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[Consultation number 0013-01 and 0013-02] [Polymeric FR chemical alternative to HBCDD] [7 July
2014]
SUBMISSION OF INFORMATION
Third party submission of information on alternatives for
Applications for Authorisation
HBCDD USE IN EPS FOR BUILDING APPLICATIONS
NON-CONFIDENTIAL
Legal name of submitter(s): Dow Europe GmbH
Dow Building Solutions
Bachtobelstrasse 3
CH-8810 Switzerland
Consultation reference nos.: 0013 – 01 and 0013 – 02 (HBCDD)
Date of submission: 7th July 2014
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
[Consultation number 0013-01 and 0013-02] [Polymeric FR chemical alternative to HBCDD] [7 July 2014]
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TABLE OF CONTENTS
1. ALTERNATIVE ID AND PROPERTIES ......................................................................... 3
2. TECHNICAL FEASIBILITY ........................................................................................ 3
3. ECONOMIC FEASIBILITY ......................................................................................... 3
4. HAZARDS AND RISKS OF THE ALTERNATIVE ............................................................. 3
5. AVAILABILITY ....................................................................................................... 6
6. CONCLUSION ON SUITABILITY AND AVAILABILITY OF THE ALTERNATIVE .................... 9
7. OTHER COMMENTS ................................................................................................ 9
REFERENCES ............................................................................................................ 9
APPENDIXES ............................................................................................................. 10
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1. ALTERNATIVE ID AND PROPERTIES
Benzene, ethenyl-, polymer with 1,3-butadiene, brominated
CAS no: 1195978-93-8
Brominated co-polymer of styrene and butadiene (also known as Polymeric FR for the purposes of this document)
Trade names: Emerald Innovation™ 3000 (Great Lakes Solutions, a Chemtura business)
FR-122P (Bromine Compounds Ltd. In the ICL Industrial Products ICL-IP segment) and
GreenCrest™ (Albemarle Corporation)
2. TECHNICAL FEASIBILITY
In March 2011, Dow Global Technologies LLC (DGTL) announced the invention and development of the Polymeric FR (Brominated styrene butadiene co-polymer), a stable, high
molecular weight, non-PBT (Persistent, Bioaccumulative,Toxic) substance.
As Dow is also a potential user via the Dow Building Solutions business the technology has
been evaluated and found to be a suitable technical solution to replace HBCDD in XPS (extruded polystyrene foam) and EPS (Expanded polystyrene foam).
As part of the announcement DGTL has made the Polymeric FR technology available to the
extruded polystyrene (XPS) and expanded polystyrene (EPS) foam insulation industry via 3rd Party Licensing. The application of the license covers only Polystyrene foams and does not
extend to textiles or other applications.
Dow has successfully converted its XPS plants in Japan and started the conversion in Europe with products for the Automotive Industry earlier this year (Appendix 1, press releases 9 and
11,)1. Other Users have also declared the technical feasibility of the technology, for instance
BASF and Swisspor have already notified that they have completed conversion in EPS beads
and foam in 2014 (see Appendix 1 press releases 10, 12 ).
The Applicants (defined as the 8 EPS Companies seeking Authorisation for HBCDD) in their
Analysis of Alternatives document acknowledge that the Polymeric FR technology is a
technically feasible solution for the EPS bead and foam Industry.
Technical Feasibility of the production of Polymeric FR has been demonstrated by the licensees
by producing and selling growing commercial quantities since 2012
3. ECONOMIC FEASIBILITY
As stated by the Applicants this is seen also as an economically viable solution (Applicants
Analysis of Alternatives document p. 81) and as such the preferred choice for the Applicants.
4. HAZARDS AND RISKS OF THE ALTERNATIVE
As an integral feature of its development the polymeric FR has been subjected to an extensive
and robust Environment, Health & Safety (EH&S) testing regimen and evaluation over and
above what was required for classification as a polymer.
Dow introduced the substance explaining the methodology of its development via a number of
global conference presentations and published a paper in a scientific journal 2. The primary
objective for the environmental testing was to evaluate whether any lower MW products could
be produced from Polymeric FR by a mechanism known to be environmentally relevant.
