vvEPA
United States
Environmental Protection Agency
EPA Document** 740-Q1-4002
August 2015
Office of Chemical Safety and
Pollution Prevention
TSCA Work Plan Chemical
Technical Supplement - Use and Exposure of the Brominated
Phthalates Cluster (BPC) Chemicals
Brominated Phthalates Cluster
Flame Retardants
CASRN
26040-51-7
183658-27-7
20566-35-2
77098-07-8
7415-86-3
*
*
NAME
1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, l,2-bis(2-
ethylhexyl) ester
Benzole acid, 2,3,4,5-tetrabromo-, 2-ethylhexyl ester
1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, l-[2-(2-
hydroxyethoxy)ethyl] 2-(2-hydroxypropyl) ester
1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrabromo-, mixed
esters with diethylene glycol and propylene glycol
1,2-Benzenedicarboxylic acid, l,2-bis(2,3-dibromopropyl) ester
Confidential A
Confidential B
* Confidential Business Information
August 2015
-------
TABLE OF CONTENTS
TABLE OF CONTENTS 2
1 PRODUCTION VOLUME AND USES 4
1.1 PRODUCTION OFTBPH (CASRN 26040-51-7) 5
1.2 PRODUCTION OF TBB (CASRN 183658-27-7) 5
1.3 PRODUCTION OF CASRN 20566-35-2, 77098-07-8 AND 7415-86-3 5
1.4 IMPORT AND EXPORT OFTBPH AND TBB 8
1.5 USES OFTBPH AND TBB 8
1.5.1 TBPH and TBB Flame Retardants: Firemaster® Products 10
1.5.2 TBPH (CASRN 26040-51-7): Use as a Flame Retardant Plasticizer 12
1.6 USES OF CASRN 20566-35-2, 77098-07-8 AND 7415-86-3 13
1.6.1 CASRNs 20566-35-2, 77098-07-8 and 7415-86-3: Flame Retardants 13
1.7 CHEMICAL ALTERNATIVES TO FIREMASTER 550® 14
1.8 REGULATORY STATUS AND FUTURE TRENDS 16
1.8.1 Standards Relating to Polyurethane Foam 16
1.8.2 Electrical and Electronic Equipment Standards 18
1.8.3 Price 22
2 ENVIRONMENTAL EXPOSURE 23
2.1 MONITORING DATA SUMMARY 23
2.2 DATA NEEDS 25
3 HUMAN EXPOSURE 26
3.1 OCCUPATIONAL EXPOSURES TO THE CLUSTER CHEMICALS 26
3.2 OCCUPATIONAL EXPOSURES™ POLYURETHANE FOAMS (PUF) CONTAINING THE CLUSTER CHEMICALS 26
3.2.1 Slabstock Polyurethane Foam 31
3.2.2 Molded Polyurethane Foam 31
3.3 OCCUPATIONAL EXPOSURE DURING THE MANUFACTURE OF PRODUCTS CONTAINING POLYURETHANE FOAMS (PUF) 33
3.4 OCCUPATIONAL EXPOSURE FROM THE USE OF PRODUCTS CONTAINING POLYURETHANE FOAMS (PUF) 33
3.5 CONSUMER EXPOSURE FROM THE USE OF PRODUCTS CONTAINING POLYURETHANE FOAMS (PUF) 33
3.6 DATA NEEDS 34
4 ENVIRONMENTAL EXPOSURE 34
4.1 BACKGROUND AND CONTEXT OF CLUSTER CHEMICAL MANUFACTURE 34
4.2 RELEASESTOTHE ENVIRONMENT DURING CLUSTER CHEMICAL MANUFACTURE 35
4.3 RELEASESTOTHE ENVIRONMENT DURING POLYURETHANE FOAMS (PUF) MANUFACTURE 35
4.4 RELEASESTOTHE ENVIRONMENT DURING THE MANUFACTURE OF PRODUCTS CONTAINING POLYURETHANE FOAMS (PUF).35
4.5 RELEASESTO THE ENVIRONMENT DURING THE OCCUPATIONAL USE OF PRODUCTS CONTAINING POLYURETHANE FOAMS
(PUF) 35
REFERENCES 37
APPENDICES 46
Page 2 of 54
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LIST OF TABLES
Table 1-1: Production Volumes of the Brominated Phthalates Cluster Chemicals 4
Table 1-2: 2012 CDR Production Data forTBPH (CASRN 26040-51-7) 6
Table 1-3: 2012 CDR Production Data forTBB (CASRN 183658-27-7) 6
Table 1-4: CDR Production Data for CASRNs 20566-35-2, 77098-07-8 and 7415-86-3 7
Table 1-5: Industrial and Consumer Use Data forTBPH (CASRN 26040-51-7) from the 2012 CDR9
Table 1-6: Loading Levels of Firemaster® 550 for Household Items 12
Table 1-7: Industrial and Consumer Use Data for CASRN 20566-35-2, 77098-07-8 and 7415-86-3
15
Table 1-8: Approved and Effective Upholstered Furniture Flammability Performance Standards
19
Table 1-9: Proposed Flammability Performance Standards 21
Table 1-10: Flammability Standards for Electronic Products 22
Table 3-1: Summary Table of TBPH Monitoring Data 27
Table 3-2: Summary Table of TBB Monitoring Data 29
Table 4-1: Comparison of Different Polyurethane Foam Products 36
LIST OF APPENDIX FIGURES
