PU magazine international 03/2011

POLY UR ETH AN ES MAGAZINE INTE RNATION A L

03/2011

www.pu-magazine.com

JUNE/JULY

s thane e r u y l SF Po A B , h Smit

. yne T a W : rson In pe am is ble fo nalys a t c Flexi efe ngs d i d l u mo Foam ts ardan t e r e ng Flam cycli e r m le foa b i x e PU fl

Mr Wu says “Yes” Even though I have been travelling to China for several years now, my Chinese language skills are still pretty much limited to saying 你好 (hello), ordering a 冰镇啤酒 (cold beer) and saying 谢谢 (thank you). Therefore, it is essential for me to rely on translators who help me to get around.

But I think I’m not the only one in the Western world who has this handicap.

Last month in China during the Chinaplas exhibition in Guangzhou – which by the way became the second largest plastics tradeshow after “K” and larger than “NPE” – I had an experience that very much reminded me of the movie “Lost in translation” with Bill Murray.

I was sitting with my translator at the booth of a Chinese company and tried to introduce myself, our company, and the various magazines we publish to the general manager of this company. So I said: “Good morning Sir, may I introduce myself? My name is Frank Gupta and I’m the editor-in-chief of the International PU Magazine.” So my translator started…

After 1 minute I started to wonder what she was telling him, after 2 minutes talking I was getting a bit nervous, but after 3 minutes she blessedly finished. Now my indirect dialogue partner started….

When he ended after approximately 5 minutes I was quite anxious to know what it was all about.

So my translator started: “Mr Wu says: Hello and Yes!” Oh… well… Should have guessed… But what again was the part in between Hello and Yes???

We seem to lose more in translation than we imagine.

Perhaps when our German bankers asked the Greek government if they were still in financial difficulties they did not realise that “Nee“ in Greek means “Yes“ and not “No” like in German…

During a recent trip to India, it was obvious that some first time visitors to the country did not understand that a head shaking does not mean “No” but can mean “Yes, I have got your point” or “Yes, but I don’t really have a clue”. It only depends on the intensity of the head shake. So body language also needs translating sometimes.

Body language being an important part of national traits was recently researched by Ikea and they found that even the way we sit reflects our nationality. As a result, the company has started to design furniture for specific national sitting habits!

So… sit back, relax and enjoy this issue of the PU Magazine.

Best regards Frank A. Gupta

PU MAGAZINE – VOL. 8, NO. 3 – jUNE/jULy 2011

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News Page.134

NO. 3 · JuNE/JuLy 2011

CONTENT Editorial............................................................................................ 131 News.

In.person.

Wayne.T..Smith Page.145

Industry.news................................................................................. 134 Technology.and.product.news. ............................................................ 137 People......................................................................................... 139 Reviews. ...................................................................................... 140.

Events......................................................................................... 140

New.trends.and.messages.from.. the.European.flexible.foam.industry................................................... 142 In person

KraussMaffei..

Competence.Forum.2011 Page.148

Wayne.T..Smith,.President,.BASF.Polyurethanes................................. 145 KraussMaffei.Competence.Forum.2011............................................. 148 Chinaplas.2011.with.record.breaking.results...................................... 150 From.the.2nd.international.SKZ.conference.on.flame.retardants........... 152 Polyurethane.glass.encapsulation.technology.. for.panorama.windscreens................................................................. 153

Chinaplas.2011.with.. record.breaking.results Page.150

E. Geiger, J. Ju

New.flame.retardant.for.flame.lamination.applications........................ 154 R. Neff, T. Smiecinski, V. Manea

MDI.slabstock.foam.–.flammability.performance.. with.out.added.flame.retardants.......................................................... 158 New.flame.retardant.. for.flame.lamination.. applications Page.154

First.meeting.of.the.Exhibitors.Council.for.K.2013.............................. 162 Pot.life.and.curing.monitor.for.PU.formulations,.. epoxy.and.polyester.resins................................................................ 163 Gentle.mould.cleaning.with.dry.ice.blasting........................................ 164 W. Michaeli, O. Grönlund, F. Meyer, S. Latz

Analysis.of.defect.formation.in.flexible.foam.mouldings...................... 166 Analysis.of.defect.. formation.in.flexible.. foam.mouldings Page.175 Collapsed areas

Recycling.flexible.foam.PUR.–.part.3.–.chemical.processes................ 176 Suppliers.list..................................................................................... 181 Publication.information.&.contacts..................................................... 186

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PU MAGAZINE – VOL. 8, NO. 3 – jUNE/jULy 2011 Peeling skin

5 cm

B. W. Naber, G. Behrendt

Exhibits:

Plastics and Rubber Materials, Machinery, Products, etc.