Common environmental degradation mechanisms include biodegradation, hydrolytic stability
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and photo-degradation. The testing demonstrated Polymeric FR would be stable in the
environment and does not break down to lower molecular products which could have toxicity,
persistency or bioaccumulation properties. This confirmed a more sustainable profile for the
Polymeric FR.
Table 1: Testing Summary
Endpoint Observation/Comment
Solution-Extraction behavior in water -OECD 120
No detectable organic compounds released into aqueous solution.
Hydrolysis - OECD 111 Not susceptible to hydrolysis
Anaerobic Biodegradation - OECD 311 No biodegradation observed.
Human Health
Acute lethality oral – Screen & OECD 425 No effects observed
LD50>2000 mg/kg/day
Irritation (Eye/Skin) – OECD 405 & OECD 406 Non-irritating
Sensitization - OECD 406 Non-sensitizing (Buehler Method)
Combined repeated dose toxicity study (28-day) with reproductive/developmental toxicity screening test - OECD 422
None observed
NOAEL>1000 mg/kg/day
Genotoxicity (i.e. DNA damage) None observed
Ecotoxicology
Acute invertebrate toxicity (Daphnia) – OECD 202
Not classified as toxic.
EL50 > 1000 mg/L (the limit loading rate tested). Study conducted using the water accommodated fraction (WAF).
Acute vertebrate toxicity (fish)* ;
Acute aquatic plant toxicity (algae);
Chronic daphnia;
Daphnia reproduction;
Fish early life stage test;
Sediment toxicity;
No toxicity classification based on Daphnia acute toxicity study of brominated polymer WAF. Testing is not required for registration purposes based on polymer exemption criteria.
Fish bioconcentration (BCF) Testing not warranted based on physico-chemical properties and polymer exemption
The advantages of the Polymeric FR, which can be seen as a plastic in its own right, lead to a
more sustainable alternative than HBCDD.
Key features can be described as
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Sharp molecular weight distribution with a high molecular weight : 60,000-160,000
g/mol; <0.1% <1,000 g/mol; <0.1% <500 g/mol , no oligomers, and low residual
content <10ppm
Large size ensures it cannot pass through cell membranes and this exclusion limits
bioavailability and toxicity XPS Foam surface photo-degradation is low and results only in non-PBT and non-CMR
substances
Thermally stable at typical processing temperatures for polystyrene (PS) foam
Moreover, the hazards and risks of the Polymeric FR have been well documented by the
Applicants in the Analysis of Alternatives document.
In addition the Polymeric FR has been one of the 3 candidates, the other two being small molecules, evaluated in the recently published final report from the Design for Environment
(DfE) Analysis of Alternatives for HBCDD project led by the U.S. EPA. The table below provides
a comparative hazard summary of the Polymeric FR relative to HBCD and two additional small
molecule alternative FRs. Overall these data highlight that the Polymeric FR has the most
favourable hazard profile of the HBCD alternatives. http://www.epa.gov/dfe/pubs/projects/hbcd/hbcd-full-report-508.pdf
The EPA concluded
‘Based on DfE AA criteria and guidance, the hazard profile of the butadiene styrene brominated
copolymer (CASRN 1195978-93-8) shows that this chemical is anticipated to be safer than HBCD for
multiple endpoints. Due to its large size, lack of low molecular weight (MW) components, and un-
reactive functional groups, human health and ecotoxicity hazard for this polymer are measured or
predicted to be low, although experimental data were not available for all endpoints. In general the
exposure potential to the butadiene styrene brominated copolymer is expected to be lower than the other
chemicals in this assessment because it is a large polymer and is unlikely to be released from the
polystyrene. However, this alternative is inherently persistent and its long-term behavior in the
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environment is not currently known. Chemical suppliers have commercialized this polymer, and
polystyrene manufacturers are testing it in their products to ensure that the polystyrene will meet all
performance standards. The hazard designations for this alternative are based upon high MW
formulations of the polymer, where all components have a MW >1,000. The polymer is regulated with a Significant New Use Rule that was finalized in June 2013. Manufacture (or import) of the polymer
requires notification to EPA except in these cases: (1) the MW of the polymer is in the range of 1,000 to
10,000 daltons, or (2) the MW of the polymer is ≥ 10,000 daltons and less than 5 percent of the particles
are in the respirable range of 10 microns or less (U.S. EPA 2013).’
