1,2,5,6,9,10-hexabromocyclododecane

from Wikipedia, the free encyclopedia
Structural formula
Structure of hexabromocyclododecane
Structural formula without stereochemistry
( complex mixture of stereoisomers )
General
Surname 1,2,5,6,9,10-hexabromocyclododecane
other names
  • Hexabromocyclododecane
  • HBCD
  • HBCDD
Molecular formula C 12 H 18 Br 6
External identifiers / databases
CAS number
  • 3194-55-6 (mixture of stereoisomers)
  • 134237-50-6 (α-HBCD)
  • 134237-51-7 (β-HBCD)
  • 134237-52-8 (γ-HBCD)
EC number 221-695-9
ECHA InfoCard 100.019.724
PubChem 18529
Wikidata Q420301
properties
Molar mass 641.73 g mol −1
Physical state

firmly

density

2.24-2.38 g · cm -3

Melting point
  • 179-181 ° C (α-HBCD)
  • 170–172 ° C (β-HBCD)
  • 207-209 ° C (γ-HBCD)
Vapor pressure
  • 3.0 · 10 −5 Pa (technical mixture, 25 ° C)
  • 3.0 · 10 −4 Pa (α-HBCD, 25 ° C)
  • 4.3 10 −5 Pa (β-HBCD, 25 ° C)
  • 2.4 · 10 −5 Pa (γ-HBCD, 25 ° C)
solubility

practically insoluble in water:

  • 2.3 10 −7 mol l −1 (technical mixture, 25 ° C)
  • 2.8 10 −6 mol l −1 (α-HBCD, 25 ° C)
  • 9.9 10 −7 mol l −1 (β-HBCD, 25 ° C)
  • 1.7 10 −7 mol l −1 (γ-HBCD, 25 ° C)
safety instructions
GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
08 - Dangerous to health

Caution

H and P phrases H: 361-362
P: ?
Authorization procedure under REACH

of particular concern : persistent, bio-accumulative and toxic ( PBT ); subject to approval

Toxicological data

> 10 g kg −1 ( LD 50 ,  rat ,  oral )

As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

1,2,5,6,9,10-hexabromocyclododecane ( HBCD or HBCDD ) is an additive flame retardant that was mainly used in polystyrene foam , in high-impact polystyrene and in upholstered furniture. It causes local sources of fire to develop more slowly. It is not chemically bound in the polymer matrix, but rather as a homogeneous dispersion . HBCD was included in the Stockholm Convention on Persistent Organic Pollutants in May 2013 , which means that its use as flame retardants is prohibited from being manufactured and used worldwide.

Presentation and extraction

Technically HBCD is by addition of bromine to 1,5,9-cyclododecatriene prepared.

properties

HBCD 16 exist stereoisomers , resulting in the spatial arrangement of six covalently bound bromine - substituents are different. The α-, the β- and the γ-isomer occur in technical products.

Structures of the six isomers, which are present in a proportion of> 1% in the technical product

use

The main areas of application for HBCD were the insulation foams EPS (expanded polystyrene rigid foam) and XPS (extruded polystyrene rigid foam), which were used on a large scale for the insulation of buildings. By equipping it with HBCD, it was achieved that polystyrene was classified as flame-retardant . In addition, HBCD was also used as a flame retardant in electrical appliance housings (especially those made from HIPS ), textiles and upholstered furniture until 2013 . In electrical average at inquiries carried out in the years 2003 and 2011 studies concentrations of 17 was  ppm or ppm found 14, which is due to the presence in the housings of electronic equipment.

Typical concentrations of HBCD used were around 0.7% in EPS, 2.5% in XPS and 6–15% in textiles.

In 2001, industrial consumption in Europe was estimated at around 9500 tons per year. The worldwide annual consumption was 16,700 tons.

The US EPA identified three alternative substances to HBCD that can be used in EPS and XPS:

  • 1,1 ′ - (2,2-Propanediyl) bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropoxy) benzene] (CAS No. 97416-84-7)
  • 1,1 ′ - (2,2-Propanediyl) bis [3,5-dibromo-4- (2,3-dibromopropoxy) benzene] (CAS No. 21850-44-2)
  • Brominated styrene-butadiene copolymer (CAS No. 1195978-93-8)

The latter has actually been used by various manufacturers since 2014 or 2015.