Sep. 6th - 9th, 2011

Show Management Contact Add: NO.33, Xihuangchenggen South Street, Xicheng District, Beijing 100032,China Tel: +86 10 66039351 66039043 Fax: +86 10 66067681 E-mail: applas@applas.com

www.applas.com 133

Industry news Huntsman and Yantai Wanhua Polyurethanes sign PO/MTBE license agreement Huntsman has signed a licence agreement with Yantai Wanhua Polyurethanes Co., Ltd. for the production of propylene oxide and methyl tertiary butyl ether.

The financial terms of the arrangement were not disclosed.

Yantai Wanhua plans to leverage the licence to build a worldscale PO/MTBE plant at its facility in Yantai, Shandong province, with construction expected to commence later this year and beneficial production due in late 2013.

Huntsman’s polyurethanes division has worldscale production facilities in the USA, the Netherlands and China, including a 240/750 kt/y PO/MTBE plant in Port Neches, TX, and is a global leader in PO technology.

Commenting on the agreement, Peter R. Huntsman, President and Chief Executive Officer of Huntsman, said “Huntsman is pleased with the negotiations and the relationship that has been

built between our company and Yantai Wanhua – one of China’s finest manufacturing companies.

We anticipate this relationship will extend into other business opportunities that will be beneficial for both companies. We look forward to working with Yantai Wanhua in building this PO/MTBE facility.”

Ding Jiansheng, Chairman of Yantai Wanhua Polyurethanes, commented “This co-operation with Huntsman is a win-win solution for both parties and for the polyurethane industry. Huntsman is one of the leading PO technology holders and definitely the right partner to work with to realise our vision: to be a first-class, green chemical producer. With China’s huge chemical market potential and Wanhua’s local expertise, the PO/MTBE license will foster a true success in our Wanhua Yantai portside integrated chemical complex.”

TDI and MDI investments at BorsodChem In the coming months, two milestones will occur at the Wanhua Group owned BorsodChem in Hungary. At the end of June, the company’s new TDI-2 plant will be commissioned with an initial capacity of 160 kt/a. According to BorsodChem, this will bring its total TDI capacity to 250 kt and will position the company as Europe’s number one TDI manufacturer. However, due to the unfavourable raw material cost evolu-

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tion, it is not expected that the full capacity will be used initially.

Furthermore, BorsodChem is carrying out a revamp of its MDI-2 plant at Kazincbarcika, Hungary, to increase its capacity from the current 150 kt to 240 kt. According to the company, this investment will further improve product quality as well as consistency and stability of supply. BorsodChem says it is the only European manufacturer that will increase its

capacity of MDI this year and together with the 800 kt MDI capacity of its sister company Yantai Wanhua Polyurethanes, the overall Wanhua Group will advance to become the world’s number three MDI manufacturer.

In order to complete the revamp of the Kazincbarcika MDI-2 plant, BorsodChem will need to shut down the plant for a period of seven weeks, starting from 22 July 2011.

BASF to build 300,000 t/y TDI plant in Europe BASF announced it will build the world’s largest single-train TDI plant in Europe. The plant will have a capacity of 300,000 t/y and will be fully integrated with precursor production. The TDI plant will be located at one of the company’s integrated Verbund sites in Antwerp, Belgium or Ludwigshafen,

Germany, and will start production in 2014. Engineering is underway and the final site selection will be announced shortly, says BASF. The company operates TDI plants in Geismar, LA, USA; Schwarzheide, Germany; Yeosu, Korea; online and Caojing, China.

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BMS invests in the USA Bayer MaterialScience announced plans to invest USD 120 million in its Baytown, TX, USA, plant. The planned investment includes environmental upgrades, reliability improvements, and minor debottlenecking of its 300 kt MDI plant as well as

the introduction of improved process technology, environmental upgrades, and energy efficiency and reliability improvements that will increase productivity at the 220 kt TDI unit. The Baytown site is the company’s largest manufacturing facility in the USA.

BMS applies for permit for new TDI plant in Dormagen As announced by Bayer Material Science in March 2010, the company plans to invest EUR 150 million in a new 300 kt/y TDI production plant at Chempark Dormagen, Germany.

Recently, BMS has submitted an application for a permit with the local government in Cologne. The

The

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online

company expects a decision at the end of this year or early next year. The plant is scheduled to go on stream in 2014. The new facility will replace the existing plants in Dormagen and Brunsbüttel, Germany. Dormagen will then be the sole BMS site in Europe for the production of TDI.

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www.pu-magazine.com Just type some keywords in the search box on the top of the website.

