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Chlorinated paraffins

March 15, 2024

Chlorinated paraffins (CPs) are complex mixtures of polychlorinated n-alkanes (paraffin wax). The chlorination degree of CPs can vary between 30 and 70 wt%. CPs are subdivided according to their carbon chain length into short-chain CPs (SCCPs, C10–13), medium-chain CPs (MCCPs, C14–17) and long-chain CPs (LCCPs, C>17). Depending on chain length and chlorine content, CPs are colorless or yellowish liquids or solids.[1]

Structure of 2,3,4,5,6,8-hexachlorodecane, an example of a short-chained chlorinated paraffin (61% Cl by weight)
Structure of 2,5,6,7,8,11,15-heptachloroheptadecane, an example of a medium-chain chlorinated paraffin (52% Cl by weight)

Production edit

Chlorinated paraffins are synthesized by reaction of chlorine gas with unbranched paraffin fractions (<2 % isoparaffins, <100 ppm aromatics) at a temperature of 80–100 °C.[2] The radical substitution may be promoted by UV-light.[3][1]

CxH(2x+2) + y Cl2 → CxH(2x−y+2)Cly + y HCl

When the desired degree of chlorination is achieved, residues of hydrochloric acid and chlorine are blown off with nitrogen. Epoxidized vegetable oil, glycidyl ether or organophosphorous compounds may be added to the final product for improved stability at high temperatures.[4][5]

Commercial products have been classified as substances of unknown or variable composition. CPs are complex mixtures of chlorinated n-alkanes containing thousands of homologues and isomers[6] which are not completely separated by standard analytical methods.[7]

CPs are produced in Europe, North America, Australia, Brazil, South Africa and Asia.[8] In China, where most of the world production capacity is located, 600,000 tons of chlorinated paraffins were produced in 2007.[9] Production and use volumes of CPs exceeded 1,000,000 tons in 2013.[10]

Industrial applications edit

Production of CPs for industrial use started in the 1930s,[11] with global production in 2000 being about 2 million tonnes.[12] Currently, over 200 CP formulations are in use for a wide range of industrial applications, such as flame retardants and plasticisers, as additives in metal working fluids, in sealants, paints, adhesives, textiles, leather fat and coatings.[13][1]

Safety edit

Short-chain CPs are classified as persistent and their physical properties (octanol-water partition coefficient (logKOW) 4.4–8, depending on the chlorination degree) imply a high potential for bioaccumulation. SCCPs are classified as toxic to aquatic organisms, and carcinogenic to rats and mice. Therefore, it was concluded that SCCPs have PBT and vPvB properties and they were added to the Candidate List of substances of very high concern for Authorisation under REACH Regulation.[14] SCCPs (average chain length of C12, chlorination degree 60 wt%) were categorised in group 2B as possibly carcinogenic to humans from the International Agency for Research on Cancer (IARC).[15] In 2017, it was agreed to globally ban SCCPs under the Stockholm Convention on Persistent Organic Pollutants, effective December 2018. However, also MCCPs are toxic to the aquatic environment and persistent; MCCPs in soil, biota, and most of the sediment cores show increasing time trends over the last years to decades; MCCP concentrations in sediment close to local sources exceed toxicity thresholds such as the PNEC.[10] In July 2021 also MCCPs were added to the Candidate List of Substances of Very High Concern (SVHC) under the REACH Regulation.

Chlorinated paraffins have been detected in marine life such as cetaceans (whales) and bivalves (molluscs). Of particular concern is fetal accumulation in whales, with the chemicals beginning to build-up in the offspring before they are even born.[16]

