Additives Used in Flame PDF

Public
T Reilly, A Beard
Div. PA - BU Specialties
BS Flame Retardants
30-Sep-2009
Additives used in Flame

Retardant Polymer
Formulations: Current
Practice & Trends
“Fire Retardants and their Potential Impact on Fire Fighter Health”
Workshop at NIST, Gaithersburg, MD USA, 30-Sep-2009
Outline
 Global consumption of polymers and key application areas

 Formulation of additives into Polymers
 Compounding of polymers
 Flammability and fire risk of polymers
 Global FR market consumption and trends
Flame Retardant Polymer Formulations

T Reilly, A Beard, Div. PA - BU Specialties, BS Flame Retardants (Copyright Clariant. All rights reserved.) 30-Sep-2009 Slide 2
World
Synthetic Polymers Production: 2007
 Synthetic Polymers production in

Thermoplastics 2007 : 315 mm mt globally
65.0%
Others  Thermoplastics
14.0% and
Polyurethanes
account for close to

70% of this market
Fibers
13.0%
Elastomers Polyurethanes
4.0% (incl. TPU)
4.0%
PUR Polyurethanes
Thermoplastics Standard Plastics + Engineering Plastics
Others Thermosets, Adhesives, Coatings, Sealants
Elastomers Synthetic Elastomers (SBR, IR, IIR, BR, NBR, CR, Others)
Fibres PA, Polyester, Acrylic, Other Synthetic Fibres
Source: PlasticsEurope Market Research Group (PEMRG)

World
Plastics Production 1950 - 2007
Mio t  Plastics are a global

300 success story
2007: 260
250 2006: 245  Continuous growth
for more than 50 years
2002: 200
200
 Compound
150
World Annual Growth Rate (CAGR) is
about 9,0%
Europe
1989: 100 (WE + CE)
100
2007: 65
1976: 50
50
1950: 1.5
0
1950 1960 1970 1980 1990 2000
Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,

Coatings and Sealants and PP-Fibers. Not included PET-, PA- and Polyacryl-
Fibers

Western Europe
Plastic Materials Demand by Segments 2007
Total: 40.5 Mio t
Packaging 43%
Building &
21%
Construction
Automotive 8%
E&E 5%
Others 23%
LDPE, HDPE PP PS EPS PVC ABS, PMMA PA PET Other PUR

LLDPE SAN Thermo-
plastics

The Plastics Pyramid – commodity
polymers are the most flammable
Global Consumption (2007)

ls ,
ca
ire mi
High Performance PI PEEK 500 kt

d f he
Polymers PES FP < 1 %

a n st c
5 ... 20 (100) EUR / kg PTFE LCP

n
he agai
at
ce
Engineering COC PA 4.6 20,000 kt

an
PC PBT/PET
t
Plastics 10 %
sis
PPO POM PA 6/6.6

Re
2.50 ... 3.50 EUR / kg
Commodity ABS 185,000 kt

Plastics PUR PPV 90 %
1.00 ... 2.00 EUR / kg PS PP
PVC PE-HD
PE-LD
data PlasticsEurope 2008
Why are Additives added to Polymers?
Three Functional Classes for Additives:
1) Additives which are essential to fabrication of parts
2) Those which improve properties
3) Those which correct problems caused by the other additives !
Source: Polymer Modifiers & Additves, Lutz, Grossman 1988

Additives for Property Enhancement

Example of Additives used in Plastics
 Mineral Reinforcement/Fillers: improve stiffness, surface hardness, cost reduction

