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The Flame Retardants Controversy: Fire Safety and Environmental Protection

Adrian Beard, EFA roundtable, 2008-01-31

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Outline

• Accidental fires cause human casualties, economic damage and environmental pollution

• The risks that flame retardant chemicals pose are small and manageable

• Flame retardants are an important element of fire protection and they can be safely used

• The manufacturers try to develop new and better flame retardants

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Fire Casualties and Damage (Europe 25)

• about 15 casualties in Europe per day• ~ 75 % of victims in private homes

• intoxication by smoke is main cause of death

• costs of 30 billion € per year • ~ 0.3 % of gross domestic product

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Effects of Combustion Products and Smoke

• heat• dense smoke can make orientation

impossible• acutely toxic:

• narcotic: CO, HCN - deadly within minutes; CO2, O2-deficiency

• irritants for eyes and breathing: HCl, SO2, NOx, aldehydes

• compounds with long term effects: • polycyclic aromatic hydrocarbons

(PAHs)

• halogenated dioxins + furans (PCDD/F)

• mostly adsorbed to soot

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Different FR systems

Load needed

• Inhibition of flame (gas phase)• most effective: halogens (Br >> Cl)• often combined with synergists• complex radical reactions with Oxygen

• Inhibition of surface burning (charring)• eg. P-Containing Systems

• Mineral FR Systems• Release of water• Temperature reduction

Effectiveness

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The Variety of Flame Retardants

• diversity in terms of physical / chemical properties, environmental fate, toxicology, and regulatory status

35Cl 31P

80Br14N

27Al

24Mg

Br

HO

Br

C

Br

OH

Br

CH3

CH3

BrBr

BrBr

Br Br

P O

ONH4

O

n

CH2

CH3

CH3 CH2Cl

CH2Cl

CH3

P

O

O

O

O

ClN N

N NH2

NH2

NH2

Al(OH)3 11B

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Halogen ContainingFlame Retardants

Product examples

Br Br

Br

Br Br

O

Br Br

Br

BrBrBr

BrBr

Br

Br Br

Br

Br

Br

Br

O

O

O

Br

HO

Br

C

Br

OH

Br

CH3

CH3 ClH

Cl

H

HCl

Cl

HH

H H H

HHHH

Cl Cl Cl Cl

Cl

Cl Cl

ClCl

Cl Cl

Cl

Decabromodiphenylether(Deca)

Hexabromocyclododecane(HBCD)

Tetrabromophthalic acid anhydride

Dodecachloropentacyclooctadecadiene(Dechlorane)

Chlorinated paraffinsTetrabromobisphenol A(TBBA)

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Phosphorus Containing Flame retardants

Examples

Triaryl phosphates

P

OO

O

O

R

R

R

P

O

OO

OP

O

OO

O

CH2

CH3

CH3 CH2Cl

CH2Cl

CH3

P

O

O

O

O

Cl

Resorcinol bis(diphenylphosphate)(RDP)

Tris(chlorpropy)lphosphate(TCPP)

Phosphinic acid derivatives Ammonium polyphosphate(APP)

Red phosphorus

P O

ONH4

O

n

P

O

CH2CH2 C

O

OCH2CH2OHHO

CH3

P

PP

PP

P PP

P

P

P

P

P

P

P

P

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Variety of Flame Retardants

usage of Flame Retardants, Europe,% of total tonnage (total 408,000 tons/year) source SRI Consulting http://www.sriconsulting.com

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When are Flame Retardants used?

• Laws and regulations define the necessary minimum levels of fire safety

• Technical standards for products define which fire test has to be applied and what the criteria are

• Fire test standards define the method of testing for reaction to fire and the measured parameters (e.g. time to ignition, heat release, ...)

• Flame retardants can be added so some materials in order to achieve the necessary safety level, i.e. pass the relevant fire test

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Television sets

• flame retarded • not flame retarded

8 min after ignition with a small flame:

www.acfse.org

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Concerns: dioxins

• Q: • Can halogenated flame retardants form

dioxins and furans during their production, use, in case of fire, when disposed of or when recycled?

• A:• Only very few out of the 75 brominated FRs

are precursors for dioxins and furans• Studies show that even after several

recycling loops, plastics containing brominated FRs can still pass the German dioxin ordinance

• Modern incinerators effectively remove dioxins and furans from the flue gas

Br Br

Br

Br Br

O

Br Br

Br

BrBr

Decabromodiphenylether(Deca)

O

O

Clx Cly

O

Clx Cly

chlorinated dibenzodioxin

chlorinated dibenzofuran

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Concerns: bio-accumulation

• Q:• Do halogenated products accumulate in organisms and are they

found in increasing amounts in human milk?