PU MAGAZINE – VOL. 8, NO. 3 –JUNE/JULy 2011

Chemtura plans to build multi-purpose manufacturing plant in China Chemtura has announced plans to build a new multi-purpose manufacturing facility in Nantong, China.

The new plant will initially support the growth of the company’s Urethanes and Petroleum Additives businesses, and is expected to provide sufficient additional capacity for other Chemtura businesses.

According to the company, growth in its Urethanes business is driven by increasing global and regional

demand for its Adiprene Du­ racast product line and its lowfree (LF) prepolymer urethanes.

The Petroleum Additives business requires local manufacturing and storage capabilities for synthetic finished fluids (refrigeration lubricants, air compressor lubricants and gear oils), and calcium sulfonate grease. The new plant will serve customers in China and the wider Asia-Pacific region.

Polytec sells interior segment to Toyota Boshoku Polytec has announced the decision to sell its interior segment to Toyota Boshoku. The company said that the key motivation for this decision is the unpromising perspective to reach a global footprint in a market that features high competitive pressure through a selective group of competitors with a global presence.

Closing is expected for end of June 2011.

At the same time, Polytec confirmed its plan to further expand

its core business (i. e. the exterior business, injection moulded products and engine components as well as motor compartment components and assemblies).

Polytec’s interior segment generated revenues of approximately EUR 340 million in 2010 with around 2,000 employees. It comprises eight sites, of which six are located in Germany, one in South Africa and one in Poland.

The Polytec facility in Zaragoza, Spain, will not be sold.

Repi further extends its capacity in the USA The Italian producer of colour pastes Repi S.p.A. is planning to open a new production site in North Carolina at the end of this year. Up to now, the company’s polyurethane pastes have been sold through the American subsidiary Repi LLC, which is located in Charlotte, NC, USA, and

has a small production and a lab.

The new production facility will be built on a 32,000 m2 property and has been planned for an annual capacity of approximately 3,000 t of colour pastes. The investment amounts to about USD 6 million.

Perstorp increases neopentyl glycol capacity Perstorp is investing in extended capacity for the polyalcohol neopentyl glycol by establishing pro-

duction at its manufacturing site in Zibo, China. Planned to start up during the second half of

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2012, the new capacity will be established through the company’s joint venture Shandong Fufeng Perstorp Chemical Co., Ltd. According to Perstorp, the investment is driven by increasing demand for neopentyl

glycol for environmentally friendly powder coatings in Asia, but specifically in China, and will amount to 40,000 t/year. The company is also producing the polyalcohol in its production facility in Perstorp, Sweden.

Berkshire Hathaway acquires Lubrizol On 14 March 2011, Berkshire Hathaway Inc. and Lubrizol have announced a definitive agreement for Berkshire Hathaway to acquire 100 % of outstanding Lubrizol shares for USD 135 per share in an all-cash transaction. The transaction is valued at approximately USD 9.7 billion, including approximately USD 0.7 billion in net debt, making it one of the largest acquisitions in Berkshire Hathaway history.

Berkshire Hathaway and Lubrizol expect the transaction to be completed during the third quarter of 2011. After closing, Lubrizol will operate as a subsidiary of Berkshire Hathaway. Lubrizol will remain located at its Wickliffe, OH, USA, headquarters and will continue to be led by its current management team.

Berkshire Hathaway is controlled

by Warren Buffett, the third wealthiest person in the world as of 2011.

Dorf Ketal starts full production at new organic titanate plant Dorf Ketal recently announced full production at its new organic titanate plant in Mundra, India.

According to the company, the plant will produce up to 10,000 t of titanates annually, making it

the largest facility of its kind in the world. The Mundra plant joins the company’s recently expanded Dadra plant in shipping Tyzor and Vertec organic titanates globally.

Dorf Ketal is a global manufacturer of process chemicals and additives for the oilfield industry, refineries, petrochemical plants, and manufacturers of fuels and plastics. In less than 15 years, the company has emerged as India’s largest manufacturer of these products. Dorf Ketal has grown rapidly through acquisitions, beginning with the Intec and Tyzor titanate brands. In April 2011, the company acquired the patents, trademarks and related intellectual property for Vertec polyester catalysts and Snapcure polyurethane catalysts. The company’s processes are certified to ISO 9001, ISO 14001, and ISO 18001 standards by Det Norske Veritas (DNV).

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Stockmeier Urethanes takes over Greenfield Polymers The Lemgo-based German company Stockmeier Urethanes GmbH & Co. KG has bought Greenfield Polymers Ltd. (GPL), a company located in Sowerby Bridge, West Yorkshire, UK. GPL is active in the fields of electronics grade potting com-

pounds and electrical encapsulants as well as adhesives and sealants for numerous industry sectors. GPL operates in the UK, Wales, Scotland, and Ireland. It also has sales and distribution in Scandinavia, the Middle East, North America and China.

