Interview with Dr Guenter Beyer

Interview realized by ADDCOM:

Q. Dr Beyer, you will be giving a paper on the new European regulations surrounding the use of flame retardants in cables – something that will be relevance to many of the attendees at AddCom. Flame retardants make up a large part of the European additives market. How are these new regulations changing the industry?

The new European regulation for cables but also for other construction products in the European market will surely demand for higher flame retardant compounds. This means that people have to increase the content of fillers like ATH or MDH, but today the fillers level is already around 60-65 %. People will look in the future to new synergistic systems which enables increased flame retardancy by only a small addition of a second flame retardant which can boost the whole FR system.

Q. In what way are these regulations specific to Europe? Given the current financial problems in the Eurozone, do you foresee these regulations being a barrier to trade and industry growth or could they play a role in aiding recovery?

Due to some severe disasters like fires at London Underground and at the airport Düsseldorf there was a general decision to specify for Europe flame retardant non halogen products for public area like tunnels, hospitals, airports etc. Also for other areas like nuclear power stations these products must be used. Now other countries outside Europe – China or South Korea – are regulating industrial sectors like Europe. The very new regulations in Europe will not be a trade barrier; it will allow the end user to choose the proper product for his requirement from all qualified suppliers of the world. Trading of such products will be free and not regulated in principle, but price or quality and reputation will also influence decisions.

Dr Guenter Beyer

Q. What is the greatest challenge in producing environmentally friendly alternatives and how has the industry responded?

The greatest challenge for the cable industry was the development of flame retardant non halogen products. In combination with the filler industry but also with the polymer years ago the application of metal hydroxides like ATH or MDH to the specific requirements was developed by the cable industry in Europe. Due to the very high filler content of ATH or MDH in the formulations the compounds must still show have high elongation and tensile strength combined with easy processing.

Q. A number of end users are registered to attend this conference. How can material suppliers work with brand owners collaboratively to ensure that their material needs are met?

New regulated fire tests in Europe are more and more complicated and expensive. If material suppliers want to check the performances of their products in real end-products they have to initiate good co-operations with their customers like the cable industry. It is more and more complicated or indeed not possible to predict passing of a fire tests by simple parameter like LOI etc.

Q. What have been the most important advances in the flame retardants sector in the last 12 months?

CPR (Construction Product Regulation) and its influence to the FR sector in Europe was the most important one. As indicated already only classical ATH-or MDH systems due to the necessary high filler content up-to-now must be improved and there will be a great demand for filler blends by combination of ATH- or MDH with synergistic systems to allow a good ranking of products to Euroclasses according to CPR.

Q. Where do you see the greatest potential for growth in the flame retardants sector in the next 5 years?

The greatest growth in the flame retardant sector in the next years will surely be the development of moderate filled compounds with high flame retardant properties. People will look to other systems like ATH or MDH…. They will also look to N-or P-based flame retardants but here problems like water-up-take must be solved…. And again: synergistic systems will dominate the market in the next 5 years. We will see an increased demand for zinc borate and silica but also for other material concepts like nanotechnology….

Q. You have been involved with both the IKV compounding conference and the Smithers Rapra plastics additives and compounding event for many years now. What are you most looking forward to about attending the newly combined AddCom conference?

The conference in 2012 is a perfect “synergistic” system, because it brings together the polymer additives and the compounding area in one place. And as we know: only an easy constant processing of a proper designed FR system in a polymer allows a perfect product to your customer…. Attending to the Aachen conference is a perfect way to participate to the future.

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Synthesis of three novel intumescent flame retardants having azomethine linkages and their applications in EVA copolymer

This article was published in Ind. Eng. Chem. Res , 9 Aug. 2012.

Abstract

Three novel intumescent flame retardants (IFRs), polyphosphate esters (designated as PDP, PEP, and PPP), were synthesized by reacting phenyl dichlorophosphate with three bis-hydroxy azomethine monomers through interfacial polycondensation. The polyphosphate esters were characterized by hydrogen nuclear magnetic resonance (1H-NMR), fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Thermal stability and flammability properties of ethylene-vinyl acetate copolymer (EVA)/30%IFRs blends were investigated by thermogravimetric analysis (TGA), limited oxygen index (LOI), and microscale combustion colorimeter (MCC). The EVA/IFRs blends exhibited high thermal stabilities and char yields at 600 °C were 11-19% in nitrogen. The results from MCC indicated that the addition of PPP to EVA reduced the PHRR by about 33%, while the LOI values increased from 19 to 22. Scanning electron microscope (SEM) observation results indicated that the existence of the tight charred layer on the surface of the residues was responsible for the improvement of the flame retardancy of EVA.