Figure 3-1: Typical Slabstock Production Line for flexible polyurethane foam (EPA, 2005) 31
Figure 1-2: Typical Molded Foam Production Line for flexible polyurethane foam (EPA, 2005). 32
Page 3 of 54
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1 PRODUCTION VOLUME AND USES
This section discusses the production volume and uses of the five brominated phthalates
cluster (BPC) chemicals. The 2006 Inventory Update Reporting (IUR) and 2012 Chemical Data
Reporting (CDR) production volumes for these chemicals are listed in Table 1-1. Additional
details on production volume for the chemicals can be found in Sections 1.1 and 1.2 for TBPH
and TBB, respectively. A summary of the available production volume data for the other three
chemicals in the cluster, CASRNs 20566-35-2, 77098-07-8, and 7415-86-3, is presented in
Section 1.3. Additionally, export volumes of all the chemicals, as reported to CDR, are found in
Section 1.1.
Use information can be found in Section 1.5 for TBPH and TBB and Section 1.6 for the other
three chemicals in the cluster. Lastly, potential alternatives to TBB/TBPH are discussed in
Section 1.7 and Section 1.8.3 presents available price information for the chemicals.
Table 1-1: Production Volumes of the Brominated Phthalates Cluster Chemicals
Cluster Member
TBPH: CASRN 26040-51-7
TBB: CASRN 183658-27-7
TBPA-Diol: CASRN 20566-35-2
TBPA-Diol (mixed esters):
CASRN 77098-07-8
Bromo Alkyl Ester:
CASRN 7415-86-3
Confidential A
Confidential B
Reporting
2006 IUR PV > 10 million pounds
2012 CDR PV = 1 to 10 million pounds
NotonTRI
2006 IUR CDR National PV information for
withheld.
2012 CDR National PV information for the
withheld.
NotonTRI
the chemical
chemical
2006 IUR PV = no record
2012 CDR PV = 1 to 10 million pounds
NotonTRI
2006 IUR PV = 1 to 10 million pounds
2012 CDR National PV information for the
withheld.
NotonTRI
chemical
2006 IUR PV = no record
2012 CDR = no record
NotonTRI
Consent Order - testing PV not triggered
2012 CDR National PV information for the
withheld.
chemical
IUR = Inventory Update Reporting; CDR = Chemical Data Reporting; PV = Production Volume; TRI = Toxic
Releases Inventory
Page 4 of 54
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1.1 Production of TBPH (CASRN 26040-51-7)
According to the 2012 CDR database, the national production volume of TBPH is between one
and 10 million pounds (EPA, 2012a): Table 1-2.
Two companies are identified in the CDR database as manufacturing/importing TBPH: Teknor
Apex and Unitex (now part of LanXess) (EPA, 2012a). Unitex developed bromine-chlorine
phthalate esters which are part of the company's Uniplex® product line. These plasticizers are
most likely combinations of TBPH and dioctyl tetrachlorophthalate oxide and are thought to
have an improved flame retardancy over TBPH alone (Weil and Levchik, 2009). No trade
literature has indicated the trade name of Teknor Apex's TBPH product. For more detailed
information, see Table 1-2.
Chemtura's website indicates that it also produces TBPH (Chemtura, 2007a). TBPH has been
identified as a component of Chemtura's flame retardant products Firemaster® 550,
Firemaster® BZ-54, and Firemaster® 552 (Bearr et al., 2010; EPA, 2005; Stapleton et al., 2008a).
1.2 Production of TBB (CASRN 183658-27-7)
EPA's 2012 publicly available CDR database does not provide any data on the production
volume of TBB; the national production volume for TBB is withheld and past production
volumes are reported as confidential business information (CBI), as shown in
Table 1-3 (EPA, 2012a). However, Chemtura's Firemaster® 550 webpage acknowledges that TBB
is the main component of its flame retardant Firemaster® 550 (Chemtura, 2013b). Evidence
that TBB is manufactured or sold for any other purpose than for Firemaster® products was not
found.