References edit

  1. ^ a b c Rossberg, M.; Lendle, W.; Pfleiderer, G.; Tögel, A.; Dreher, E. L.; Langer, E.; Rassaerts, H.; Kleinschmidt, P.; Strack (2006). "Chlorinated Hydrocarbons". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a06_233.pub2. ISBN 978-3527306732.
  2. ^ Brooke, Crookes & Merckel 2009, pp. 4, 23.
  3. ^ Lassen 2014, p. 50.
  4. ^ Kellersohn 1998.
  5. ^ Brooke, Crookes & Merckel 2009, p. 5.
  6. ^ Tomy 1997, pp. 2764–2765.
  7. ^ Lassen 2014, p. 30.
  8. ^ Lassen 2014, pp. 50–51.
  9. ^ De Boer et al. 2010, p. 8.
  10. ^ a b Glüge, Juliane; Schinkel, Lena; Hungerbühler, Konrad; Cariou, Ronan; Bogdal, Christian (2018). "Environmental Risks of Medium-Chain Chlorinated Paraffins (MCCPs): A Review" (PDF). Environmental Science & Technology. 52 (12): 6743–6760. Bibcode:2018EnST...52.6743G. doi:10.1021/acs.est.7b06459. PMID 29791144.
  11. ^ Kenne & Ahlborg 1996.
  12. ^ "SETAC SciCon Session Summaries – SETAC Globe". Chlorinated Paraffins – State of Science, Insights, Challenges and the Way Forward. Retrieved 10 August 2021.
  13. ^ De Boer et al. 2010, p. 9.
  14. ^ "Candidate List of substances of very high concern for Authorisation: Alkanes, C10–13, chloro (Short Chain Chlorinated Paraffins)". ECHA. Retrieved 2 January 2020.
  15. ^ "Chlorinated paraffins" (PDF). IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. 48: 70. 1990. ISBN 978-92-832-1248-5. PMC 7681329. PMID 2197463.
  16. ^ Yuan, Bo; McLachlan, Michael S.; Roos, Anna M.; Simon, Malene; Strid, Anna; de Wit, Cynthia A. (9 August 2021). "Long-Chain Chlorinated Paraffins Have Reached the Arctic". Environmental Science & Technology Letters. 8 (9): 753–759. Bibcode:2021EnSTL...8..753Y. doi:10.1021/acs.estlett.1c00470.

Sources edit

  • De Boer, J.; El-Sayed, Ali T.; Fiedler, H.; Legler, J.; Muir, D. C.; Nikiforov, V. A.; Tomy, G. T.; Tsunemi, K. (2010). The handbook of environmental chemistry 10: Chlorinated paraffins. Berlin: Springer-Verlag. ISBN 978-3-642-10760-3.
  • Brooke, DM; Crookes, MJ; Merckel, MD (2009). Environmental risk assessment: long-chain chlorinated paraffins (PDF). Bristol, UK: Environment Agency.
  • Kellersohn, Thomas (1998). "Chlorinated paraffins". Ullmann’s encyclopedia of industrial chemistry, electronic release (6th ed.). Weinheim: Wiley-VCH.
  • Kenne, Kerstin; Ahlborg, Ulf G (1996). Chlorinated paraffins. Environmental Health Criteria 181. Geneva: World Health Organization. ISBN 9241571810.
  • Lassen, Carsten; et al. (2014). (PDF). Copenhagen: Danish Ministry of Environment, Environmental Protection Agency. Archived from the original (PDF) on 2016-10-16.
  • Tomy, Gregg T.; et al. (1997). "Quantifying C10–C13 polychloroalkanes in environmental samples by high-resolution gas chromatography/electron capture negative ion high-resolution mass spectrometry". Analytical Chemistry. 69: 2764–2765. doi:10.1021/ac961244y.

Further reading edit

  • Bayen, Stéphane; Obbard, Jeffrey Philip; Thomas, Gareth O. (2006). "Chlorinated paraffins: A review of analysis and environmental occurrence". Environment International. 32 (7): 915–929. doi:10.1016/j.envint.2006.05.009. PMID 16814386.
  • Cherrie, J. W.; Semple, S. (2009). "Dermal Exposure to Metalworking Fluids and Medium-Chain Chlorinated Paraffin (MCCP)". Annals of Occupational Hygiene. 54 (2): 228–35. doi:10.1093/annhyg/mep081. PMID 19959560.
  • European Chemicals Bureau (2000). European Union Risk assessment report Vol. 4: Alkanes, C10-13, chloro, Luxembourg: Office for Official Publications of the European Community.
  • European Chemicals Bureau (2008). European Union Risk assessment report Vol. 81: Alkanes, C10-13, chloro (update), Luxembourg: Office for Official Publications of the European Community.
  • European Chemicals Bureau (2005). European Union Risk assessment report Vol. 58: Alkanes, C14-17, chloro (MCCP), Part I-Environment, Luxembourg: Office for Official Publications of the European Community.
  • European Commission (2011). European Union Risk assessment report: Alkanes, C14-17, chloro; Addendum to the final report (2007) of the risk assessment – Environment part. Luxembourg: Office for Official Publications of the European Community.
  • European Commission (2011). European Union Risk assessment report: Alkanes, C14-17, chloro (MCCP), Part II-Human Health, Luxembourg: Office for Official Publications of the European Community.
  • Pellizzato, Francesca; Ricci, Marina; Held, Andrea; Emons, Hendrik (2007). "Analysis of short-chain chlorinated paraffins: A discussion paper". Journal of Environmental Monitoring. 9 (9): 924–30. doi:10.1039/b710053a. PMID 17726552.
  • Tolbert, Paige E. (1997). "Oils and Cancer". Cancer Causes & Control. 8 (3): 386–405. doi:10.1023/A:1018409422050. JSTOR 3552699. PMID 9498901. S2CID 24166011.

