Posted on 20/06/2022 in Fire Safety Regulatory Recycling 2022
Flame retardants, Classification, recycling

Analysis of 69 FRs suggests that 12 (7 halogenated/ATO, 5 PIN) may lead to Classification of plastic wastes, so posing a regulatory obstacle to recycling. In total, 23 out of 69 FRs are identified as potentially posing regulatory obstacles to recycling: 16 halogenated (2 no longer used, 7 Classified, 7 under ECHA evaluation) and 7 PIN (5 Classified, 2 under ECHA evaluation).
Data on flame retardant use, including concentrations susceptible to be used in plastics, and Hazard Classification statements, were collated from the Plastics Additives Initiative (PAI), ECHA, the pinfa website and FR manufacturers catalogues. A list of 69 flame retardants used in the EU was established from these sources and, within this list, twelve FRs were identified as susceptible to be present in plastics at concentrations leading to Classification of end-of-life plastics as Hazardous waste.

Sorting and management options for plastics containing these FRs are discussed, concluding that the concentration limit for sorting of 0.2% bromine should be maintained because this includes all the brominated flame retardants currently under reassessment by ECHA.
Seven of the twelve currently-used FRs identified as susceptible to lead to Hazardous Classification of plastic wastes are halogenated FRs and their synergists:

  • [not counted – banned] HBCDD, EINECS 221-695-9 = Hexabromocyclododecane (POP and other)
  • [not counted – banned] DecaBDE, EINECS 214-604-9 = Bis(pentabromophenyl) ether (POP and other)
  • TBBPA, EINECS 201-236-9 = 2,2′,’,6′-tetrabromo-’,4′-isopropylidenediphenol (H410)
  • DBNPG, EINECS 221-967-7 = Dibromoneopentyl glycol = 2,2-Bis(bromomethyl)-1,3-propanediol = 2,2-bis(bromomethyl)propane-1,3-diol
  • TBNPA, EINECS 253-057-0 = Tribromoneopentyl alcahol
  • TBP, EINECS 204-278-6 = 2.4.6-tribromophenol
  • TDCP, EINECS 237-159-2 = Tris[2-chloro-1-(chloromethyl)ethyl] phosphate (H351, H411)
  • MCCP = Alkanes, C14-17, chloro (PBT, H400, H410, H362)
  • ATO = Diantimony Trioxide (H351)

Five are non-halogenated FRs:

  • Reaction mass of p-t-butylphenyl diphenyl phosphate and bis(p-t-butylphenyl) phenyl phosphate and triphenyl phosphate (H410, H411), EINECS 700-9990-0
  • PIP = TrTPP, EINECS 273-066-3 = Phenol, isopropylated, phosphate (3:1) (H361, H410, H411)
  • Dimethyl propylphosphonate (H360), EINECS 242-555-3
  • Melamine = 1,3,5-triazine-2,4,6-triamine (H361)
  • Melamine cyanurate = 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, compound with 1,3,5-triazine-2,4,6-triamine (1:1) (H373)

In addition to the above, it is noted that ECHA re-assessment is underway for 12 FRs, of which 4 are already listed above (TBBPA, DBNPG, PIP, TDCP) plus an additional 6 halogenated and 2 non-halogenated FRs:

  • 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (PBT), EINECS 426-040-2
  • DBDPE, EINECS 262-680-7 = Decabromodiphenyldioxyethane = 1,1′-(ethane-1,2-diyl)bis[pentabromobenzene] (PBT),
  • EBTBP, EINECS 251-118-6 = Ethylene-bistetrabromophthalimide = N,N’-ethylenebis(3,4,5,6-tetrabromophthalimide) (PBT)
  • FR720, EINECS 244-617-5 = Tetrabromobisphenol A, bis (2,3-dibromopropyl ether)) = 1,1′-(isopropylidene)bis[3,5-dibromo-4-(2,3-dibromopropoxy)benzene] (PBT, ED)
  • 1,1′-(isopropylidene)bis[3,5-dibromo-4-(2,3-dibromo-2-methylpropoxy)benzene] (ED), EINECS 306-832-3
  • Dechlorane plus, EINECS 236-948-9 = Dodecachlorodimethan-o-dibenzocyclooctane (PBT, POP)
  • EINECS 252-813-7 = 6H-dibenz[c,e][1,2]oxaphosphorin 6-oxide (SS = skin sensitising)
  • TEP, EINECS 201-114-5 = Triethyl phosphate (H302)

Graphic: Distribution of total bromine in the dense fraction of plastic scraps of screens, mainly cathode ray tubes (CRT) (from Hennebert 2019, Proceedings of the 17th International Waste Management and Landfill Symposium (Sardinia 2019), 30/09 – 04/10/2019, Cagliari, Italy – with permission).
“Hazardous properties of brominated, phosphorus, chlorinated, nitrogen and mineal flame retardants in plastics which may hinder their recycling”, P. Hennebert, Detritus, Volume 17, December 2021, pages 49-57
“The substitution of regulated brominated flame retardants in plastic products and waste and the declared properties of the substitutes in REACH”, P. Hennebert, Detritus, Volume 16, 2021, pages 16-25

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