1.3 Production of CASRN 20566-35-2, 77098-07-8 and
__7415-86:3
According to the 2012 CDR, the production volume of CASRN 20566-35-2 is between 1 and 10
million pounds per year, as shown in Table 1-4 below (EPA, 2012a). Rubicon and Pelron, Inc.
are identified in the CDR database as manufacturers/importers of CASRN 20566-35-2 (EPA,
2012a).
CDR data identifies Albemarle Corporation as a manufacturer/importer of CASRN 77098-07-8.
However, national production volumes for CASRN 77098-07-8 are withheld from the 2012 CDR
and past production volume are reported as Confidential Business Information (CBI)(EPA,
2012a), as shown below in Table 1-4.
Page 5 of 54
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There are no records for CASRN 7415-86-3 in the 2012 CDR database (EPA, 2012a).
Table 1-2: 2012 CDR Production Data for TBPH (CASRN 26040-51-7)
Manufacturing
Site
Teknor Apex
751 Dupree
Street
Brownsville,
TN 38012-
1708
CBI
Unitex
Chemical
Corp.
520 Broome
Road
Greensboro,
NC 27406-
3799
Domestic
Manufacturing
Withheld
CBI
Withheld
Imported
Withheld
Withheld
Volume
Exported (Ibs)
64,000
CBI
781,125
Volume
Used on the
Site (Ibs)1
0
311,796
0
Past Production
Volume (2010)
(import+
manufacture)
1,600,000
CBI
3,483,600
National
Production
Volume
(2012)
1 Million to
10 million
Ibs/year
^he total volume (domestically manufactured and imported) of the chemical used at the reporting site. This number
represents the volume of the chemical that did not leave the manufacturing site.
CBI = Confidential Business Information
Table 1-3: 2012 CDR Production Data for TBB (CASRN 183658-27-7)
Manufacturing
Site
CBI
Domestic
Manufacturing
CBI
Imported
No Data
Reported
Volume
Exported
CBI
Volume
used
on the
site
0
Past
Production
Volume
(2010)
CBI
National
Production
Volume
for the
Chemical
Withheld
Page 6 of 54
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Table 1-4: CDR Production Data for CASRNs 20566-35-2, 77098-07-8 and 7415-86-3
CASRN
20566-35-2
77098-07-8
7415^86-3
Chemical Name
1,2-
Benzenedicarboxylic
acid, 3,4,5,6-
tetrabromo-, 1-
bis[(2-(2-
hydroxyethoxy)ethyl]
2-(2-hydroxypropyl)
ester
1,2-
Benzenedicarboxylic
acid, 3,4,5,6-
tetrabromo-, mixed
esters with
diethylene glycol and
propylene glycol
1,2-
Benzenedicarboxylic
acid, l,2-bis(2,3-
dibromopropyl) ester
Manufacturing
Site
Rubicon, LLC
9156 Hwy 75
Geismar, LA
70734
CBI
Pelron, Inc.
7847 West 47th
St.
Lyons, IL
60534
Albemarle
Corporation
725 Cannon
Bridge Road
Orangeburg, SC
29115
No reports
Domestic
Manufacturing
Withheld
Withheld
CBI
CBI
No reports
Imported
CBI
Withheld
Withheld
Withheld
No
reports
Volume
Exported
(Ibs)
CBI
CBI
0
CBI
No
reports
Volume
Used on
the Site
(Ibs)1
CBI
CBI
CBI
CBI
No
reports
Past
Production
Volume (2010)
(import+
manufacture)
CBI
CBI
19,793
CBI
No reports
National
Production
Volume
(2012)
1 Million to
10 million
Ibs/year
Withheld
No reports
•'The total volume (domestically manufactured and imported) of the chemical used at the reporting site. This number represents the volume of the chemical
that did not leave the manufacturing site.
CBI = Confidential Business Information
Page 7 of 54
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CDR data do not indicate whether either TBPH or TBB is imported (EPA, 2012a). The only
reported product containing TBB is Firemaster® 550; when Chemtura began manufacturing
Firemaster® 550, it did so at the company's El Dorado, AR plant (Tullo, 2003). According to the
2012 CDR, Teknor Apex exported 64,000 Ibs of TBPH and Unitex exported 781,125 Ibs (see
Table 1-2).
Pelron, Inc. reported that it did not export CASRN 20566-35-2 and withheld reports on import
volumes; import and export data for Rubicon are reported as CBI (EPA, 2012a).
The CDR database does not provide any data on the import or export of CASRN 77098-07-8.