Analytics

For analysis, the isomer mixture is mostly separated by chromatography (e.g. by HPLC ) on selected cyclodextrin phases . The detection takes place by mass spectrometry mostly with the HPLC / MS or the GC / MS coupling . In the case of biological matrices , more complex sample preparation is required , usually with primary extraction of a total lipid extract and subsequent purification using silica gel separation columns and / or by lipophilic gel chromatography .

By extraction of EPS or XPS pieces in acetone and subsequent X-ray fluorescence spectroscopy (XRF), it is easy to distinguish between equipment with hexabromocyclododecane or the polymeric flame retardant brominated styrene-butadiene copolymer . The use of nuclear magnetic resonance (NMR) is also possible.

Environmental relevance

HBCD can get into the environment through various processes and occurs in trace concentrations in all environmental compartments such as air, water and in the soil. High concentrations of the α-isomer were found in sediments, sewage sludge and fish. In a study carried out by the WWF , HBCD was also found in the blood of MEPs. HBCD is also contained in many food packaging in lower concentrations.

HBCD is persistent and therefore difficult to break down in the environment. It is bioaccumulating, i.e. it accumulates in living things through the food chain. Toxic effects have been proven for aquatic organisms such as crustaceans and algae. In addition, animal experiments have shown damage to embryonic and infant development.

In 2008, HBCD was therefore added to the list of substances of very high concern as a PBT substance . The substance was included in the Stockholm Convention on Persistent Organic Pollutants in May 2013 . A worldwide production and application ban applies to use as a flame retardant. For the main area of ​​application as an additive in insulation boards, there was a one-year exception rule. The EU had granted approval for use in EPS for construction purposes, with the review period ending on August 21, 2017.

In Germany, HBCD-containing polystyrene insulation materials had to be disposed of as hazardous waste from October 1, 2016 following a change in the Waste Catalog Ordinance . This classification led to disposal bottlenecks as many waste incineration plants did not have the appropriate permit. In order to continue to enable disposal in these waste incineration plants, some federal states have issued decrees that polystyrene insulation materials containing HBCD are permitted up to a certain percentage in mixed construction waste. Following a further amendment to the Waste Catalog Ordinance, HBCD-containing polystyrene insulation materials are considered non-hazardous waste from December 28, 2016 and can be disposed of in waste incineration plants. On July 17, 2017, the POP Waste Monitoring Ordinance and an amendment to the Waste Catalog Ordinance were issued ( BGBl. I p. 2644 ). HBCD-containing polystyrene insulation materials can therefore continue to be disposed of in waste incineration plants, but they are subject to a separate collection requirement, a ban on mixing, and obligations to provide evidence and register.

In Austria, EPS insulation materials containing HBCD are classified as non-hazardous waste (waste code number 57108 “Polystyrene, Polystyrene foam”). They may be incinerated in incineration plants for non-hazardous waste (waste incineration plants).

