.5

Gardner Multi Axial 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

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 FR-1/PPE is equivalent to FR/ATO at 200 C

PC/ABS* Blends (80/20)

% FR-1 Burn Time,

seconds

UL-94

1.6 mm

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

FR-1 = Emerald Innovation 1000 PC = Lexan 141 ABS = Hival G

ATO Free PC/ABS Blends (80/20) FR-1 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, 3.2mm 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

All formulations contain 0.1% Ultranox 626 & PETS wax FR-6 formulation contains 0.1% PTFE


FR-1 vs. FR-7

0

20

40

60

80

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

ATO-free PC/ABS Blends (Variable Composition)

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


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

V.2.0

Sustainable, Innovative, High Performance Polymeric Flame Retardant for Polystyrene Foams

V 2

.0

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

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.

V 2

.0


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

CAS# 1195978-93-8

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

V 2

.0

Emerald Innovation™ 3000 demonstrates comparable fire safety performance versus HBCD at similar bromine levels

Flammability Performance

V 2

.0

DfE Screen Results for Polymeric FR1

vL= very Low L= Low vH= veryHigh NE= no evidence

1.Davis, J.W. et. al., Strategic Approach Towards Developing More Environmentally Sustainable Flame Retardants, 12th Workshop on Brominated and Other Flame Retardants, 2011.

The polymeric nature of Emerald Innovation™ 3000 renders it more sustainable than other flame retardant alternatives. Emerald Innovation™ 3000 is the best choice when developing a sustainable product portfolio.

In EPS and XPS, Emerald Innovation™ 3000 demonstrates comparable efficiency at similar bromine content to HBCD.

Handling and processing of Emerald Innovation™ 3000 is comparable to HBCD.

Unlike HBCD, Emerald Innovation™ 3000 does not interfere in polystyrene polymerization chemistry, providing improved control of molecular weight during EPS production.

The high solubility of Emerald Innovation™ 3000 in styrene monomer allows for easy introduction into EPS production processes.

Emerald Innovation™ 3000 can be easily incorporated into a masterbatch for use in XPS.

Emerald Innovation™ 3000: Your Sustainable FR Solution for EPS and XPS

V 2

.0

Conclusions

GREAT LAKES SOLUTIONS IS

COMMITTED TO GREENER INNOVATION

4/19/2013 48

CONCLUSIONS

Recent introductions of new polymeric flame retardant platforms demonstrates the feasibility of sustainable flame retardant

This approach applies to both halogenated and non-halogenated flame retardants

Versatile, cost-effective approach across most polymer

systems Great Lakes Solutions provides Versatile, Sustainable

Flame Retardant Solutions for a variety of applications

Acknowledgements and Thanks

Great Lakes Solutions Applications Research Laboratory

Dr. Subra Narayan

Harry Hodgen

Julie McKeown

Ken Bol

Applied Market Information Ltd

2013 SKZ China

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