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March 25, 2015 11:00 PM

Special Report: EU and industry may lock horns over 2017 MbOCA regulation

Jane Denny
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    As European Union (EU) regulators and manufacturers prepare for the 2017 REACH sunset date on the polyurethane curative MbOCA (MOCA), Jane Denny outlines the history of its use globally and considers its replacements.

    EU businesses using MbOCA will be forced to stop production unless they can persuade the European Chemical Agency (ECHA) to allow each individual use.

    An ECHA report admits there are no viable alternatives to MbOCA. Industry acknowledges there are alternative curing products available but products made with them will not have as good properties, industry claims.

    Abid Dost, health safety and environment director of the British Rubber and Polyurethane Products Association (BRPPA), said MbOCA-based polyurethanes elastomers are ideal in numerous applications in engineering due to their outstanding properties such as hardness, resilience, electrical resistance as well resistance to harsh atmospheric conditions and oil and chemical attack.  Examples of their use include escalator rollers in London’s underground system, gravel pipelines in mining and wheels for hospital trolleys.

    It was in 2011 that MbOCA was named in the ECHA Annex XIV document as a material that “may cause cancer.”

    The appearance of MbOCA in the Annex XV document that followed prohibits its use by EU companies beyond November 2017, unless the individual companies using 1 tonne/year or more secure authorisation for its use from REACH by 22 May, 2016.

    An ECHA statement said: “It is recommended that the applicant notifies ECHA approximately 8 months in advance of the date it intends to submit an application for authorisation. At the same time, the applicant may request a pre-submission information session with ECHA to ask case-specific questions regarding regulatory and procedural aspects.

    “This is not a legal requirement but rather a way of ensuring smooth processing of all incoming applications and of providing support to applicants,” it added.

    According to Dost, it will take many years to find adequate replacements for MbOCA in many product lines, particularly those in defence, aircraft and marine applications.  For this reason, he said, BRPPA members are actively working towards submitting an application for the authorisation of MbOCA under REACH and it is hoped that authorisation for use of MbOCA could be secured for up to 12 years.

    MbOCA history and usage

    The material was developed by DuPont and is known as MOCA (or MbOCAor4,4'-Methylenebis(2-chloroaniline)). MbOCA is a tan-coloured chemical compound used as a chain extender and curative for pre-polymers found in the cast polyurethane elastomer industry.

    In the hot cast PU sector, once MbOCA is reacted in the matrix it is no longer available in the final product. Since it is a solid material at room temperature, it is not used for cold cast elastomers.

    In the late 1970s and early 1980s, it was adopted by the flexible foam industry and used to enhance the load bearing properties of automotive seating.

    In 1979, MbOCA contamination was found in high concentrations around the site of the Anderson Development Co – a specialty organic chemical manufacturer in Adrian, Michigan. Lower concentrations were discovered in a two-mile radius of the plant and the area was not considered officially cleaned up until 1993.

    According to ECHA, there are no manufacturing sites in the EU. The organisation found that imports of the agent amounted to somewhere between 1kT and 10kT in 2010. Using information sourced from the IARC, ECHA said that from 1986 to 2002 production volumes were 450 tonnes/year to 4.5kT/year. From 2006, production dropped below that, perhaps to as little as 225 tonnes a year.

    In the UK, for 2006 the estimated import figure was 200 tonnes, the HSE report concluded.

    Safety and workplace exposure

    According to the UK HSE, airborne exposure to MbOCA in the PU industry from 2005 to 2007 was very low and well below the workplace exposure limit of 0.005mg/m3.

    People working with MbOCA absorb the chemical directly through the skin, according to ECHA guidance. However, the HSE also monitored MbOCA levels in the urine of people working with the chemical. This showed that 90% of those exposures were about half the biological monitoring guidance value of 15 µmol set by the HSE in UK and noted in the ECHA’s Annex XV dossier on the chemical.

    However, because MbOCA is used in casting elastomers, skin exposure was more likely to happen during casting and mould trimming and a need for improving guidance on suitable glove materials was identified.