Purplan continues to expand The German plant manufacturer for mixing tanks for the storage and converting of liquids, Purp­ lan GmbH from Hollage/Wallenhorst near Osnabrück, plans to strengthen its position in the Chinese market and intends to open a sales office with a later extension by a plant. With the establishment of a manufacturing plant, the company would be present not only with human resources but also with its own products locally.

In addition to the Shanghai Pur­ plan Mechanical Engineering

Ltd., the company also has commercial agencies in Egypt, Saudi Arabia, and Turkey. Furthermore, a production and distribution facility will be established in North America this year. Also planned is a collaboration with a Russian company in St. Petersburg. In 2012, Purplan will also be present with a sales and maintenance base in India. With more than 120 employees, the company has established itself internationally, but will continue to keep its headquarters in Lower Saxony Wallenhorst.

Purplan was nominated for the “Lower Saxony foreign trade award” as well as the “Grand Award for Medium-Sized Enterprises” (Großer Preis des Mittelstandes) of the Oskar-Patzelt foundation, honouring small and medium-sized businesses in Germany for extraordinary activities in home and foreign countries.

Sonderhoff at Auto Shanghai 2011 Sonderhoff (Suzhou) Sealing Systems Co. Ltd. has exhibited at the 14 th Auto Shanghai show. It was the third time that the system supplier for FIPFG sealing technology attended this important trade show. Auto Shanghai 2011 has attracted more than 2,000 exhibitors from 20 countries and over 700,000 visitors – the largest scale in the history of this event.

Sonderhoff (Suzhou) Sealing Systems was established in 2009.

The company is located in the Singapore Industrial Park (SIP) in Suzhou, the second largest industrial park in China. It provides sales and technical application service, machine maintenance, spare parts supply, contract gasketing and sampling as well as online training programmes.

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PU MAGAZINE – VOL. 8, NO. 3 –JUNE/JULy 2011

Technology and product news New urethane gel coat for the wind energy market PPG Industries will globally market a new urethane gel coat for the wind energy market, developed and manufactured by Plasti­ colors, Inc. of Ashtabula, OH, USA. The gel coat is available in clear for wind blades and pigmented for nacelles. The clear gel coat AGC200 features good adhesion to epoxy, polyester, vinyl ester, and urethane composite substrates, low viscosity for smooth application, and the op-

tion of having open time for lamination up to three days. The clear and transparent liquid remains as such in a cured film. The pigmented gel coat AGC10000 series features similar adhesion properties and open time for lamination along with good outdoor durability and dimensional stability.

Benefits offered by both gel coats include solvent-free composition, flexible urethane film, and the ability to be modified to meet

application requirements. The clear gel coat enables visual inspection of composite laminate for defects and may be recoated using high-solids urethane and epoxy primers and urethane top-

coats. The pigmented gel coat can be applied at lower film thickness than traditional gel coats and provides high gloss and dis- online tinctness of image.

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RadiciGroup develops eco-friendly spandex fibre RadiciSpandex Corp., part of the Italian RadiciGroup, is engaged in the production of Rad­ Elast spandex using a 100 % renewably-sourced biopolymer.

According to the company, the product line will be the world’s first spandex consisting of 80 % biomaterial made from a 100 % renewable source (corn). The new “green” elastane fibre will ensure environmental sustainabil-

ity while providing good performance (greater stretch and highspeed spinning) and quality, says the company. The project aims to respond to the “green” commitment of the main players in the medical/personal care sectors as well as in the textile and quality apparel businesses. The new fibre will be produced in the USA and meets CAFTA, NAFTA and CBI standards.

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Sartomer introduces new oligomer for coatings S a r t o m e r has introduced CN9025, a highly functional aliphatic urethane acrylate developed for UV/EB-cured hardcoats for both rigid and flexible plastics.

Sartomer says that the new product is ideal for plastic window films, automotive headlamps, encasements for consumer electronics, and ophthalmic lenses.

Coatings formulated with the new oligomer are said to demonstrate better abrasion resistance, chemical resistance, and weatherability compared to products formulated with hexafunctional urethane acrylate oligomers.

The product is non-yellowing, chemical resistant, fast curing, and PETA-free.

