Clariant FR

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
Thermoplastics
65.0%
Others
14.0%
Thermoplastics
and
Polyurethanes
account for close to
70% of this market
Fibers
13.0%
Elastomers
4.0%
PUR
Thermoplastics
Others
Elastomers
Fibres
Synthetic Polymers production in

2007 : 315 mm mt globally
Polyurethanes
(incl. TPU)
4.0%
Polyurethanes
Standard Plastics + Engineering Plastics
Thermosets, Adhesives, Coatings, Sealants
Synthetic Elastomers (SBR, IR, IIR, BR, NBR, CR, Others)
PA, Polyester, Acrylic, Other Synthetic Fibres
Source: PlasticsEurope Market Research Group (PEMRG)

30-Sep-2009
Slide 3
World
Plastics Production 1950 - 2007
Mio t
300
Plastics are a global

success story
2007: 260
250
2006: 245
Continuous growth
for more than 50 years
2002: 200
200
World
150
Europe
(WE + CE)
1989: 100
100
Compound
Annual Growth Rate (CAGR) is
about 9,0%
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 PolyacrylFibers
30-Sep-2009
Slide 4
Western Europe
Plastic Materials Demand by Segments 2007
Total: 40.5 Mio t
Packaging
43%
Building &
Construction
21%
Automotive
8%
E&E
5%
Others
23%
LDPE, HDPE
LLDPE
PP
PS
EPS
PVC
ABS, PMMA
SAN
PA
PET
Other PUR
Thermoplastics

30-Sep-2009
Slide 5
Re
sis
t
an
ce
he agai
at
n
a n st c
d f he
ire mi
ca
ls ,
The Plastics Pyramid commodity

polymers are the most flammable
Global Consumption (2007)
High Performance
Polymers
5 ... 20 (100) EUR / kg
Engineering
Plastics
2.50 ... 3.50 EUR / kg
500 kt
PI PEEK
PES FP < 1 %
PTFE LCP
COC
PA 4.6
20,000 kt
PC
PBT/PET
10 %
PPO POM PA 6/6.6
Commodity
Plastics
1.00 ... 2.00 EUR / kg
ABS
PUR
PS
PVC
185,000 kt
90 %
PPV
PP
PE-HD
PE-LD
data PlasticsEurope 2008

30-Sep-2009
Slide 6
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

30-Sep-2009
Slide 7
Additives for Property Enhancement

30-Sep-2009
Slide 8
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
30-Sep-2009
Slide 9
Limiting Oxygen Index (LOI)

ASTM 2863
Pigments & Additives

Division
A High LOI value

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

Extrusion
Rotational Molding
Film Blowing
Injection Molding
Sheet Thermoforming
Blow Molding

30-Sep-2009
Slide 11
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)

30-Sep-2009
Slide 12
Many different chemistries can achieve

Flame Retarding effects
Br
CH3
HO
R1
OH
CH3
Br
Br
R2
Br
M n+
O
n
31P
35Cl
N
H2N
N
Al(OH)3
O
P
ONH4
11B
NH2
N
Cl CH2
80Br
NH2
14N
27Al
Br
Br
Br
Br
Br
CH2Cl
O P O
CH3
CH3
O
CH3
CH2Cl
24Mg
Br
different physical / chemical properties, environmental fate, toxicology, and

regulatory status

30-Sep-2009
Slide 13
Global Consumption of Flame Retardants

(2007)
Quantity ca. 1,800,000 tons
Other
11%
Aluminium
Hydroxide
40%
Brominated
23%
Value ca. 4.2 billion US$

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

30-Sep-2009
Slide 14
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%).
30-Sep-2009
Slide 15
Flame Retardants Consumption by Region

global consumption 1,8 mm mt (2007)
Source: SRI consulting

30-Sep-2009
Slide 16
Global FR Uses by Polymers all applications

(Estimates kt 2007)
source: European FR Association/BSEF

30-Sep-2009
Slide 17
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

30-Sep-2009
Slide 18
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,
Toxicity (PBT) ?
risk assessments, scientific

studies for materials of concern

Created for ES&T by Andreas Sjdin of the U.S. Centers for Disease
Control, shows the levels of the most bioaccumulative PBDE
congener, BDE-47, and the most bioaccumulative PCB congener, CB153, in U.S. human blood samples. ES&T, 37, p. 384, 2003
30-Sep-2009
Slide 19

30-Sep-2009
Slide 20
Legal compliance and ecological trends are

key drivers for increased usage of HF FRs
Legal Compliance &
Industry Standards
WEEE-Directive
Ecological Trends &

NGO Initiatives
RoHS-Directive
REACH
Original Equipment Manufacturers (OEMs)
APPLE

30-Sep-2009
Slide 21
pina
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
2 Minutes
6 minutes
7 Minutes
30-Sep-2009
Slide 23
Small Scale External Ignition Source in contact

with Household Appliances (non-FR)
1 minute
2 minute
5 minutes
12 minutes
30-Sep-2009
Slide 24
Station Nightclub Fire

West Warwick, Rhode Island, February 2003

30-Sep-2009
Slide 25
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.

30-Sep-2009
Slide 26
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

30-Sep-2009
Slide 27
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

30-Sep-2009
Slide 28

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Public

Additives used in Flame

Global consumption of polymers and key application areas

Formulation of additives into Polymers

Flammability and fire risk of polymers

Global FR market consumption and trends

Flame Retardant Polymer Formulations

Synthetic Polymers production in

Source: PlasticsEurope Market Research Group (PEMRG)

Plastics are a global

Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,

Total: 40.5 Mio t

Source: PlasticsEurope Market Research Group (PEMRG)

The Plastics Pyramid commodity

Flame Retardant Polymer Formulations

Why are Additives added to Polymers?

Source: Polymer Modifiers & Additves, Lutz, Grossman 1988

Additives for Property Enhancement

Flame Retardant Polymer Formulations

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

Limiting Oxygen Index (LOI)

Pigments & Additives

A High LOI value

Compounding of Additives into Polymers

Source: Industrial Polymers, E. Campo

Processor Method Examples:

Flame Retardant Polymer Formulations

Flame Retardant Selection Criteria

Adequate Thermal Stability

Combustion Products (corrosives, toxics, smoke)

Flame Retardant Polymer Formulations

Many different chemistries can achieve

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

Flame Retardant Polymer Formulations

Global Consumption of Flame Retardants

Value ca. 4.2 billion US$

Source: SRI Consulting (2008)

Global Flame Retardant Market

Flame Retardants Consumption by Region

Source: SRI consulting

Global FR Uses by Polymers all applications

source: European FR Association/BSEF

Flame Retardant Polymer Formulations

FR Consumption by final application

Source: SRI Consultants, Freedonia and company reports

Concerns about Flame Retardants

findings of certain brominated

some concern about certain

source of endocrine disruption ?

risk assessments, scientific

Flame Retardant Polymer Formulations

Flame Retardant Polymer Formulations

Legal compliance and ecological trends are