External links edit

  • Short Chain Chlorinated Paraffins – Proposal for identification of a substance as a CMR, PBT, vPvB or a substance of an equivalent level of concern

March 15, 2024
chlorinated, paraffins, complex, mixtures, polychlorinated, alkanes, paraffin, chlorination, degree, vary, between, subdivided, according, their, carbon, chain, length, into, short, chain, sccps, medium, chain, mccps, long, chain, lccps, depending, chain, leng. Chlorinated paraffins CPs are complex mixtures of polychlorinated n alkanes paraffin wax The chlorination degree of CPs can vary between 30 and 70 wt CPs are subdivided according to their carbon chain length into short chain CPs SCCPs C10 13 medium chain CPs MCCPs C14 17 and long chain CPs LCCPs C gt 17 Depending on chain length and chlorine content CPs are colorless or yellowish liquids or solids 1 Structure of 2 3 4 5 6 8 hexachlorodecane an example of a short chained chlorinated paraffin 61 Cl by weight Structure of 2 5 6 7 8 11 15 heptachloroheptadecane an example of a medium chain chlorinated paraffin 52 Cl by weight Contents 1 Production 2 Industrial applications 3 Safety 4 References 5 Sources 6 Further reading 7 External linksProduction editChlorinated paraffins are synthesized by reaction of chlorine gas with unbranched paraffin fractions lt 2 isoparaffins lt 100 ppm aromatics at a temperature of 80 100 C 2 The radical substitution may be promoted by UV light 3 1 CxH 2x 2 y Cl2 CxH 2x y 2 Cly y HClWhen the desired degree of chlorination is achieved residues of hydrochloric acid and chlorine are blown off with nitrogen Epoxidized vegetable oil glycidyl ether or organophosphorous compounds may be added to the final product for improved stability at high temperatures 4 5 Commercial products have been classified as substances of unknown or variable composition CPs are complex mixtures of chlorinated n alkanes containing thousands of homologues and isomers 6 which are not completely separated by standard analytical methods 7 CPs are produced in Europe North America Australia Brazil South Africa and Asia 8 In China where most of the world production capacity is located 600 000 tons of chlorinated paraffins were produced in 2007 9 Production and use volumes of CPs exceeded 1 000 000 tons in 2013 10 Industrial applications editProduction of CPs for industrial use started in the 1930s 11 with global production in 2000 being about 2 million tonnes 12 Currently over 200 CP formulations are in use for a wide range of industrial applications such as flame retardants and plasticisers as additives in metal working fluids in sealants paints adhesives textiles leather fat and coatings 13 1 Safety editShort chain CPs are classified as persistent and their physical properties octanol water partition coefficient logKOW 4 4 8 depending on the chlorination degree imply a high potential for bioaccumulation SCCPs are classified as toxic to aquatic organisms and carcinogenic to rats and mice Therefore it was concluded that SCCPs have PBT and vPvB properties and they were added to the Candidate List of substances of very high concern for Authorisation under REACH Regulation 14 SCCPs average chain length of C12 chlorination degree 60 wt were categorised in group 2B as possibly carcinogenic to humans from the International Agency for Research on Cancer IARC 15 In 2017 it was agreed to globally ban SCCPs under the Stockholm Convention on Persistent Organic Pollutants effective December 2018 However also MCCPs are toxic to the aquatic environment and persistent MCCPs in soil biota and most of the sediment cores show increasing time trends over the last years to decades MCCP concentrations in sediment close to local sources exceed toxicity thresholds such as the PNEC 10 In July 2021 also MCCPs were added to the Candidate List of Substances of Very High Concern SVHC under the REACH Regulation Chlorinated paraffins have been detected in marine life such as cetaceans whales and bivalves molluscs Of particular concern is fetal accumulation in whales with the chemicals beginning to build up in the offspring before they are even born 16 References edit a b c Rossberg M Lendle W Pfleiderer G Togel A Dreher E L Langer E Rassaerts H Kleinschmidt P Strack 2006 Chlorinated Hydrocarbons Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a06 233 pub2 ISBN 978 3527306732 Brooke Crookes