Acrylic polymers for wood and concrete coatings Interpolymer has launched Syntran acrylic polymers for wood and concrete coatings. The integration of speciality functional groups allows the new polymers to be a solution for many specific applications, according to the company. Formulated as a unique component or in combination with Hauthane PU dispersions, distributed by Interpolymer, the new polymers offer good protection with chemical and abrasion resistance. They also provide good adhesion on

various substrates like wood, concrete or plastic. The waterbased cationic polymer Syntran FX310­1 offers also blocking of stains like wood and cork extractives while providing good adhesion properties on even difficult substrates. The discolouration of coatings is thus effectively and permanently prevented. In addition, its very good sandability makes Syntran FX310-1 a good choice for wood coatings, says the company.

Binder for wood coating systems Alberdingk Boley has brought Alberdingk LignoCure to the coatings market. The product is the company’s latest generation of binder for creating long term stability wood protection systems. LignoCure uses the long term durability of the natural material lignin, a substantial component of wood, to provide a polymeric stabilisation of the substrate. The life cycle of the entire coating system is thereby significantly extended, says the company.

The product offers improved adhesion of the coating to substrate on all types of wood

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through its optimised wetting characteristics. Thus, additional application areas are opened to wood. A major factor is the active conservation of resources realised by extended renovation intervals, says the company. The binder system offers added value as a preservation coating for windows and panelling. Garden furniture and floorboards as well as all wood protection systems where the focus is on maximum service life of the substrate or coating are ideal application areas. Film formation through a low minimum film forming temperature (MFFT) guarantees good

dispersion. The harmonised crosslinking properties of LignoCure also allow for optimum mix-

ability with the corresponding top coat dispersions offered by Alberdingk Boley.

Baytec Spray chosen for “Metropol Parasol“ project in Seville With its polyurethane spray-on elastomer system Baytec Spray, Bayer MaterialScience offers an effective, long-lasting coating solution for various applications. The system is economical in application and adheres well to a variety of substrates, says BMS. Recently, the product was chosen to be part of the “Metropol Parasol” project in Spain, where one of the large squares in the historic district of Seville has been given a complete facelift. The product was used to provide a wooden structure with long-term weather protection.

As part of the project, an area of around 10,000 m2 of the Plaza de la Encarnación has been covered over with a multifunctional sunshade, spanning the square at a height of more than 20 m.

To implement the concept, the most economical solution proved to be a hybrid construction consisting of steel tensioning elements and convex, three-dimensional grid-like structures made

of wood. The wooden structure is made from laminated veneer panels up to 16 m long with a diameter of 7 cm. The total volume of timber is 3,500 m3. Apart from offering protection from the weather, the 3 mm thick polyurethane coating also contributes to the homogeneous appearance for the six parasols. To apply the coating, the liquid raw material components were first mixed in a mobile spraying machine. The coating solidified just a few minutes after application, but remains permanently elastic.

According to the company, Baytec Spray is free of solvents, plasticisers and mineral fillers, and offers lasting and reliable protection for wood, concrete and metal. The flame-retardant system used in Seville is characterised by its good adhesion to the primer on which it is applied and for its long-term crack bridging behaviour. Although the spray-on system is water-impermeable, it has good water vapour permeability, says BMS.

New look for the central square in the historic district of Seville

PU MAGAZINE – VOL. 8, NO. 3 –JUNE/JULy 2011

People Personnel changes at BorsodChem In the course of BorsodChem’s integration into the Chinese Wanhua Industrial Group, Li Junyan has been appointed Chief Financial Officer of BorsodChem Group, with effect from 18 May 2011.

She succeeds Viktor Katona, who is leaving the Hungarian isocyanates manufacturer.

Furthermore, BorsodChem will consolidate its sales and market-

ing divisions of the polyurethanes and PVC/chloralkali businesses.

This integration effort will be led

by Eugene Wu from Wanhua, previously President of Asia Pacific for Greif, Inc. Rik de Vos, former head of the business management polyurethanes and Vladimir Karkoska, the former head of the business unit PVC will pursue other career opportunities.

New Executive Director of AFPF and CertiPUR-US programme Douglas A. Sullivan has been named Executive Director of the CertiPUR-US certification programme of the Alliance for Flexible Polyurethane Foam, Inc. (AFPF). Sullivan succeeds Bob Luedeka, who was appointed to

Douglas A. Sullivan

serve as interim Executive Director until the programme reached a level of success that allowed for the hiring of a permanent director. Luedeka continues to serve as the Executive Director of the Polyurethane Foam Association (PFA), the organisation that initiated the CertiPUR-US programme.

Sullivan’s career in the flexible PU foam industry spans more than three decades. For nearly 20 years he served at Hickory Springs Manufacturing Co. Previously, he worked at Union Carbide’s Urethane Chemicals division and at Dow Chemical. Sullivan currently serves as Chairman of the ASTM International subcommittee on furniture flammability.

