EuroPUR Awards 2016: Covestro and Milliken

Two companies were honoured in the first EuroPUR/Urethanes Technology International European Flexible Polyurethane Foam Awards in Brussels in early June.

The awards were presented at EuroPUR’s 50^th anniversary dinner at Brussels’ Royal Museum of Fine Art. Awards were presented in two categories: Innovation and the Environment. In both cases the high standard of entries meant that there were runners up too.

Milliken won the Innovation award for its Milliguard AOX-1 antioxidant technology. Milliken said its polymer-bound chemistry allows the polyurethane industry to reduce antioxidant use, improve oxidation protection, and reduce the emissions of finished articles.

Dow Polyurethane’s range of Specflex Activ Additive Polyols won an honourable mention.

Covestro won the sustainability award for its cardyon carbon-dioxide derived polycarbonate polyols and the runner up was Dendro Poland which has been successfully using polyols from polyurethane process scrap in a range of foams.

"The Jury was not only impressed by the product itself, which they all thought was a real innovation that is of benefit to the industry."

Simon Robinson, Editor 

In presenting the Innovation Award Simon Robinson, editor, Urethanes Technology International said that a number of things impressed the judges with Milliken’s entry and the claims made for the product: “The product interacts with other antioxidant classes and improves the overall stabilisation of the polyurethane. It does not create the coloured species that other antioxidant classes have been known to form and also has shown very good performance with foams based on natural oil polyols.  The Jury was not only impressed by the product itself, which they all thought was a real innovation that is of benefit to the industry. They were also particularly impressed with the effort that went into drafting the entry and submitting a wealth of technical evidence to prove that the company deserved to win the award.

Jean-Pierre De Kesel from Recticel, presented the Sustainability Award. He said:

“The development of the product has taken several years and it has been tested with quite a number of foam producers in this room. And it works: several life cycle assessments have shown that the incorporation of CO₂ allows for substantial Greenhouse Gas emission reductions. The major foam producers represented in the jury all agreed that it was the kind of innovation that can help our industry become more sustainable and help to address the challenges we all face in the coming years, namely how to reduce the environmental footprint of our product over its lifecycle.”

How the awards were decided

The winners were decided by a panel of judges: the President of EuroPUR, Bart ten Brink, the Chairs of the association’s working groups, Adri Aerts, Vita; Jean-Pierre De Kesel, Recticel; and Clint Raine, Covestro as well as Urethanes Technology International’s Simon Robinson.

The judges read and scored the entries before reaching consensus on the winners.

The Innovation Award was open to innovations relating to the production or use of PU foam that is commercially available and one the market. The Sustainability Award was open to products or process innovations that have a positive impact on the environmental footprint of flexible polyurethane foam or foam-containing products.

Covestro and CO₂

Thanks to a catalytic process developed by Covestro and its partners, it has become possible to get carbon dioxide to react with other polymer building blocks so that it can be used as a raw material for all kinds of products.

Covestro inaugurated its 5kT/year plant in Dormagen, Germany in June 2016. The successful first-in-market implementation of this process in a dynamic scientific/technical environment illustrates the impressive innovative achievement, in which the integrative development process at the interface of science and industry plays a key role.

The chemical industry is eager to play its part in tackling challenges such as global warming and the depletion of petroleum resources. The technology presented here makes it possible to use CO₂ as a carbon building block for polymers and replace part of the traditional petroleum-based precursors. It also makes a limited direct contribution to climate protection. Above all, it saves fossil hydrocarbons and reduces emission of CO₂, which is generated during the energy-intensive processing of crude oil to create petrochemical raw materials. The new process reduces the amount of these raw materials needed.

This project owes its success to two previously publicly funded projects jointly run by industry and academia.

The first project Dream Reaction funded by the German Federal Ministry of Education and Research (BMBF) made a breakthrough observation on how to chemically incorporate CO₂ in the polymeric chain. The second project Dream Production took this from the lab to industrial scale, was also supported by the BMBF. In parallel with the technology a marketing plan was developed and the first target market is mattresses and upholstered furniture.

A key aspect in this project involved systematically linking technical development with an analysis of the environmental impact of the new technology. Environmental effects are normally only analysed once a product is available on the market, but in this case, comprehensive life cycle assessments were prepared from the outset to identify potential for ecological improvements early on and incorporate these directly into the development of the technology. This is now a blueprint for future projects. Investigating CO₂-based polymer building blocks made it possible to derive a general procedure for the ecological analysis of CO₂ usage. This procedure has been published in leading international chemical and environmental science journals and is attracting global attention.