In 2012 the new Polymeric FR technology received positive and supportive feedback from
external evaluations on the basis of innovation and sustainability 3,4,5.
In conclusion, the Polymeric FR is persistent by design but due to the experimentally confirmed
stability of this substance the environmental (and human health) risks are low. It is recognised to be non-PBT and non vPvB and also not a POP substance and a more sustainable alternative
to HBCDD.
5. AVAILABILITY
5.1 Supply/Demand
The Polymeric FR is being made available to the whole of the PS foam industry via 3rd party
licensing technology for manufacture of the Polymeric FR. The 3 Companies are Chemtura
Corporation, Bromine Compounds Ltd. (an ICL-IP Company) and Albemarle Corporation with the Polymeric FR being marketed as Emerald Innovation™ 3000, FR-122P and GreenCrest™
respectively.
Press releases announcing the licensing agreements for the technology and updates on
continued capacity increases, after the initial announcement of the development by Dow was first made in 2011, have been published (See Appendix 1 for all press releases). These
confirm the global availability of sufficient volumes of the Polymeric FR for the Polystyrene
foam industry (EPS and XPS).
Our supply/demand assessment is consistent with what has been shared by other parties
contributing to this public consultation (Chemtura Sales Europe BV- Comment number 553).
The most recent press release from Dow in April 2014 confirmed that the 3 international
licensees, have built commercial production capacity for the new polymeric flame retardant
amounting to more than 12,000 MT at the end of 2013 which will be expanded to more than
22,000 MT by the end of 2014 ahead of the REACH sunset date of August 2015. This is in line with the applicant’s assessment. The capacity is expected to increase beyond 25,000 MT in
2015 and more than 30,000 by the end of 2016 essentially in line with the Applicants
numbers. Besides Polymeric FR, it is acknowledged that volumes of small molecule
alternatives (see EPA table 1 section 4. Hazards and Risks) are also used within the EPS and XPS industries adding to the general availability of alternatives to HBCDD.
5.1.1 EU Demand
One additional data point we would want to highlight around demand development of HBCDD in EU are the Euroconstruct numbers 6. Euroconstruct provides an update on the past and
future growth of the EU construction industry twice a year. From the below graph it becomes
clear that the EU Construction industry peaked in 2007 – 2008 and since then has been going
through a very significant downturn.
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Past Demand PS Foam demand, as such also HBCD, directly correlates to the
construction demand. .Since 2007 both the residential & non-residential sector’s
output (key segements for PS foams) have dropped by 15 & 18 points respectively.
This is in contrast to the Applicants’ information which estimated demand growth of
3% to 4% for this period. Future Demand Going forward Euroconstruct predicts a modest growth of 1.8% for
all segments. This in contrast to the Applicants who predict 3-5% growth for the
same period depending on the PS foam technology.
As a result, the total demand for Polymeric FR in 2015 and beyond will be less than predicted by the Applicants.
5.1.2 Non–EU Demand
In the case of Non EU demand, even if we take the Applicants assumptions around the
polymeric FR demand as correct, we don’t understand how the predicted volumes have been reached. We assume there are calculation errors.
5.2 Qualification of Polymeric FR for downstream users
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The Applicants claim they need time to a) complete a product testing programme with
commercial grade Polymeric FR, b) ensure customer acceptability and c) meeting of relevant
safety standards ( page no. of AoA document).
Regarding a) complete product testing and c) meeting relevant safety standards:
EPS and XPS foams are construction products having European harmonized technical
specification described in hEN13163 and hEN13164 respectively. All harmonized product
properties are defined therein and provide a basis for CE marking (covering basic works
requirements incl. safe use).
The Plastics Europe EPS bead group, of which the Applicants are members, has been aware of
the sunset date for HBCD of August 2015 and was evaluating the Polymeric alternative and
others in their foam since 2010 and concluded that Polymeric FR was a commercial alternative
in 2012 (Applicants Analysis of Alternatives document page 49).