2011 Flexible Polyurethane Foam Hall of Fame inductions The Polyurethane Foam Association (PFA) has announced the posthumous induction of two promi-

nent foam industry pioneers and innovators into the Flexible Polyurethane Foam Hall of Fame.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Bob Bush, Sr., one of the Hall of Fame inductees, was a founding father of the PFA. He played a pivotal role in the development of the flexible PU foam and furniture industries throughout his 50year career at Hickory Springs Manufacturing Company. Accepting the Hall of Fame honour for Bob Bush, Sr. were his sons Bob Bush, Jr. and Jimmy Bush.

Both are members of the Hickory Springs management team and are active members of the US flexible PU foam, furniture and bedding industries.

Also inducted was E. Rhodes Carpenter, founder of Carpenter Co., a producer of comfort cushioning products. Ed Ma­ lechek, President of Carpenter, Myron H. (Bud) Reinhart, retired President of Carpenter, and Ann Day, E. Rhodes Carpenter’s step-daughter and President and Chair of the Board of Directors of the E. Rhodes and Leona B. Carpenter Foundation, accepted the Hall of Fame honour on behalf of E. Rhodes Carpenter. online

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PlasticsEurope appoints new President Patrick Thomas, CEO of Bayer MaterialScience, succeeds Jacques van Rijckevorsel as President of PlasticsEurope.

Thomas began his career with British chemicals company Imperial Chemical Industries (ICI). He held various positions in chemical companies, ICI Pharmaceuticals and Agrochemicals and Huntsman, before joining BMS in 2006.

Along with his new assignment as PlasticsEurope’s President, Thomas is Chairman of the Oxford University Business Economics Programme Board (OUBEP), Chairman of the advisory board of the European Institute for Industrial Leadership and Non-Executive Director of the board of online BG Group plc.

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Patrick Thomas

Jon Cheele to head Vita’s Cellular Foams Division The Vita Group announced the appointment of Jon Cheele as Cellular Foams Divisional CEO, following the decision by Peter David to step down from this role. Cheele takes up his new appointment with immediate effect.

Cheele has been with the Vita Group since March 2006 in the role of Regional Director for the Cellular Foams North Region

responsible for Vita’s businesses in the UK, including Ball & Young and Vita Cellular Foams (UK) Ltd., as well as Caligen, Breda and Radium Foam, Maastricht in the Netherlands. He started his career with ICI, subsequently moving to Zeneca Specialty Chemicals. He later moved to Elementis, a UK speciality chemical supplier.

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Reviews

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Events

Handbook of UV Degradation and Stabilization

Polyurethanes 2011 Technical Conference

George Wypych (ed.), ChemTec Publishing, Toronto, 2011, 362 p., hardcover, USD 275.00, ISBN 978-1-895198-46-1

The Polyurethanes 2011 Technical Conference will be held by the Center for the Polyurethanes Industry (CPI) of the American Chemistry Council (ACC) from 26 – 28 September 2011 at the Gaylord Opryland Hotel in Nashville, TN, USA. Featuring more than 60 technical presentations, this year’s event will include sessions on the following topics: appliances and cold chain; automotive; coatings, adhesives, sealants and elastomers; chemistry and fundamentals; construction; elastomers and footwear; environment, health and safety; flame retardants and combustibility; flexible foams; building codes; consumer trends; processing innovations; and renewable content polyols.

The event will also include poster sessions. In addition, CPI will offer its Professional Development Program (PDP) with course topics ranging from introductory polyurethane chemistry and technology to physical testing and raw materials. Furthermore, CPI will present its annual Innovation Award and host tabletop exhibitions where companies can showcase their products.

The Handbook of UV Degrada­ tion and Stabilization has 12 chapters, each discussing different aspects of UV-related phenomena. The introduction explains how plants, animals and humans protect themselves against UV radiation, and which of these concepts can be applied to the protection of man-made materials. The second chapter discusses physical phenomena occurring in materials when they are exposed to UV radiation. Potentially useful UV stabilisation methods are described in chapter 3. The fourth chapter contains information on available UV stabilisers. Stability of UV stabilisers, important for predicting life-

time of their protection, is discussed in chapter 5. Principles of stabiliser selection are given in chapter 6. Chapters 7 and 8 give specific information on degradation and stabilisation of 50 different polymers and rubbers as well as 40 groups of final products manufactured from them, respectively. In addition, more focused information is provided in chapter 9 for sunscreens. Specific effects of UV stabilisers which may affect formulation are described in chapter 10. Analytical methods are discussed in chapter 11. The book is concluded with the effect of UV stabilisers on the health and safety.