 

Textile industry: Novel flame retardant systems point to the future

Cutting the Economic and Human Cost of Fire. By Dr Ian Holme (source: World Textile Information Network (WTiN))

It has been reported that the 7-8 million fires each year in the industrialised nations claim the lives of some 70,000 – 80,000 people, with another 500,000 – 800,000 suffering injury.1 Most people die in fires in homes, buildings and transportation, and the fire victims die as a result of toxic gases (50%), burns (25%), toxic gases and burns (20%), as well as from cases that are unclear (5%).

Fires cost around 1% of the gross national product of the industrialised nations, with around two-thirds of this amount being spent on fire-preventative measures and the remaining one-third on the losses from the fire.

Flame retardants save lives and protect property from damage, but increasingly the flame-retardant manufacturers are under pressure to phase out well-established products and introduce novel flame retardants with enhanced ecotoxicological properties for all types of materials, including textiles.

The incorporation of flame retardants into textile materials is particularly important in upholstered furniture, but the markets for flame retardants are increasing. The main end-use applications for flame retardants currently include:

home textiles: curtains, blinds, upholstery fabrics, carpets and mattress ticking

technical textiles: seat coverings and carpets for cars, rail vehicles and aircraft

functional textiles: industrial protective clothing, eg. firemen, welders, metalworkers and workers in the petroleum industry

military textiles: uniforms, backpacks and tents

In upholstered furniture the use of flame retardants can potentially give rise to different risks, such as:

• exposure to flame retardants during manufacture of the product (worker acute and chronic toxicity)

• exposure to flame retardants under normal living conditions. This risk mainly results from the accumulation of release flame retardants in indoor air via inhalation and/or skin contact and migration of substances (chronic toxicity)

• the environmental risk during recycling or incineration of the products (mainly ecotoxicity)

• the risk of increasing the emissions of toxic gases from accidental fires due to cigarettes or matches on upholstered furniture (acute toxicity)

The flame retardants for textiles operate by a variety of different chemical mechanisms. Thus, inorganic and organic phosphorusbased flame retardants dehydrate the fibres, leading to the production of a black carbonaceous char. Nitrogen-based flame retardants are often used in combination with phosphorusbased flame retardants, which can lead to crosslinking that supports the carbonisation process. Halogen-based flame retardants generally interfere with the free-radical reactions in the gaseous phase, slowing down the reactions that lead to heat generation. Intumescent systems utilise an acid catalyst, a carbon-rich source and a spumific (blowing agent) to form a protective heat-insulative and carbon-rich foam layer, which is expanded by the blowing agent to provide a thick, carbon-rich barrier to heat, oxygen and flame.

Flame-retardant coatings for textile fabrics often rely upon the use of antimony trioxide and a halogen-based flame retardant such as DecaBDE (decabromodiphenyl ether). DecaBDE has been extensively studied over a long number of years and the Risk Assessment Report compiled over a period of 10 years by the European Union concluded that DecaBDE does not pose a risk to the environment or human health. Nevertheless, the US Environmental Protection Agency (EPA) has supported and encouraged the voluntary phase-out of the manufacture and importation of commercial versions of DecaBDE and has received commitments from the principal manufacturers and importers to initiate reductions in the manufacture, import and sales of DecaBDE in the USA. This started in 2010, with all sales to cease by December 31, 2013.

In addition, the UK REACH Competent Authority is considering the listing of DecaBDE as a substance of very high concern (SVHC). This is based upon fears expressed by the UK Health & Safety Executive and Environment Agency that DecaBDE might degrade to lower polybrominated diphenyl ether (PBDE) congeners, meeting the PBT (Persistent, Bioaccumulative and Toxic) criteria.

However the BSEF (Bromine, Science & Environmental Forum) has asserted that degradation was minimal and posed no serious risk to the environment. The industry needed an SVHC classification that was based solely on science and not on emotional arguments or reputation, otherwise this would remove a chemical substance of high value to society without due scientific process.

Against this background of debate, new flame-retardant chemicals are emerging, with product developments focused upon:

• polymeric solutions: large molecules

• reactive products that can become bound to the final polymer

• non-toxic, non bioaccumulative molecules

• mineral products

• life-cycle performance and carbon footprint.

In addition, the flame retardants must also be non-PBT (persistent, bioaccumulative, toxic) and non-CMR (carcinogen, mutagen, reprotoxic), be durable (non-leaching) and insoluble and non-hydrolysable. Preferably, the flame retardant should be used at a decreased total loading and enable a lower antimony trioxide (ATO) loading to be used.

