recent developments in flame retardants for sustainable...

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 – stabilization in XPS

Conclusions

2

What are flame retardants?

How do they work?

3

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 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

5

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

6

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

7

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


EPDM

DP 45™ Firemaster® 2100R Emerald Innovation™ 1000

Reofos® 95 Reofos® RDP Reofos® BAPP


7

8

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


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


8

9

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


ABS

BA-59P™ BC-52™, BC-58™ Firemaster® 2100R Emerald Innovation™ 1000


PC/ABS

PDBS 80™ Firemaster® CP-44HF Firemaster® PBS-64 HW BC-52™ , BC-58™ Firemaster® 2100R Emerald Innovation™ 1000

Reofos® RDP Reofos® BAPP


PPE/HIPS

PDBS 80™ Emerald Innovation™ 1000

Reofos® RDP, Reofos® BAPP


9

10

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™

10

11

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


Epoxy

*BA-59P™ Firemaster® BZ-54 Firemaster® 2100R Emerald Innovation™ 1000

Reofos® 50, 65, 95 Kronitex® CDP Reofos® RDP Reofos® BAPP


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

12

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


Timonox®/TMS®Blue Star Ultrafine® Blue Star ZB 467

12

13

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™


PET



PC Firemaster® PBS-64 HW BC-52™ BC-58™

ZB 467

13

14

Developing Sustainable Flame Retardant Solutions

Great Lakes Solutions &

Emerald Innovation™ series of flame retardants

14

15

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

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

A Sustainable, Versatile, Brominated Polymeric Flame Retardant

16

17

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

18

19

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


19

20

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

21

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-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTE® 2100R)

21

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

FR-3 2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE

22

23

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


Firemaster 2100R

Impact Strength in Impact Modified HIPS

With 12% FR and 4% ATO

23

COMPARISON OF MELT VISCOSITIES

220 0C

LABEL DESCRIPTION


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


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

25

High efficiency and excellent balance of properties

26

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

28

29

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

29

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)

30

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

31

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

32

• 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

33

34

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

37

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

43

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

43

44

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

44

Emerald Innovation™ 1000 is very versatile in producing UL 94 VO over a wide range of different PC/ABS compositions

45

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

46

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

46

47

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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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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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


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


Emerald PS + Innovation™ 3000 + AO1/P1/E1

Emerald PS + Innovation™ 3000

Emerald PS + Innovation™ 3000 + alternative AO

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Yello

wn

ess

Ind

ex

Excellent Color Stability

Color stability superior to neat polystyrene resin

AO1/P1/E1

A01 Anox® 20

P1 Ultranox® 626


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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