Contact: American Chemistry Council Tel. +1 202 2496121 E-mail online@americanchemistry.com Internet www.americanchemistry.com/polyurethane

Polymer Physics

ASC 2011 Fall Convention & Expo

Leszek A. Utracki, Alexander M. Jamieson (eds.), John Wiley & Sons, Inc., Hoboken, 2010, 780 p., hardcover, EUR 140.40, ISBN 978-0-470-19342-6

The Adhesive and Sealant Council, Inc. (ASC) invites to the ASC 2011 Fall Convention & Expo, which is set to take place from 16 – 18 October 2011 in Indianapolis, IN, USA. The event will feature a conference programme, networking events as well as an exposition of raw materials, equipment and service providers. In addition, the co-located two-day Pressure Sensitive Adhesives (PSA) Short Course will be offered from 16 – 17 October 2011 focusing on PSA markets, raw materials, characterisation, production, and end user opportunities and issues.

Providing a comprehensive review of the state-of-the-art advanced research in the field, Polymer Physics: From suspensions to nanocomposites and beyond explores the interrelationships among polymer structure, morphology, and physical and mechanical behaviour. The book is divided into four parts: Rheology, Thermodynamics, Positron Annihilation Lifetime Spectroscopy (PALS), and Physics of the Polymeric Nanocomposites. Chapters

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from renowned experts in the field emphasise the most important trends in polymer physics, from nanorheology and molecular modelling to PALS applications and physical ageing. Key topics include: the viscosity of suspensions and solutions; kinetics of polymer ageing; molecular dynamics; free volume; solid-state physics, thermodynamics, and dynamics; multi-component polymeric systems; and rheology of polymers with nanofillers.

Contact: The Adhesive and Sealant Council, Inc. · Malinda Armstrong Tel. +1 301 986-9700 ext. 106 · Fax +1 301 986-9795 E-mail malinda.armstrong@ascouncil.org · Internet www.ascouncil.org

www.pu-magazine.com PU MAGAZINE – VOL. 8, NO. 3 –JUNE/JULy 2011

Abrafati 2011 From 21 – 23 November 2011, the city of São Paulo, Brazil, will host Abrafati 2011, the main Latin American scientific and business event in the coatings industry, combining the 12th International Coatings Congress and the 12th International Exhibition of Coating Industry Suppliers. According to the organiser, the Brazilian Coatings Manu­ facturers Association, the exhibition comprises 165 exhibitors (as of May 2011) on a total area of 24,500 m2. Approximately 20,000 visitors are expected. The congress will feature 72 technical lectures, four plenary sessions as well as a poster session.

17 – 19 April 2012 at the Maastricht Exhibition and Congress Centre (MECC) in Maastricht, the Netherlands. At the triennial event more than 150 companies are expected to exhibit their products and services to over 3,000 visitors from Europe and other world regions, according to the organiser Crain Communications Ltd. In addition, the three-day event will feature a conference programme with lectures from all key sectors including amongst others: automotive, building and construction, furniture and bedding, refrigerated appliances, raw materials, and CASE. Contact: Crain Communications Ltd. · Sarah-Jayne Gardner

Contact:

Tel. +44 20 82539623

Abrafati – Brazilian Coatings Manufacturers Association

E-mail sjgardnerutech@crain.com · Internet www.utecheurope.eu

Tel. +55 11 3054-1480/-1487 E-mail abrafati@abrafati.com.br · Internet www.abrafati2011.com.br A comprehensive overview on these and other upcoming events can be

UTECH Europe 2012

found on the internet at www.pu-magazine.com under the heading of events. The listing provides links to the event websites for detailed

The 10th international exhibition and conference for the global polyurethanes industry, UTECH Europe, will take place from

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PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

24/05/2011 15:50

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New trends and messages from the European flexible foam industry Interzum, Cologne, 25 – 28 May 2011, Europur & Euro-Moulders GA, Paris, 9 – 10 June 2011

Europur opening in Paris

The Interzum exhibition attracted nearly 53,000 visitors from 147 countries, with 24 % more visitors from outside Germany than in 2009. The polyurethane industry was represented by equipment manufacturers, flexible foamers, adhesive manufacturers and even a polyol manufacturer. A major feature was the trend towards product differentiation through a huge range of materials.

Mixed messaging Suppliers at this year’s Interzum were offering a huge variety of components including scented, anti-bacterial, and anti-mosquito textiles, in addition to eco-friendly textiles made from soy, bamboo, milk and organic cotton. Mattresses on show included full foam compositions of slabstock and moulded flexible foams. Many foams incorporated natural polyols based on palm, soy bean and castor oils. Mattresses also included TPE cubes, hydro gels and natural fibres such as coir, bamboo and soy.