There is no CDR record for CASRN 7415-86-3 (EPA, 2012a).
The 2012 CDR provide data on the industrial and consumer uses of TBPH (EPA, 2012a). These
data are summarized in Table 1-5 which presents the percent of each site's production volume
used in a specific industrial or commercial and consumer use category. As stated in the
Instruction for the 2012 TSCA Chemical Data Reporting (EPA, 2012a) the percentage of
production volume for the industrial sector is the amount that is attributable to the unique
combination of type of processing, industrial sector and industrial function1. Alternatively, the
percentage of production volume for consumer/commercial use is the percent of the
production volume is attributed "to each specific consumer and commercial end use carried
out". Note that the industrial uses and consumer uses are exclusive of one another.
Sites must report industrial processing and use information for each chemical substance
manufactured (including imported) in an amount of 100,000lbs or more in the reporting year
2011. To identify industries using a chemical in the CDR data EPA used 48 Industrial Sectors (IS)
Codes adapted from the European Union's (EU's) "Guidance on Information Requirements and
Chemical Safety Assessment".
The CDR also collected data on consumer and commercial uses of chemicals. Commercial use is
defined as the use of a chemical substance or a mixture (including as part of an article) in a
commercial enterprise providing saleable goods or a service. A consumer use, on the other
hand, means the use of a chemical substance or a mixture (including as part of an article) when
sold to or made available to consumers for their use (EPA, 2012a) (p4-34).
Definitions of the consumer use categories are provided in Appendix B.
Note, industrial function is not displayed in the tables below.
Page 8 of 54
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Table 1-5: Industrial and Consumer Use Data forTBPH (CASRN 26040-51-7) from the 2012 CDR
Manufacturing
Site
Teknor Apex
751 Dupree Street
Brownsville, TN
38012-1708
CBI
Unitex Chemical
Corp.
520 Broome Road
Greensboro, NC
27406-3799
Type of
Processing
Processing-
incorporation into
formulation, mixture,
or reaction product
Processing-
incorporation into
formulation, mixture,
or reaction product
Processing-
incorporation into
formulation, mixture,
or reaction product
Industrial Use Data
Sector
(NAICS Code)
Custom
Compounding of
Purchased
Resins
(325991)
Furniture and
Related Product
Manufacturing
(337)
Construction
(23)
Electrical
Equipment,
Appliance, and
Component
Manufacturing
(335)
Industrial
Use
Plasticizer
Flame
retardants
Flame
retardants
Plasticizer
Flame
retardants
Percent of
Production
Volume
100
90
10
50
50
Consumer Use Data
Consumer Use
Product
Category
Electrical and
Electronic
Products
Furniture and
Furnishings not
covered
elsewhere
Building/
Construction
Materials not
covered
elsewhere
Electrical and
Electronic
Products
Commercial
or Consumer
Use
Both
Commercial
Commercial
Both
Percent of
Production
Volume
100
90
10
100
Page 9 of 54
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TBPH (CASRN 26040-51-7) and TBB (CASRN 183658-27-7) are two components of Chemtura's
flame retardant Firemaster® 550, an additive flame retardant (Chemtura, 2013b; Stapleton et
al., 2008a). Additive flame retardants are incorporated into polymers via physical mixing, and
are not chemically bound to the polymer. This is contrary to reactive flame retardants which
are incorporated into polymers via chemical reactions and must be incorporated at an early
stage of manufacturing. Since additive flame retardants can be incorporated into the product
up until the final stages of manufacturing, it is usually easier for manufacturers to use additive
flame retardants than reactive flame retardants. Additionally, reactive flame retardants have a
greater effect on the chemical and physical properties of the polymer into which they are
incorporated than do additive flame retardants.
The ratio of TBB to TBPH in this product is 4:1 (CECBP SGP, 2008). The formulation of
Firemaster® 550 comprises TBPH, TBB and two phosphates: triphenyl phosphate (TPP; CASRN
115-86-6) and isopropylated triphenyl phosphate (ITPP; CASRN 68937-41-7 (Chemtura, 2010).
Bearr, et al. (Bearr et al., 2010) states that Firemaster® BZ-54 is made up of the same TBB-TBPH
formulation as is in Firemaster®550. The product's technical data sheet describes it as a
"tetrabromophthalic anhydride derivative," with a bromine content of 54% (Chemtura, 2007b).
According to one source, Firemaster® 552 also has the same components as Firemaster® 550
(EPA, 2005). Chemtura began marketing Firemaster® 552 in 2003 for use in mechanically
cooled, flexible polyurethane foam and for improved processing efficiency (Plastics Additives
and Compounding, 2003).