Already in September 2012, the EU Notified Bodies Sector Group 19 Thermal Insulation (SG19)
of the reviewed the impact of Polymeric FR on XPS and EPS foam properties (produced for the
German market and evaluated by FIW (Forschungs-Institut für Wärmeschutz, Deutschland).
The Notified Bodies concluded that all EPS and XPS foams are in compliance such that foam
properties are not influenced by the change in flame retardant from HBCDD to Polymeric FR. A further conclusion made was that Initial type testing (ITT) for product properties, does not
require full recertification for EPS and XPS foam. See the official Q&A document (Minutes of
CEN TC88 N3037 Question no.52- Appendix 2) where it states that only testing for fire
properties is required.
This conclusion means:
The change to the Polymeric FR does not alter the final foam properties and quality will
be maintained
As a result only limited product testing (i.e. only fire performance) time is needed to ensure compliance for the PS foam products containing Polymeric FR.
The above is a reassurance and confirmation for the PS foam Industry using Polymeric
FR and their downstream users.
Point b) customer acceptability
As a consequence of the above, point b) customer acceptability is also satisfied for the whole
PS foam industry including the Applicants. It is therefore hard to see that the EPS Applicants do need so much additional time for certification in Europe, leading to the request for an
authorisation.
The original time of 6 months for product confirmation quoted by the Applicants would thus appear to be more than sufficient for the downstream user conversion. As Polymeric FR is
available in the market place there is no obstacle to product confirmation regarding meeting
safety standards and this phase can be smoothly completed. Further evidence for a quick
transition is that in Oct. 2013 the IVH (Industrie Verband Hartschaum) communicated that conversion to Polymeric FR will be completed by mid 2014 (Appendix 3.). This is a clear
indication that all required compliance testing and application validation was possible within
less than 12 months in a highly regulated German market. Some of the other EPS bead and
foam producers in Europe have already started making the transition to Polymeric FR (See for
example BASF, Sunpor, Swiss EPS industry Appendix 1, 10) so this is achievable.
In conclusion the PS foam industry has been aware of the phase-out dates for HBCDD since
the original Official decision from the European Commission was published in 2011 confirming
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the sunset date for HBCDD of August 2015 thus sending a clear message that if a suitable
alternative is available substitution should be the goal. The EPS Industry responded to this.
The EPS Industry has conducted comprehensive research in the development and
implementation of alternatives and has reassured both technical bodies, downstreamers and
customers of the quality of the new product in due time (2012). It is therefore possible to transition away from HBCDD by the EU sunset date.
6. CONCLUSION ON SUITABILITY AND AVAILABILITY OF THE ALTERNATIVE
The Polymeric FR has been demonstrated to be a suitable and more sustainable alternative to
HBCDD in Polystyrene foam. Even the consortium Applicants have accepted Polymeric FR for
use in EPS foam.
It is therefore recognized to be technically feasible and accepted by the EPS market place as
all required and declared properties of the final product are able to be met. The decision from
the EU Sector group of Notified Bodies for Thermal Insulation (SG19) conclusion ensures
Polystyrene foams containing Polymeric FR to be in compliance with product safety requirements thus satisfying customer requirements. This demonstrates that the EPS foams
containing Polymeric FR will be able to replace foams containing HBCDD and in a transition
time of at most 6 months for product confirmation phase of implementation.
The most recent press release from Dow in April 2014 confirmed that the 3 international
licensees, have built commercial production capacity for the new polymeric flame retardant amounting to more than 12,000 MT at the end of 2013 which will be expanded to more than
22,000 MT by the end of 2014 and increasing to more than 25,000 MT in 2015 ahead of the
REACH sunset date of August 2015 for HBCDD thereby meeting demand in a timely manner for
the EU phase-out of HBCDD. Dow’s supply/demand assessment is consistent with what has been shared by other parties contributing to this public consultation (e.g. Chemtura
Corporation Comment No.553). Of course capacity can be increased to meet future market
demand if and when needed and we query the applicant’s demand volumes.