 Dyes and Pigments: color & appearance
 Antioxidants & stabilizers: delay/prevent oxidation during processing/application
 UV Stabilizers: interfere with light-induced degradation, weathering
 Blowing Agents: production of foams, weight reduction
 Lubricants: improvement in processing, release properties
 Coupling Agents: impart compatibility between polymer & additives
 Antistats/Conductives: prevent electrostatic discharge, improve conductivity
 Antimicrobials: prevent microbiological attack and property degradation
 Impact Modifiers: enhance toughness of material to impact
 Optical Brighteners: enhance appearance, off-set yellow color
 Flame Retardants: prevent ignition & flame spread, prolong escape time
Limiting Oxygen Index (LOI)
ASTM 2863
Pigments & Additives
Division
A High LOI value

indicates a Lower
Flammability !
T Reilly, AFlame
Clariant Beard, Div. PA - BU Specialties,
Retardants BS Flame Retardants
for Thermoplastics November (Copyright
2007, Clariant.
Public, All
T. rights reserved.)
Reilly, Specialties, Flame Retardants 30-Sep-2009 Slide 10
Compounding of Additives into Polymers
Compound
Source: Industrial Polymers, E. Campo Shipped to
Processor
Processor Method Examples:
Extrusion Rotational Molding
Film Blowing Injection Molding
Sheet Thermoforming Blow Molding

Flame Retardant Selection Criteria
some considerations:
 Efficiency/Cost
 Ease of Compounding
 Adequate Thermal Stability
 Corrosivity Issues
 Physical Properties
 Appearance
 Compatibility (Migration?)
 Environment/Toxicity
 UV Stability/Weathering
 Electrical Properties
 Combustion Products (corrosives, toxics, smoke)

Many different chemistries can achieve
Flame Retarding effects
_
Br
CH3
Br O
R1
HO C OH P O M n+
CH3 R2
Br Br
n
35Cl 31P 27Al

H2N N NH2
N N Cl CH2 O CH2Cl
Al(OH)3 NH2
80Br CH3
O P O
O
CH3
CH3 CH2Cl
O
P O 14N Br
Br Br
Br
ONH4
n 24Mg
11B Br Br
 different physical / chemical properties, environmental fate, toxicology, and

regulatory status
Global Consumption of Flame Retardants
(2007)
Quantity ca. 1,800,000 tons Value ca. 4.2 billion US$

Other Other
11% Brominated 10%
23% Aluminium
Hydroxide Brominated
13% 34%
Antimony Oxides
Aluminium 8%
Hydroxide Chlorinated Organo
40% 7% Phosphorus
20%
Organo
Phosphorus Chlorinated Antimony Oxides
11% 7% 16%
Source: SRI Consulting (2008)

Global Flame Retardant Market
Recent BCC Research Study: the global market for flame retardant chemicals
will grow to $6.1 B in 2014 (Compound annual growth rate of 7%).
Flame Retardants Consumption by Region
global consumption 1,8 mm mt (2007)
Source: SRI consulting

Global FR Uses by Polymers all applications
(Estimates – kt 2007)
source: European FR Association/BSEF

FR Consumption by final application
12%
15% 39%
34%
E&E Building/Construction TAC Transportation

TAC : textile, adhesives, coatings
Source: SRI Consultants, Freedonia and company reports

Concerns about Flame Retardants
 findings of certain brominated

flame retardants in the
environment, biota, humans
 some concern about certain
phosphate esters in indoor air
 source of endocrine disruption ?
 FR Persistence, Bioaccumulation, Created for ES&T by Andreas Sjödin of the U.S. Centers for Disease
Control, shows the levels of the most bioaccumulative PBDE
Toxicity (PBT) ? congener, BDE-47, and the most bioaccumulative PCB congener, CB-
153, in U.S. human blood samples. ES&T, 37, p. 384, 2003
 risk assessments, scientific

studies for materials of concern

Legal compliance and ecological trends are
key drivers for increased usage of HF FRs
Legal Compliance & Ecological Trends &
Industry Standards NGO Initiatives
WEEE-Directive RoHS-Directive
REACH
Original Equipment Manufacturers (OEMs)
APPLE

pinƒa
Phosphorus, Inorganic & Nitrogen Flame Retardants Association
Small Scale External Ignition Source in contact
with Household Appliances (non-FR)
Needle Flame Source (30 w) 1 Minute 6 minutes
2 Minutes 7 Minutes
Small Scale External Ignition Source in contact
with Household Appliances (non-FR)
1 minute 5 minutes
2 minute 12 minutes
Station Nightclub Fire
West Warwick, Rhode Island, February 2003