Firemaster® 550 is a liquid flame retardant for flexible polyurethane applications. Polyurethane
foams are the reaction products of a polyol and an isocyanurate. Polyurethane foams can vary
in stiffness and are broken into two categories - flexible and rigid: attributes that may be
imparted by the use of other additives and/or mechanical processes during manufacture.
Flexible foam, the type of foam in which Firemaster®550 is typically used, is made using toluene
diisocyanate (TDI) as the isocyanurate (Global Insight, 2006; Polyurethane Foam Association,
1991a). Most flexible foams have an open-cell structure, which allows for the movement of air
within the foam (North Star Polymers, 2013). Flexible foam is most often used in cushioning
applications (Polyurethane Foam Association, 1991b). Flexible foams can be divided into many
subsets, including molded, slabstock and viscoelastic and can vary widely by density and pore
size, see Appendix B for more details on these foam types.
EPA could not find any indication that TBB/TBPH is used in rigid foam. It replaces
pentabromodiphenylether (pentaBDE), which was the most widely used flame retardant for
furniture foams, that are flexible, in the United States before being phased out at the end of
2004 (Chemtura, 2007b, 2007c; Tullo, 2003; Utech, 2007). Firemaster® 550 is mainly applied to
furniture containing polyurethane foam, such as couches, ottomans and chairs. According to
Page 10 of 54
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the 2008 End-Use Market Survey on the Polyurethane Industry in the US, Canada, and Mexico,
230 million pounds of flexible slabstock2 was used in furniture in the United States in 2008, of
which 210 million pounds was used in residential furniture and 20 million pounds was used in
non-residential furniture (ACC, 2009). However, the percentage of this market that utilizes
Firemaster® products is unknown. Firemaster® BZ-54 is also used for flexible polyurethane foam
applications and can be blended with alkyphenyl diphenyl phosphate or used alone (Chemtura,
2007b; Weil and Levchik, 2009).
Firemaster® 550 assists furniture manufactures in meeting the State of California Department
of Consumer Affairs Bureau of Home Furnishings and Thermal Insulation's Technical Bulletin
117 (California TB117), which requires that polyurethane foam in upholstered furniture sold in
the State of California withstand exposure to a small open flame for 12 seconds (California
Department of Consumer Affairs, 2000; Stapleton et al., 2011). Baby products that are
considered juvenile furniture must also comply with California TB117 (Stapleton et al.,
2011).These products include rocking chairs, portable mattresses, changing table pads, and car
seats (Stapleton et al., 2011). See Section 1.8 for further discussion of TB117 and the regulatory
status of flame retardants in upholstered furniture. Table 1-6 shows the concentrations of
Firemaster 550® detected in furniture foam and baby products.
TBPH and TBB have also been detected in gymnastics equipment, including foam pit cubes,
landing mats, sting mats, and vault runway carpets (Carignan et al., 2013). These chemicals may
therefore possibly be found in other facilities containing foam pits or equipment. Further,
Firemaster® 550 can also be used in high resiliency (HR) polyurethane foam (Chemtura, 2007b).
HR foams are flexible polyurethane foams, with applications including high-quality mattresses
(Dimaflex, 2009). Different additives are used in these types of foam to increase heat transfer,
bounce back time, etc. so many HR foam formulae exist and are generally proprietary formulae.
Information on the specific HR foam products that Firemaster® 550 is used in could not be
located.
Although flexible polyurethane foam applications include mattress foam, trade associations and
personal communication with industry have indicated that it is unlikely that TBPH and TBB are
used in mattresses. Mattress manufacturers use barrier technologies rather than flame-
retardant-treated foam to meet fire safety standards (Polyurethane Foam Association, 1992a;
Trainer, 2013). Additionally, full scale burn tests have shown that the ignitability and rate of
burning can be reduced by certain foam fillers, cover materials and inter-liners and therefore
flame-retardants are not needed (Randall and Lee, 2010).
PentaBDE was also known to be used in carpet, but current literature does not indicate that
Firemaster® 550 is added intentionally to carpet backing. However, carpet cushions are
manufactured largely from flexible polyurethane slabstock foam scraps and recycled foam (EPA,
2005) and have lifespans of five to 15 years (Luedeka, 2012). Given that carpet backing is often
' The main type of polyurethane foam used in furniture.
Page 11 of 54
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manufactured from recycled foam scrap, carpet backing may have the same amount of
TBB/TBPH as furniture foam if the scrap foam is from a manufacturer that uses Firemaster®
550 (Polyurethane Foam Association, 2012). The recovery of foam scraps to make carpet
cushions is practiced mainly in the United States, Canada, and Mexico, and, to a lesser extent,
exported by China to the United States (Luedeka, 2012). According to the Polyurethane Foam
Association, in 2010, 212 million pounds of slabstock foam were produced for use in US
manufactured upholstered furniture, and 50 million pounds of foam scrap were recovered for
use in US manufactured carpet cushions (Luedeka, 2012).