    Work carried out by Chemtura Europe showed that the choice of glove material is important to reduce the risk of dermal exposure.  Tests indicated that nitrile or butyl rubber gloves were more effective in delaying migration of MbOCA through the glove than the more commonly used natural rubber latex gloves found in workplaces.

    US use of MbOCA

    Ray Scott, vp at US-based specialty industrial chemicals company The Hanson Group, told Urethanes Technology International magazine, it was the US flexible foam industry that led to such widespread MbOCA use. Scott was part of a team from UOP that developed an alternative to MbOCA around three decades ago.

    As ecological issues increasingly gained attention worldwide– coupled with the Anderson contamination, some US companies stopped using it and found replacements. From the 220kT or so used yearly back in the 1980s, Scott said users changing to alternatives reduced the MbOCA market’s size by roughly one third.

    However, he also said the flexible foam industry dropped its use of MbOCA almost overnight during the 1980s and adopted alternatives such as HR polyols and Graft polyols. Generally they changed from TDI/PTMG to MDI/Hydroxyl and eliminated the need to use MbOCA.

    According to Scott, MbOCA replacements include Cyanacure (developed by American Cyanamid) and Polacure (developed by Polaroid). Both were bought by Air Products, he said. Polacure is the base of their current product line Polamines.

    Another MbOCA replace is Polycure and is still made and sold by PTM&W in Los Angeles, California. Other MbOCA replacements include PolyLink 4230 (The Hanson Group) and "probably the most effective replacement" is Ethacure 300 by Albemarl, added Scott.

    Today, he said, the use of MbOCA isn’t much lower in the US than it was 40 years ago but it would be cause for concernif US legislators took heed of the EU and decided to initiate a ban on the chemical there too.

    Given that, according to Scott, the chemical is “significantly lower in price today than during the 1980s,” those still using it will probably never stop,” he said.

    US users of the chemical are fully supported by the US Polyurethane Manufacturers Association (PMA), an organisation that Scott said some believe built its reputation on the battle over MbOCA use. From 1973, the PMA campaigned vigorously against the US Occupational Health and Safety Organisation’s bid to classify the agent a carcinogen, and prevailed in many instances.

    The PMA says that “If recommended material handling and use procedures are followed when working with MOCA, along with routine urinalysis being performed to monitor employee exposure, exposure to workers will be at a safe level, assuming that there is any measurable exposure at all.”

    Classification of MbOCA as a carcinogen

    It was in 2012 that the International Agency for Research on Cancer changed MOCA’s classification from probable human carcinogen to known human carcinogen – a decision the PMA’s Mike Kocak branded “arbitrary” in absence of further information since IARC’s prior listing for the chemical.

    The PMA says “mechanistic evidence is not necessarily sufficient to determine carcinogenicity” and said studies of workers with MbOCA urine levels of more than 20 times the suggested safe limit indicate a lack of human carcinogenicity.

    The organisation points to several studies that it says refute the idea that MOCA as a human carcinogen. Among these are a DuPont study, Fayerweather et al study and a further one by Dost, Straughan and Sorahan published in Occupational Medicine in June 2009. 

    Andrew Davies, lead application development field chemist at Dow Hyperlast, thinks the sunset on the use of MbOCA under REACH regulations “provides an opportunity for the industry to change the way it thinks about the material it uses and why.”

    Davies believes it is “likely to be a difficult adaptation process for users to phase out MbOCA” but that the “versatility of urethane chemistry means suitable alternatives are available.”

    He thinks material selection will depend on the application needs in terms of physical performance. “MDI-based technologies whether polyester or polyether have demonstrated that they are equal and if not better than those using TDI/MbOCA, in wear resistance requirements such as pipeline scrapers or mining screens.

    “While MDI/PTMEG systems are significantly better than polyester TDI/amine cured elastomers and have been proven to outperform TDI/PTMEG in hot wet or humid environments.”

    Many responses to the ECHA’s consultation for the identification of MbOCA as a SVHC (substance of very high concern) were supportive of the move however, French company COURBIS – which uses it as a PU hardener – told the regulator that “in some families of polyurethanes, there can be no substitute.”

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