This being the case there is adequate supply of Polymeric FR and sufficient time to implement to meet the European market needs and transition away from HBCDD before the sunset date
of August 2015. In conclusion in our opinion an authorization for HBCDD for EPS foams is not
warranted as an alternative is available.
7. OTHER COMMENTS
REFERENCES
1. POPRC 9 Side event on Alternatives to HBCDD October 2013
http://chm.pops.int/Implementation/TechnicalAssistance/Webinars/tabid/1529/Default.
aspx?overlayId=ArtId-11407
2. Beach, et al. Cellular Polymers Vol. 32, No.4, 2013, New Class of Brominated Polymeric Flame Retardants for Use in Polystyrene Foams.
3. 4th Annual Michigan Green Chemistry Governor’s Award
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http://www.michigan.gov/deq/0,4561,7-135-3585_49005-315030--,00.html
4. 2012 R&D 100 Award http://www.rdmag.com/articles/2012/06/2012-r-d-100-award-
winners
5. 2012 Wall Street Journal Technology Innovation Runners-up Award in the Materials and Other Base Technologies Category
6. Euroconstruct – Euroconstruct 77th Conference Oslo, June 2014 http://www.euroconstruct.org/conference
APPENDIXES
Appendix 1: Press releases for the original Polymeric FR invention and the licensing
agreements and conversion
1. Dow Chemical corporate press release, March 29, 2011: http://www.dow.com/news/corporate/2011/20110329b.htm
2. Great Lakes Solutions/Chemtura press release, March 29, 2011:
http://news.greatlakes.com/press-release/chemtura-corporation-first-sign-license-agreement-dow-chemical-company-polymeric-flame
3. BASF corporate press release, April 5, 2011:
“Dow’s new polymer ensures the same flame retardancy as HBCD while offering a superior
environmental profile.”
http://www.basf.com/group/corporate/en/function/conversions:/publish/content/news-and-media-relations/news-releases/downloads/2011/P230-HBCD-e.pdf
4. Bromine Compounds Limited (Israeli Chemicals Limited – Industrial Products (ICL-IP)) press release, January 25, 2012:
http://www.prnewswire.com/news-releases/icl-ip-ensures-its-leading-position-in-flame-retardants-with-new-eco-friendly-polymeric-offering-138026018.html
5. Albemarle Corporation – Polymer Solutions press release, April 12, 2012:
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http://phx.corporate-ir.net/phoenix.zhtml?c=117031&p=irol-newsArticle&ID=1682369
6. Great Lakes (Chemtura) Nov 20, 2012:
http://news.greatlakes.com/press-release/great-lakes-solutions-chemtura-business-
commissions-commercial-production-facility-new
7. Great Lakes (Chemtura) April 22, 2013:
http://news.greatlakes.com/press-release/great-lakes-solutions-sees-continued-success-new-flame-
retardant-technology
8. ICL-IP Completing Second Production Facility for Polymeric Flame Retardant April 22, 2014
-Additional 10,000MT Capacity for its FR-122P
Flame Retardant to Meet Expected Demand
http://www.prnewswire.co.uk/news-releases/icl-ip-completing-second-production-facility-for-polymeric-flame-retardant-256176891.html
9. Dow Chemical Company - Dow’s Japanese XPS Plants First In World To Use New Polymeric
Flame Retardant Feb 14, 2014
http://www.dow.com/news/press-releases/article/?id=6436
10. Plasteurope.com – EPS Industry, Switzerland and Germany well on their way Mar 11 2014
http://www.plasteurope.com/news/eps_insulation_market_t227738
11. Dow Chemical Company - Dow Produces First XPS Foam Material With New Sustainable
Polymeric Flame Retardant In Europe APRIL 2014 http://www.dow.com/news/press-
releases/article/?id=6487
12. BASF - BASF XPS products converted May 19 2014
http://www.basf.com/group/pressrelease/P-14-240
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Appendix 2:
Minutes of CEN TC88 N3037 Question no.52
CEN-TC88_N3073_Sector_Group_19_-_Questions_and_answers_-_rev.pdf
Appendix 3
IVH statement
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