Conclusion
 Plastics are widely used in our society. The global consumption of plastic
materials is increasing. New materials and applications are being developed.
 It is necessary to add FRs to some plastics (dependent on application).
 Flame retardant consumption is growing globally due to increased standard of

living and fire safety requirements..
 There is a trend towards more environmentally compatible FRs, driven by

NGOs, OEMs and legislation like RoHS, REACH, & some U.S. state legislation.
 FR additives are beneficial to prevent ignition, flame spread & prolong escape
time.
More Information - Links
 Flame Retardants
– www.flameretardants.eu European Flame Retardants Association (EFRA)
– www.flameretardants-online.com
– www.exolit.com
– www.halogenfree-flameretardants.com
– www.flameretardants-online.com/news/frame_news_downloads.htm
 REACH:
– http://ec.europa.eu/environment/chemicals/reach/reach_intro.htm
– http://www.reachcentrum.eu/
– http://ecb.jrc.it/REACH/
– http://ec.europa.eu/echa/home_en.html
 WEEE and RoHS Europe:
– http://ec.europa.eu/environment/waste/weee/index_en.htm
 Ecolabel EU
– http://ec.europa.eu/environment/ecolabel/news/index_en.htm
Thank you for your attendance !
Contact Information:
 Dr. Adrian Beard

Clariant Produkte (D) GmbH
adrian.beard@clariant.com
+49 2233 48 6114
 Timothy Reilly
Clariant Corporation, USA
timothy.reilly@clariant.com
401-823-2444


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Additives used in Flame

 Global consumption of polymers and key application areas

Flame Retardant Polymer Formulations

 Synthetic Polymers production in

account for close to

Source: PlasticsEurope Market Research Group (PEMRG)

Mio t  Plastics are a global

Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,

Flame Retardant Polymer Formulations

Total: 40.5 Mio t

LDPE, HDPE PP PS EPS PVC ABS, PMMA PA PET Other PUR

Source: PlasticsEurope Market Research Group (PEMRG)

Flame Retardant Polymer Formulations

Global Consumption (2007)

High Performance PI PEEK 500 kt

Polymers PES FP < 1 %

5 ... 20 (100) EUR / kg PTFE LCP

Engineering COC PA 4.6 20,000 kt

PPO POM PA 6/6.6

2.50 ... 3.50 EUR / kg

Commodity ABS 185,000 kt

Three Functional Classes for Additives:

1) Additives which are essential to fabrication of parts

2) Those which improve properties

3) Those which correct problems caused by the other additives !

Source: Polymer Modifiers & Additves, Lutz, Grossman 1988

Flame Retardant Polymer Formulations

Flame Retardant Polymer Formulations

 Mineral Reinforcement/Fillers: improve stiffness, surface hardness, cost reduction

A High LOI value

Film Blowing Injection Molding

Sheet Thermoforming Blow Molding

Flame Retardant Polymer Formulations

Flame Retardant Polymer Formulations

35Cl 31P 27Al

 different physical / chemical properties, environmental fate, toxicology, and

Quantity ca. 1,800,000 tons Value ca. 4.2 billion US$

Source: SRI Consulting (2008)

Source: SRI consulting

source: European FR Association/BSEF

Flame Retardant Polymer Formulations

E&E Building/Construction TAC Transportation

Source: SRI Consultants, Freedonia and company reports

Flame Retardant Polymer Formulations

 findings of certain brominated

 risk assessments, scientific

Flame Retardant Polymer Formulations

Original Equipment Manufacturers (OEMs)

Flame Retardant Polymer Formulations

Needle Flame Source (30 w) 1 Minute 6 minutes

Flame Retardant Polymer Formulations

 It is necessary to add FRs to some plastics (dependent on application).

 Flame retardant consumption is growing globally due to increased standard of

 There is a trend towards more environmentally compatible FRs, driven by

 Dr. Adrian Beard

Flame Retardant Polymer Formulations

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