• A:• Only very few halogenated FRs have the potential to bio-

accumulate (pentaBDE, PBBs).• Only pentaBDE is found in breast milk and latest publications

show that the level is falling again since 1997.• PentaBDE is banned in Europe since July 2004.• PBBs have been voluntarily phased out by the industry in 2000.

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Concerns: toxicity

• Q: • Are flame retardants potentially toxic chemicals which are

generally objectionable in consumer products? Can they be taken up by humans and be harmful to their health?

• A: • FRs are as safe as other common chemicals.• The amounts of FRs released from products are usually minimal

and pose no significant risk; reactive FRs do not migrate at all.• No report exists of humans or organisms having had adverse

effects or having died from exposure to FRs. • Most FRs are not classified as dangerous (toxic) substances

according to EU legislation.• Several FRs are used as reactive substances and hence do not

exist as such anymore in the consumer product.

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EU Risk Assessments

Substance Rapporteur Priority List

Status

Antimony trioxide ATO Sweden 4 (00) Under way Short-chain Chlorinated Paraffins SCCP UK 1 (94) Published Medium-chain Chlorinated Paraffins MCCP UK 3 (97) Draft circulated Pentabromodiphenyl ether PBDE UK 2 (95) Published Octabromodiphenyl ether OBDE UK/France 1 (94) Published Decabromodiphenyl ether DBDE UK/France 1 (94) Published Hexabromocyclododecane HBCD Sweden 2 (95) Finalized Tris(2-chloroethyl) phosphate TCEP Germany 2 (95) Finalized Tetrabromobisphenol A TBBPA UK 4 (00) Finalized Tris(2-chloroisopropyl) phosphate TCPP Eire/UK 4 (00) Under way Tris(1,3-dichloroisopropyl)phosphate TDCPP Eire/UK 4 (00) Under way 2,2-bis(chloromethyl)trimethylene bis(bis(2-chloroethyl)phosphate)

V6 Eire/UK 4 (00) Under way

http://ecb.jrc.it/existing-chemicals/

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Evaluation of Flame Retardants

• Following the current risk assessments, only 2 FRs have been banned whereas for the others, either no risk has been identified, or risks have been found manageable for those where the risk assessment is finalised.

• A large number of FRs have not been associated with any environmental or health risks, some even received approval from environmental authorities.

• For some FRs, the European risk assessments have found no risks, but still they remain in the political discussion.

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The Perception of Risk

Hazard = harmful property of a chemical

Risk = the chance the harm will occur

Risk = Probability x Hazard

Probability is linked to Exposure

Media, green and consumer groups often confuse hazard with risk

Translated into the everyday world:• Alcohol is a deadly poison• Sacharin is a known carcinogen

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REACH and Flame Retardants

• The new European chemicals legislation REACH requires that all chemicals – old and new – have to be registered and a basic set of health and environmental data must be submitted (dependent on production volume).

• => all chemicals will be assessed on an equal basis• The FR industry is well prepared for REACH, because of

long experience with EU Risk Assessments.• Industry and consumers hope that in exchange for the

high cost of REACH, we can build trust in the chemicals we use.

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Demands on flame retardants

flame retardant

compatibility with the target polymer and the production

process

flame retardant effect

toxicology,ecology cost

Often, combinations of FRs are used

No single, “best” flame retardant

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Upholstered Furniture LCA Project

• Life Cycle Analysis • different flame retardants: P and Br based • in comparison with non flame retardant

components• combined with fire statistics

• The project was contracted by EFRA to SP & IVL (Swedish Environmental Research Institute)

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Upholstered Furniture LCA - Results

• flame retarded sofas produced chlorinated / brominated dioxins and furans

• non-flame retarded sofas produce markedly higher emissions of HCN and PAHs• due to much higher number of fires• therefore, non-flame redarded sofas have

a more negative impact on the environment

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Summary and Conclusion

• Accidental fires cause human casualties, economic damage and environmental pollution

• The risks that flame retardant chemicals pose are small and manageable

• Flame retardants are an important element of fire protection and they can be safely used

• The manufacturers try to develop new and better flame retardants

www.flameretardants.eu

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Thank you for your attention