Web links

Commons : Hexabromocyclododecane  - collection of images, videos and audio files

Individual evidence

  1. ↑ a b c d Persistent Organic Pollutants Review Committee: Report of the Persistent Organic Pollutants Review Committee on the work of its sixth meeting: Addendum: Risk profile on hexabromocyclododecane , 2010.
  2. ↑ a b c d e f g h Jon Arnot, Lynn McCarty, James Armitage, Liisa Toose-Reid, Frank Wania, Ian Cousins: An evaluation of hexabromocyclododecane (HBCD) for Persistent Organic Pollutant (POP) properties and the potential for adverse effects in the environment . Ed .: UNECE . May 26, 2009 ( unece.org [PDF; 3.0 MB ]).
  3. ↑ Entry on hexabromocyclododecane, isomers in the GESTIS substance database of the IFA , accessed on February 1, 2016(JavaScript required) .
  4. ↑ Entry on 1,2,5,6,9,10-hexabromocyclodecane in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on February 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .
  5. ↑ Entry in the SVHC list of the European Chemicals Agency , accessed on July 16, 2014.
  6. ↑ Entry in the register of substances subject to authorization of the European Chemicals Agency , accessed on July 16, 2014.
  7. ↑ Entry on 1,2,5,6,9,10-hexabromocyclododecane in the Hazardous Substances Data Bank , accessed on November 19, 2014.
  8. ↑ Åke Bergman , Andreas Rydén, Robin J. Law, Jacob de Boer, Adrian Covaci, Mehran Alaee, Linda Birnbaum, Myrto Petreas, Martin Rose, Shinichi Sakai, Nele Van den Eede, Ike van der Veen: A novel abbreviation standard for organobromine , organochlorine and organophosphorus flame retardants and some characteristics of the chemicals . In: Environment International . tape 49 , 2012, p. 57–82 , doi : 10.1016 / j.envint.2012.08.003 , PMC 3483428 (free full text).
  9. ↑ BSEF: Application of HBCD ( Memento of May 8, 2009 in the Internet Archive ).
  10. ^ The new POPs under the Stockholm Convention. In: pops.int. Accessed May 10, 2018 .
  11. ↑ G. Oenbrink, T. Schiffer: Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene. In: Ullmann's Encyclopedia of Technical Chemistry . Wiley-VCH Verlag, Weinheim 2012; doi : 10.1002 / 14356007.a08_205.pub2 .
  12. ^ RJ Law, M. Kohler et al .: Hexabromocyclododecane challenges scientists and regulators. In: Environ. Sci. Technol. 39 (13), 2005, pp. 281A-287A. doi: 10.1021 / es053302f , PMID 16053062 .
  13. ^ A b Johanna Wurbs, Inga Beer, Til Bolland, Malgorzata Debiak, Folke Dettling, Juliane Koch-Jugl, Lars Tietjen, Mareike Walther, Joachim Wuttke, Hans-Christian Stolzenberg, Caren Rauert, Petra Apel: Hexabromcyclododecan (HBCD): Answers to frequently asked questions . Ed .: Federal Environment Agency . 7th edition. Dessau-Roßlau December 2017 ( Umweltbundesamt.de [PDF; 2.5 MB ]).
  14. ^ Ruedi Taverna, Rolf Gloor, Urs Maier, Markus Zennegg, Renato Figi, Edy Birchler: Material flows in Swiss electronic waste . Metals, non-metals, flame retardants and polychlorinated biphenyls in small electrical and electronic devices . Federal Office for the Environment , Bern 2017. Environmental status No. 1717: 164 p.
  15. ↑ Flame Retardants Fact Sheet. Hexabromocyclododecanes (HBCD). (PDF) (No longer available online.) In: www.cefic-efra.com. November 2006, archived from the original on December 26, 2015 ; accessed on February 1, 2019 .
  16. ↑ a b BSEF: Major Brominated Flame Retardants Volume Estimates - Total Market Demand By Region in 2001 ( Memento from April 2, 2015 in the Internet Archive ) (DOC file; 85 kB).
  17. ↑ US EPA : Flame Retardant Alternatives for Hexabromocyclododecane (HBCD) , 2014, p. Vi.
  18. ↑ External identifiers or database links to 1,1 ′ - (2,2-propanediyl) to [3,5-dibromo-4- (2,3-dibromo-2-methylpropoxy) benzene] : CAS number: 97416-84-7, EC number: 306-832-3, ECHA InfoCard: 100.097.074 , PubChem : 22345068 , ChemSpider : 11364088 , Wikidata : Q81987750 .
  19. ↑ External identifiers of or database links to 1,1 ′ - (2,2-propanediyl) bis [3,5-dibromo-4- (2,3-dibromopropoxy) benzene] : CAS number: 21850-44- 2, EC number: 244-617-5, ECHA InfoCard: 100.040.546 , GESTIS substance database : 24390 , PubChem : 62753 , ChemSpider : 56497 , Wikidata : Q27294521 .
  20. ↑ BASF: European EPS, XPS portfolio switched to PolyFR nine months ahead of REACH deadline , Plasteurope.com, November 27, 2014.