J^L^
Typical polyvinyl chloride (PVC) emits its ester plasticizers when strongly heated, and these
plasticizers are flammable. One solution to this problem is to use less flammable or
nonflammable plasticizers, such asTBPH (CECBP SGP, 2008; Weil and Levchik, 2009). According
to the CDR TBPH is manufactured for use as a plasticizer by two companies. These two
companies state that TBPH ends up in consumer and commercial electrical and electronic
products that are mainly made of PVC (EPA, 2012a). TBPH is usually used in combination with
other additives, such as antimony trioxide. It can also be used with phosphate esters, zinc
borates, and Ongard® 2, which is a composition from Chemtura containing magnesium oxide
and zinc oxide (Weil and Levchik, 2009). Additionally, chemical manufacturers claim that TBPH
is also used as a flame retardant additive for EPDM (ethylene propylene diene monomer (M-
class) rubber), styrene-butadiene rubber (SBR), and neoprene (Chemtura, 2007a; Unitex, 2009).
The use of TBPH in these polymers constitutes a minor portion of the total PV.
Table 1-6: Loading Levels of Firemaster® 550 for Household Items
Household Item
Couches
Resilient foam3
Firemaster® 550
Loading Amount
(i.e., the amount of
chemical within the
foam)
19.76 mg/g
(5.18-36.85mg/g)
4.2% by weight
3.3% (3. 1-3.5) or
6.0% (5.5-6.2)
depending on the foam
sample.
Chemicals
Representing
Firemaster ® 550
TPP, TBB, TBPH
TBB, TBPH
TPP, tri(propylphenyl)
phosphate, octyl
tetrabomobenzoate
Source
(Stapletonetal.,2012)
Novel and high use flame
retardants in US couches
reflective of the 2005
pentaBDE phaseout.
(Stapleton et al., 2009)
Detection of
organophosphate flame
retardants in furniture
foam and US house dust.
(Cobb and Chen, 2005)
Analysis of FR
Chemicals Added to
Page 12 of 54
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Household Item
Children's
products0
Firemaster® 550
Loading Amount
(i.e., the amount of
chemical within the
foam)
18.51mg/g(5.85mg/g
- 42.5 mg/g)
Chemicals
Representing
Firemaster ® 550
TBB,TBPH
Source
Foams, Fabric, Batting,
Loose Fill and Barriers.b
(Stapletonetal.,2011)
Identification of flame
retardants in polyurethane
foam collected from baby
products.
a The types of products that the foam studied in this report was taken from is unclear.
b This report is cited as the basis for the amount of Firemaster® 550 used in the CPSC risk assessment of Flame
Retardant Chemicals in Upholstered Furniture Foam (Babich, 2006), which used a loading level of 6%.
c The products which contained TBB and TBPH included rocking chairs, portable mattress, changing table pad
and car seat. Products which were examined that did not contain TBB and TBPH include sleep positioners,
nursing pillow, baby carrier, high chair, infant bath mat, baby walkers, stroller, bath toy, car seat pillow, Bumbo
chair, nap mat, and toilet seat.
The 2012 CDR data for industrial and consumer uses of CASRN 20566-35-2 and CASRN
77098-07-8 are summarized in Table 1-7 below. CASRN 7415-86-3 was identified as potentially
used as a flame retardant in polyester fibers [textiles; (WHO, 1997)]. However, there are no
records for CASRN 7415-86-3 in the CDR database (EPA, 2012a).
CASRN 20566-35-2 is listed as an ingredient in Ele Corporation's PEL-RON 9457-LE, a flame
retardant in polyurethane (Ele Corporation, 2013). The type of polyurethane this flame
retardant can be used in was not specified by Ele Corporation's website.
CASRN 77098-07-8 can be used as a reactive flame retardant in rigid polyurethane foam, as
well as in polyurethane reaction injection molding, elastomers, coatings, adhesives, and fibers
applications (GLCC, 2010). These foams, elastomers, and coatings are often used in building
insulation and specialty coatings (Albemarle - GLCC, 2004). CASRN 77098-07-8 flame retardants
are applied to polyurethane in concentrations of 5-15% (Albemarle - GLCC, 2004). Great Lakes
Chemical Corporation lists CASRN 77098-07-8 as an ingredient in its PHT4-Diol™ flame
retardant. In addition, Albemarle manufactures a similar product, Saytex® RB-79, which is also
used in rigid polyurethane foams (Weil and Levchik, 2009).