As a result of these Life Cycle Assessments, the incorporation of CO₂ allows for Greenhouse Gas emission reductions of 11–19% and a reduction in the use of fossil resources by 13–16%.

The CO₂ polyol offers customers in the flexible foam and mattress industries the opportunity to differentiate themselves by positioning themselves as sustainability-focused. At the same time, the pioneering role of such companies as co-innovators in the sustainable use of raw materials also has a significant external impact.

Plans for successful marketing of the invention are in full swing. Following successful industrial testing on large foaming lines in standard industrial quantities it is clear that the product can be readily implemented into existing production lines for polyurethane foams.

The CO₂ technology is a platform on which further research work is being built to extend the range of applications for existing CO₂ polyols, increasing the proportion of alternative carbon building blocks in polyols and further reducing the carbon footprint of polyols. The company is also planning to synthesize other CO₂ polyols for applications outside the flexible foam market so as to make production even more sustainable.

Milliguard improves stability reduces volatiles

Milliguard AOX-1 (AOX-1), a novel antioxidant, is a reactive oligomeric carbon-centred radical scavenger used to protect polymers from thermal degradation. This chemical is a polymer-bound benzofuranone antioxidant that provides unparalleled efficiency in polyurethane systems due to its unique active structure and its reactive nature.

Owing to its polymeric and reactive advantage, AOX-1 has an improved regulatory profile, enhanced efficiency, and reduced emissions over industry standard antioxidant packages while enhancing the quality of protection for the article. The oxidation improvements possible with AOX-1 are especially important in meeting the changing requirements for automotive and sustainability needs within the flexible polyurethane foam industry.

Today antioxidants are added at various points in the polyurethane value chain to protect the articles from thermal degradation associated with normal manufacture and processing.

Traditional PU antioxidants are dominated by three classes of compounds: Substituted diphenyl amines, hindered phenols, and organophosphites. Each of these reduces degradation generated by thermal energy during manufacture and processing of the polyurethane. Free radicals can extract hydrogen from the polymer backbone to form carbon-centered radicals which, in turn, react with oxygen to form peroxy and other oxygen-centered radicals. This continued radical formation can degrade the polymer, cause discoloration and eventually, physical property failure.

Milliguard AOX-1 is a unique variation to a very limited class of antioxidants based on benzofuranone-type chemistry. It is built to be polymer-bound, it has reactive hydroxyl functionality and it gives improved performance.

The reactive, polymeric nature of AOX-1 has shown clear benefits to the market in the way of oxidative efficiency, improved synergistic interactions, and significantly reduced emission profiles making it safer for the environment.

Typical antioxidant systems have a blend of primary antioxidants which react with oxygen-centred radicals. Secondary antioxidants scavenge the hydroperoxides, converting them to harmless water and alcohol molecules and breaking the degradation cycle.

Only a true carbon centred radical scavenger, like AOX-1, addresses the first stage of the oxidation cycle and interrupts the propagation of further detrimental attacks on the polymer backbone by various other radical types.

The correct balance of carbon centred radical scavengers and conventional peroxy- and alkoxy-radical stabilisers provides the ultimate thermal stability for an organic based polymer. This synergy is demonstrated by using differential scanning calorimetry to measure the Oxidation Induction Time (OIT), where the combination of the different types of stabilizers is significantly more effective than the sum of the individual components. In each case, Milliguard AOX-1 combined with phenolic antioxidants enhances the overall stabilization.

Milliguard AOX-1 is covalently bound with a polymer that is terminated with a reactive hydroxyl group. This allows AOX-1 to be chemically bound into the polymer during the reaction of the polyol and isocyanate. Reacting into the polyurethane backbone reduces volatile emissions and highlights the VOC advantage compared to industry available antioxidants in the strict automotive emission standard VDA-278.

Additionally AOX-1 interacts synergistically with other antioxidant classes, improving the overall stabilization of the polyurethane resulting in a lower use level. Also, unlike other antioxidant classes, AOX-1 does not create coloured species while performing the oxidation stabilization process.

Finally, AOX-1 has proven to be extremely effective when used to enhance the performance of more environmentally friendly materials such as natural oil polyols (NOP) and non-halogenated flame retardants.