  21. ↑ ICL IP and BASF make progress in switch to polymeric flame retardant. In: Additives for Polymers. 2014, 2014, p. 8, doi: 10.1016 / S0306-3747 (14) 70123-X .
  22. ^ R. Koeppen, R. Becker, F. Emmerling, C. Jung, I. Nehls: Enantioselective preparative HPLC separation of the HBCD stereoisomers from the technical product and their absolute structure elucidation using X-ray crystallography. In: Chirality . 19 (3), 2007, pp. 214-222. PMID 17226748 .
  23. ↑ MA Abdallah, C. Ibarra, H. Neels, S. Harrad, A. Covaci: Comparative evaluation of liquid chromatography-mass spectrometry versus gas chromatography-mass spectrometry for the determination of hexabromocyclododecanes and their degradation products in indoor dust. In: J Chromatogr A. 1190 (1-2), 2008, pp. 333-341. PMID 18359486 .
  24. ↑ L. Roosens, AC Dirtu, G. Goemans, C. Belpaire, A. Gheorghe, H. Neels, R. Blust, A. Covaci: Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium. In: Environ Int. 34 (7), 2008, pp. 976-983. PMID 18400299 .
  25. ↑ C. Thomsen, HK Knutsen, VH Liane, M. Frøshaug, HE Kvalem, M. Haugen, HM Meltzer, J. Alexander, G. Becher: Consumption of fish from a contaminated lake strongly affects the concentrations of polybrominated diphenyl ethers and hexabromocyclododecane in serum. In: Mol Nutr Food Res. 52 (2), 2008, pp. 228-237. PMID 18186101 .
  26. ↑ M. Schlummer, J. Vogelsang, D. Fiedler, L. Gruber, G. Wolz: Rapid identification of polystyrene foam wastes containing hexabromocyclododecane or its alternative polymeric brominated flame retardant by X-ray fluorescence spectroscopy. In: Waste Management & Research . 33, 2015, pp. 662-670, doi: 10.1177 / 0734242X15589783 .
  27. ↑ D. Jeannerat, M. Pupier, S. Schweizer, YN Mitrev, P. Favreau, M. Kohler: Discrimination of hexabromocyclododecane from new polymeric brominated flame retardant in polystyrene foam by nuclear magnetic resonance. In: Chemosphere . 144, 2016, pp. 1391-1397, doi: 10.1016 / j.chemosphere.2015.10.021 . PMID 26492426 .
  28. ↑ Robert Köppen, Susanne Esslinger, Roland Becker, Irene Nehls: Hexabromcyclododecane in domestic freshwater fish. In: News from chemistry. 57, 2009, pp. 901-904.
  29. ^ A. Covaci, AC Gerecke et al .: Hexabromocyclododecanes (HBCDs) in the environment and humans: a review. Environ. Sci. Technol. 40 (12), 2006, pp. 3679-88. doi: 10.1021 / es0602492 , PMID 16830527 .
  30. ↑ WWF Detox Campaign: Bad Blood? A Survey of Chemicals in the Blood of European Ministers . 2004.
  31. ↑ M. Rani, WJ Shim, GM Han, M. Jang, YK Song, SH Hong: Hexabromocyclododecane in polystyrene based consumer products: An evidence of unregulated use. In: Chemosphere . Vol. 110, 2014, pp. 111-119; doi: 10.1016 / j.chemosphere.2014.02.022 .
  32. ↑ ECHA : Member State Committee Support Document for Identification of Hexabromocyclododecane and All Major Diastereoisomers Identified as a Substance of Very High Concern , October 8, 2008.
  33. ↑ UBA: Worldwide "off" for flame retardants HBCD , press release 23/2013, May 8, 2013.
  34. ↑ Summary of the decisions of the European Commission on authorizations for placing on the market for the use and / or use of substances listed in Annex XIV of Regulation (EC) No. 1907/2006 of the European Parliament and of the Council on registration, evaluation, authorization and Restriction of chemical substances (REACH) are listed. Official Journal of the European Union, C 10, 13 January 2016.
  35. ↑ Bernd Freytag: Disposal emergency for insulation boards . FAZ. October 1, 2016. Accessed February 1, 2017.
  36. ^ Pia Grund-Ludwig: The first federal states regulate the disposal of HBCD insulation . EnBauSa. October 20, 2016. Retrieved February 1, 2017.
  37. ↑ Current development on HBCD (D) -containing insulation materials, change in the Waste Catalog Ordinance . Bavarian State Office for the Environment, Information Center UmweltWirtschaft (IZU). January 11, 2017. Archived from the original on February 1, 2017. Retrieved February 1, 2017.
  38. ↑ Federal Council simplifies disposal of Styrofoam . Federal Council. July 7, 2017. Retrieved July 13, 2017.
  39. ↑ Information on HBCDD-containing insulation waste . Federal Ministry for Agriculture, Forestry, Environment and Water Management, January 25, 2017.