EPA could not located evidence of where CASRN 7415-86-3 may be used as a flame retardant.
Page 13 of 54
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EPA's Design for the Environment program recently updated the Alternative Assessment for
flame retardants in furniture foam (To be published). In this analysis they identified nineteen
flame retardants which may be used any upholstered consumer product containing flexible
polyurethane foam. Information on some of the alternative is listed below. For a list of flame
retardants which may be used in flexible polyurethane foam in upholstered consumer products
see Appendix A.
• Tris (1,3-dischloroisopropyl) phosphate (TDCPP), known to be a major FR in FPUF and
produced in a volume between 10 and 50 million pounds per year, was listed by
California as a Proposition 65 chemical in late 2011 for concerns about carcinogenicity
(EPA, 2012a; OEHHA, 2011). The Proposition 65 listing is expected to have an impact on
the marketplace, even though TDCPP need not be labeled outside of California. TDCPP
was identified by Stapleton et al (2012) in more than half of samples tested since 2005.
In 2012, the major US manufacturer of TDCPP announced a voluntary phase-out of
TDCPP production by 2015 (Betts, 2013).
• There has been recent opposition from consumer and environmental groups to the use
of halogenated FRs, and this opposition may shape the market suitability of these FRs,
regardless of hazard data. For example, the New York State Assembly passed a bill
prohibiting the use of halogenated FRs in furniture; the bill has not passed the upper
house of the Legislature as of this writing, and appears stalled (NY State Assembly 2013).
Some shift away from halogenated FRs appears to have already occurred. While the
2005 FFRP report assessed a number of brominated FRs, the two brominated
components of Firemaster 550 (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, or TBB, and
bis (2-ethylhexyl)-2,3,4,5-tetrabromophthalate, or TBPH) are the only brominated FRs
included in the current update report (although several chlorinated FRs were assessed).
• Although TCEP was previously not thought to be used in foam, it has been identified in
upholstered FPUF products (Stapleton et al., 2011). TCEP is a TSCA work plan chemical
for 2013-14, so the DfE AA process is a useful contribution to other EPA activities on this
compound (EPA, 2013).
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Table 1-7: Industrial and Consumer Use Data for CASRN 20566-35-2, 77098-07-8 and 7415-86-3
CASRN
20566-35-2
77098-07-8
7415-86-3
Chemical Name
1,2-
Benzenedicarbo
xylic acid,
3,4,5,6-
tetrabromo-, 1-
[2-(2-
hydroxyethoxy)
ethyl] 2-(2-
hydroxypropyl)
ester
1,2-
Benzenedicarbo
xylic acid,
3,4,5,6-
tetrabromo-,
mixed esters
with diethylene
glycol and
propylene glycol
1,2-
Benzenedicarbo
xylic acid, 1,2-
bis(2,3-
dibromopropyl)
ester
Manufacturing
Site
Rubicon, LLC
9156 Hwy 75
Geismar, LA
70734
Pelron, Inc.
7847 West 47th
St.
Lyons, IL
60534
CBI
Albemarle
Corporation
725 Cannon
Bridge Road
Orangeburg, SC
29115
No Reports
Type of
Processing
N/A
N/A
N/A
Processing-
incorporation
into
formulation,
mixture, or
reaction
product
No Reports
Industrial Use Data
Sector
N/A
N/A
N/A
Construction
No Reports
Industrial
Use
N/A
N/A
N/A
Flame
retardants
No Reports
Percent of
Production
Volume
N/A
N/A
N/A
100
No Reports
Consumer Use Data
Consumer
Use Product
Category
Building/
Construction
materials not
covered
elsewhere
Withheld
Withheld
Building/
Construction
materials not
covered
elsewhere
No Reports
Commercial
or
Consumer
Use
Commercial
Withheld
Withheld
Both
No Reports
Percent of
Production
Volume
100
Withheld
Withheld
100
No Reports
N/A = Not Applicable
Page 15 of 54
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• tris(2-Carboxyethyl)phosphine (TCPP) and melamine are the major FRs used in the
United Kingdom to meet the stringent "Crib 5" standard, but use of this mixture is not
known to be common in the United States. However, since TCPP was identified in FPUF
products by Stapleton et al (2011), it is included in this report.
• The larger molecule "V6" (CAS 38051-10-4) has been used in automobile foam, due to
its lower volatility, but was also identified by Stapleton et al (2011) in baby products. V6
is a dimer of TCEP, and contains TCEP as an impurity.
There is a lack of reactive or polymeric flame retardants for flexible polyurethane foam.