amp Merckel 2009 pp 4 23 Lassen 2014 p 50 Kellersohn 1998 Brooke Crookes amp Merckel 2009 p 5 Tomy 1997 pp 2764 2765 Lassen 2014 p 30 Lassen 2014 pp 50 51 De Boer et al 2010 p 8 a b Gluge Juliane Schinkel Lena Hungerbuhler Konrad Cariou Ronan Bogdal Christian 2018 Environmental Risks of Medium Chain Chlorinated Paraffins MCCPs A Review PDF Environmental Science amp Technology 52 12 6743 6760 Bibcode 2018EnST 52 6743G doi 10 1021 acs est 7b06459 PMID 29791144 Kenne amp Ahlborg 1996 SETAC SciCon Session Summaries SETAC Globe Chlorinated Paraffins State of Science Insights Challenges and the Way Forward Retrieved 10 August 2021 De Boer et al 2010 p 9 Candidate List of substances of very high concern for Authorisation Alkanes C10 13 chloro Short Chain Chlorinated Paraffins ECHA Retrieved 2 January 2020 Chlorinated paraffins PDF IARC Monographs on the Evaluation of Carcinogenic Risks to Humans 48 70 1990 ISBN 978 92 832 1248 5 PMC 7681329 PMID 2197463 Yuan Bo McLachlan Michael S Roos Anna M Simon Malene Strid Anna de Wit Cynthia A 9 August 2021 Long Chain Chlorinated Paraffins Have Reached the Arctic Environmental Science amp Technology Letters 8 9 753 759 Bibcode 2021EnSTL 8 753Y doi 10 1021 acs estlett 1c00470 Sources editDe Boer J El Sayed Ali T Fiedler H Legler J Muir D C Nikiforov V A Tomy G T Tsunemi K 2010 The handbook of environmental chemistry 10 Chlorinated paraffins Berlin Springer Verlag ISBN 978 3 642 10760 3 Brooke DM Crookes MJ Merckel MD 2009 Environmental risk assessment long chain chlorinated paraffins PDF Bristol UK Environment Agency Kellersohn Thomas 1998 Chlorinated paraffins Ullmann s encyclopedia of industrial chemistry electronic release 6th ed Weinheim Wiley VCH Kenne Kerstin Ahlborg Ulf G 1996 Chlorinated paraffins Environmental Health Criteria 181 Geneva World Health Organization ISBN 9241571810 Lassen Carsten et al 2014 Survey of short chain and medium chain paraffins PDF Copenhagen Danish Ministry of Environment Environmental Protection Agency Archived from the original PDF on 2016 10 16 Tomy Gregg T et al 1997 Quantifying C10 C13 polychloroalkanes in environmental samples by high resolution gas chromatography electron capture negative ion high resolution mass spectrometry Analytical Chemistry 69 2764 2765 doi 10 1021 ac961244y Further reading editBayen Stephane Obbard Jeffrey Philip Thomas Gareth O 2006 Chlorinated paraffins A review of analysis and environmental occurrence Environment International 32 7 915 929 doi 10 1016 j envint 2006 05 009 PMID 16814386 Cherrie J W Semple S 2009 Dermal Exposure to Metalworking Fluids and Medium Chain Chlorinated Paraffin MCCP Annals of Occupational Hygiene 54 2 228 35 doi 10 1093 annhyg mep081 PMID 19959560 European Chemicals Bureau 2000 European Union Risk assessment report Vol 4 Alkanes C10 13 chloro Luxembourg Office for Official Publications of the European Community European Chemicals Bureau 2008 European Union Risk assessment report Vol 81 Alkanes C10 13 chloro update Luxembourg Office for Official Publications of the European Community European Chemicals Bureau 2005 European Union Risk assessment report Vol 58 Alkanes C14 17 chloro MCCP Part I Environment Luxembourg Office for Official Publications of the European Community European Commission 2011 European Union Risk assessment report Alkanes C14 17 chloro Addendum to the final report 2007 of the risk assessment Environment part Luxembourg Office for Official Publications of the European Community European Commission 2011 European Union Risk assessment report Alkanes C14 17 chloro MCCP Part II Human Health Luxembourg Office for Official Publications of the European Community Pellizzato Francesca Ricci Marina Held Andrea Emons Hendrik 2007 Analysis of short chain chlorinated paraffins A discussion paper Journal of Environmental Monitoring 9 9 924 30 doi 10 1039 b710053a PMID 17726552 Tolbert Paige E 1997 Oils and Cancer Cancer Causes amp Control 8 3 386 405 doi 10 1023 A 1018409422050 JSTOR 3552699 PMID 9498901 S2CID 24166011 External links editShort Chain Chlorinated Paraffins Proposal for identification of a substance as a CMR PBT vPvB or a substance of an equivalent level of concern Retrieved from https en wikipedia org w index php title Chlorinated paraffins amp oldid 1178684441, wikipedia, wiki, book, books, library,

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