Albemarle has introduced Saytex 8010, which is based upon ethylene 1,2 bis(pentabromophenyl) (EBP).4 Saytex 8010 is claimed to be the most widely applicable alternative to DecaBDE, with enhanced thermal stability, non-blooming properties, UV stability for colour applications and also recyclability. Saytex 8010 is available in powder or pellet form, is EU RoHS-compliant and meets European dioxin ordinances. It has also been shown to be safe for human health and the environment.

Another new product from Albemarle is a polymeric flame retardant, Green Armor. This is claimed to be the first in a family of sustainable solutions, Green Armor being non-bioaccumulative and non-toxic for mammals and the environment.

The Great Lakes Solutions division of Chemtura has introduced Emerald Innovation 1000 as an effective replacement for DecaBDE and decabromodiphenyl ethane. It is designed to be used as a replacement in polyolefin and styrenic-resin systems and can be easily substituted into existing production technologies, such as textile backcoating, with minimal adjustments. It maintains comparable fire-safety performance with similar load levels to other high-efficiency brominated flame retardants.

ICL-IP has introduced TexFRon as a replacement for DecaBDE and hexabromocyclododecane (HBCD). It is applied via backcoating to polyester and polyester/cotton blends. With a solids content up to 65%, it offers 10-15% better efficiency compared with DecaBDE and is durable to washing. TexFRon 9020 is also durable and applicable via backcoating and offers 30-50% better efficiency over DecaBDE. In addition, the ATO loading can be decreased by 50-70%.

TexFRon is based upon pentabromobenzyl acrylate. Thus the bromine is chemically bound into the polymer backbone, offering wash durability to 50 cycles on polyester/cotton. Both TexFRon P and TexFRon P+ are applicable by backcoating, the latter offering improved efficiency over the former. TexFRon P+ offers a reduction of 40% in bromine loading and 70% in ATO loading, giving excellent low-smouldering performance and wash durability to 20 cycles.

Clariant has introduced the newgeneration flame-retardant Pekoflam ECO/ SYN system, hailing it as a fundamental breakthrough in durable flame-retardant finishes. This innovative bicomponent system, based upon Pekoflam ECO and Pekoflam SYN, is designed for application on existing equipment and is free of any SVHC2- restricted chemicals and free of Oeko-Tex restricted materials.

ECO stands for ecological and economic and SYN for synergy. The new bicomponent flame-retardant system from Clariant has a low impact upon fabric strength, no formaldehyde emissions, and offers excellent wash fastness in domestic washing, as well as good performance in industrial applications. Processing can be conducted on common finishing lines with high-temperature curing and a suitable wash range.

Clariant has also introduced a powderbased flame retardant, Pekoflam HFC, designed for application via coating technology. This utilises organic phosphinate compounds as a substitute for halogenbased systems. This non-halogenated coating system decreases smoke emissions to provide high flame-retardant performance on upholstery and carpeting containing synthetic fibres and blends. Compared with other phosphorus-based powder flame retardants, Pekoflam HFC offers better binder compatibility and a lower impact on the rheological behaviour, which can be increased in the presence of phosphorus-based flame retardants.

Huntsman Textile Effects has introduced Pyrovatex EXP, a durable-flame retardant finish for 100% polyester, which can be applied on white and pale-shade fabrics. Applicable via exhaust methods, it is normally applied at pH 4.5-6.0, using Pyrovatex EXP PLUS accelerator and acetic acid at 90°C for 15 minutes, followed by a wash-off treatment. Pad application is normally followed by drying at 100-120°C. While a curing step is not necessary to obtain durability, curing at 150°C is necessary on automotive fabrics in order to pass the fogging requirements. For dark shades a top finish is recommended, to improve the rub fastness and thermomigration performance. Pyrovatex EXP has a little/ negligible influence on light fastness and a negligible influence on handle.

Avocet Dye & Chemical Company (Brighouse, UK) has introduced Cetaflam DB EXL, which is a halogen-free, antimony-free and solvent-free durable flame retardant that is REACH-compliant and suitable for use with fluorescent brightening agents and fluorescent dyestuffs. Compared with a conventional pad application, Avocet claims that Cetaflam DB EXL – which is applied via an exhaust procedure – saves up to 40% on processing time, energy and resources, enabling the production of sustainable textiles. Designed for use on polyester fabrics, Cetaflam DB EXL is suitable for application to automotive, domestic and contract upholstery, masstransit fabrics, workwear and tents. Cetaflam DB EXL does not require curing, so that there is no risk of shade change or loss of colour fastness and this low-environment-impact system generates no toxic effluent.

An overview of flame retardancy of polymeric materials: application, technology, and future directions

This overview was published in Fire and Materials.