Reactive/polymeric products would be expected to have lower volatility, lower mobility out of
the product, and greatly reduced bioavailability; concerns about impurities and breakdown
products prevent making a general conclusion about hazard. DfE's alternatives assessment for
decaBDE included a number of polymeric flame retardants. In the flexible polyurethane foam
market, however, reactive/polymeric flame retardants present technical challenges, in part
because of the extremely small nozzle size typically used in mixing the polyols, and more
generally because of their limited viscosity and flexibility.
^.8^
In order to understand the potential future trends of flame retardant chemicals it is important
to understand the standards and regulations which require and or ban their use.
1.8.1 Standards Relating to Polyurethane Foam
California Technical Bulletin (TB) 117 has been an influential standard driving the use of flame
retardants in furniture manufacturing, as no federal performance standard currently exists to
regulate the flammability of upholstered furniture (CPSC, 2013). California remains the only
state to have passed a performance standard; however, because manufacturers prefer to
produce one product for the entire U market, TB117 subsequently became the de facto
standard for upholstered furniture manufacturers nationwide. TB117 required residential
upholstered furniture foam to withstand an "open flame test," in which an open flame is
applied to uncovered foam for 12 seconds. Although the standard did not explicitly require the
use of flame retardants, the most cost effective way to meet this standard was often to add a
flame retardant to the furniture foam. However, it has been argued that applying an open
flame to an uncovered piece of polyurethane foam does not accurately measure the fire
resistance of furniture (DiGangi et al., 2010). This is because the open flame standard only tests
uncovered foam and does not account for the ability of many fabrics covering the foam to
withstand the flame. A flame large enough to ignite the furniture fabric and reach the foam
beneath will most likely be larger than the flame used in the open flame test, which in effect
renders the open flame standard ineffective (CPSC, 2012).
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Given this information, California recently revised the open flame requirement for upholstered
furniture manufactured and sold in the state. The new regulation, TB117-2013, only requires
residential furniture to pass a "smolder test." In this test, a small assembly of cover fabric,
barrier materials, and filling materials must withstand a smoldering cigarette (Cal/DCA 2013). It
is anticipated that most fabrics will be able to meet this standard without the addition of any
flame retardants.
However, TB 117-2013 only addresses the flammability of residential furniture. California
TB133, which pertains to furniture manufactured and sold for use in public buildings (e.g.
dormitories, hospitals), is a more rigorous test that requires assembled furniture to withstand a
large open flame, provided by a gas burner, for 80 seconds (Polyurethane Foam Association,
1992b). Other states, including Massachusetts, Illinois, Minnesota, North Carolina, and Ohio,
have adopted TB133 as the standard for their own public furniture flammability regulations
(see Table 1-8). Given the large open flame standard, it is likely that manufacturers are adding
flame retardants to their products to meet the test requirements.
In addition to TB117, the Upholstered Furniture Action Council (UFAC), US National Fire
Protection Association (NFPA), and ASTM International have all developed voluntary smolder
test standards. Although UFAC states that 90% of industry has adopted its standard, this is likely
due to manufacturers complying with TB117, which exceeds the requirements of the voluntary
standards. Since 2008, the Consumer Product Safety Commission (CPSC) has also been
developing a federal furniture flammability requirement (CPSC, 2008). Although the initial 2008
standard proposes a smolder test applied to cover materials, in March 2013 CPSC posted a
notice in the Federal Register requesting comments on introducing an open flame standard
(CPSC, 2013). See Table 1-8 for a summary of approved and effective upholstered furniture
flammability performance standards.
It is unclear how the introduction of TB 117-2013 will affect the furniture and flame retardant
industries. With the growing health and environmental concerns about flame retardants,
manufacturers may choose to introduce furniture without flame retardants to this "green"
market; however, it is uncertain how wide-spread this market will be. Whether manufacturers
will switch to foams that are not treated with flame retardants will also depend on state and
local regulations. Many states and local entities reference or model their standards after TB117.
For example, in Massachusetts and Illinois, furniture in public buildings equipped with a
sprinkler system must meet TB117 standards (State of Illinois, No date; State of Massachusetts,
1994). Thus, the update to TB117 will not have an effect in these locations unless they revise
their own regulations. If they do choose to update their standards to match TB117-2013, it may
be a number of years before any legislation is passed.
New York and New Jersey are also proposing their own flammability performance standards for
residential furniture (New Jersey Assembly, 2012; New York Senate, 2013). Because both bills
currently include an open flame test, if either passes it is possible that the open flame will once
again become the de facto nationwide standard. Manufacturers will also need to consider a
possible CPSC national standard. Whether a federal regulation is passed and whether that
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