Summary:

Flame retardancy of polymeric materials is conducted to provide fire protection to flammable consumer goods, as well as to mitigate fire growth in a wide range of fires. This paper is a general overview of commercial flame retardant technology. It covers the drivers behind why flame retardants are used today, the current technologies in use, how they are applied, and where the field of flame retardant research is headed. The paper is not a full review of the technology, but rather a general overview of this entire field of applied science and is designed to get the reader started on the fundamentals behind this technology. This paper is based upon presentations given by the authors in late 2009 at the Flame Retardants and Fire Fighters meeting held at NIST.

EPA draft report on potential alternatives of Decabromodiphenyl ether

Decabromodiphenyl ether is not much of a household word.  It has been used in some flame retardants but its environmental effects are far from clear.  In its quest to identify possible substitutes for a toxic flame retardant chemical known as decabromodiphenyl ether, the U.S. Environmental Protection Agency (EPA) has released a draft report on potential alternatives. This comprehensive assessment, developed with public participation under EPA’s Design for the Environment (DfE) program, profiles the environmental and human health hazards on 30 alternatives to decaBDE, which will be phased out of production by December 2013.

An important scientific issue is whether decaBDE debrominates in the environment to PBDE congeners with fewer bromine atoms, since such PBDE congeners may be more toxic than decaBDE itself. Debromination may be “biotic” (caused by biological means) or “abiotic” (caused by nonbiological means). In September 2004 an Agency for Toxic Substances and Disease Registry (ATSDR) report asserted that “DecaBDE seems to be largely resistant to environmental degradation.

As of mid-2007 two states had instituted measures to phase out decaBDE. In April 2007 the state of Washington passed a law banning the manufacture, sale, and use of decaBDE in mattresses as of 2008; the ban “could be extended to TVs, computers and upholstered residential furniture in 2011 provided an alternative flame retardant is approved.”  In June 2007 the state of Maine passed a law “ban[ning] the use of deca-BDE in mattresses and furniture on January 1, 2008 and phas[ing] out its use in televisions and other plastic-cased electronics by January 1, 2010.”

On December 17, 2009, as the result of negotiations with EPA, the two U.S. producers of decabromodiphenyl ether (decaBDE), Albemarle Corporation and Chemtura Corporation, and the largest U.S. importer, ICL Industrial Products, Inc., announced commitments to phase out voluntarily decaBDE in the United States

DecaBDE is a common flame retardant used in electronics, vehicles, and building materials. It can cause adverse developmental effects, can persist in the environment and can bioaccumulate in people and animals. This technical assessment can help manufacturers identify alternatives to decaBDE.

“EPA is using all of its tools to reduce the use of hazardous flame retardant chemicals like decaBDE and identify safer, functional substitutes to protect people’s health and the environment,” said Jim Jones, acting assistant administrator for EPA’s Office of Chemical Safety and Pollution Prevention (OCSPP). “Virtually everyone agrees that EPA needs updated authority under the Toxic Substances Control Act (TSCA) to more effectively assess and regulate potentially harmful chemicals like flame retardants. As EPA continues to stress the need for comprehensive legislative reform to TSCA, we are also targeting actions on a broader group of flame retardants to reduce human and environmental risks.”

On June 1, 2012, EPA released a TSCA work plan of 18 chemicals which the agency intends to review and use to develop risk assessments in 2013 and 2014, including three flame retardant chemicals. EPA is currently developing a strategy, scheduled for completion by the end of this year that will address these three and a broader set of flame retardant chemicals.

On April 2, 2012, EPA proposed actions under TSCA that will require manufacturers, importers, and processors of polybrominated diphenyl ether (PBDE) flame retardants to submit information to the agency for review before initiating any new uses of PBDEs after Dec 31, 2013. Those who continue to manufacture, import, or process after December 31, 2013, would be subject to a testing requirement under TSCA. EPA is accepting comments on this proposal until July 31, 2012.

In 2009, EPA developed action plans on PBDEs (including pentaBDE, octaBDE, and decaBDE) and hexabromocyclododecane (HBCD) that summarized available hazard, exposure and use information; outlined potential risks; and identified the specific steps the agency is pursuing under the TSCA. The alternatives analysis for decaBDE was included in the action plan.

The alternatives to decaBDE characterized in the report are already on the market and will be used increasingly as decaBDE is phased out. The alternatives have differing hazard characteristics and are associated with trade-offs. For example, some alternatives that appear to have a relatively positive human health profile may be more persistent in the environment. Some alternatives appear to be less toxic than decaBDE. Preliminary data suggests that these flame retardants may have a lower potential for bioaccumulation in people and the environment. It is important to understand that these health and environmental profiles are largely based on computer-model generated estimates, and that the models are limited in their ability to predict concern. (source: ENN)

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