Kaymed, Ireland’s only remaining foamer, exhibited its latest products based upon a

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combination of TPE gels, viscoelastic and conventional PU foams in pressure relieving mattresses.

Courtesy of Kaymed

Some exhibitors expressed concern that the variety of materials was confusing for the consumer, and may dilute the main message that the main benefit of a comfortable mattress is to provide a good night’s sleep. A simple message used successfully by companies such as TempurPedic. Another concern expressed by Europur board members was that the growing variety of mattress and furniture construction eliminates opportunities for recycling. “Complex design really only allows for a used mattress to be burned. Since there is no demand for recycled materials, Europur members are of the

opinion that incineration remains the best disposal option”, stated Ward Dupont, Chairman, Europur, during the recent general assembly.

Demand for “bio-foam” slow to develop Although many flexible foamers exhibiting at Interzum offered a foam with some bio-content, few reported significant demand. In the USA, demand for “bio-foam” is much stronger. There appears to be three problems with the acceptance of these types of foam in Europe, whereas only two of these problems affect “green” uptake in the USA and elsewhere, according to Jeff Rowlands, Green Urethanes. Firstly, in Europe there is a stronger environmental lobby driving the “crop oil versus crude oil replacement” debate, this issue is rarely discussed at all outside Europe. Foamers at Interzum dismissed this debate saying that they could sell these foams into niche markets where they commanded a premium price, which reflected the higher raw material costs. “The Europeans agree with the Americans that “money” is “green”, too. Green alternatives would really fly, if they were available at least at the same cost as present technology”, Rowlands continued.

The other two problems preventing green technologies penetrating the PU market are therefore cost and development. Low consumer demand creates a vicious circle, with European companies unwilling to invest in this technology. Green Urethanes, a UK technology company, offers solutions to solve the first problem of making available a very simple, room temperature, cheap method of reorganising the structure of natural oil polyols so that flexible slabstock foams with 50 and 75 % of NOP can be made. This technology does not degrade the physical foam properties but creates a better SAG factor and FR characteristics than conventional foams. However, the main obstacle to large scale use of green alternatives in the PU industry remains the problem of price fluctuations due to commodity market manipulations.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Unlike in the USA, European mattress makers do not see any value in offering foams with renewable content and automotive OEMs are not asking for these types of foams in their vehicles either – despite Ford Motor Co. currently using soy-based foams for seating in 23 models produced in the USA. In contrast, European seat makers are specifying lighter weight materials, approaching “greenness” from the perspective of greater fuel economy. Data collected by the VWI in Germany suggests that mattresses manufactured here contain less than 4 % natural materials, most of which is natural fibre. Despite the lack of demand for foams using natural oil polyols, amongst European foamers, at least one Malaysian foamer and mattress manufacturer, exhibiting at Interzum, reported shipping 20 – 30 containers per month of viscoelastic mattresses into Europe.

Body language research also affects design How you sit can say a lot about you, according to research commissioned by Ikea – even your nationality. Using observations, researchers at Ikea have helped to design a new sofa and armchair based specifically on British sitting habits. Until now, Ikea’s furniture has been designed for Scandinavian consumers. Research suggests that Swedish people sit on their furniture, while the British sit in their furniture. According to An­ ders Jarlsson, Deputy Test Lab Manager “In Sweden we think we sit normally, in Germany people sit “hard” and in England people sit “soft”, in America people are so relaxed that they are virtually lying down and therefore don’t require as much structure in their furniture.” So Ikea has launched the 

Tidafors range which has a high back, deep seat, cosy corners and memory foam seat cushions.

Courtesy of Ikea

Good news from the USA!

Europur aims to restore confidence Approximately 150 delegates attended this year’s Europur General Assembly in Paris.

This was 40 or so fewer than usual, as some foamers stayed away due to concerns over such meetings in relation to the current EU and FBI market fixing investigation. “We are optimistic that we can restore confidence amongst our members in the benefits of our meetings. Trade associations play an essential role in helping industries to face technical, economic and legislative challenges”, stated Ward Dupont during the opening session.

Presentations during the two-day event included one from Michel Loubry, Plastics­ Europe, illustrating that using plastics was “eco-friendly” when considering their ability to reduce weight and fuel consumption, be recycled, and achieve major benefits to our lifestyle, while using only 4 % of the world’s oil consumption. A report from AIPEF, the Italian flexible foam association, presented the results of their three year programme

Tab. 1: Production of polyether slabstock foam 2005 – 2010 (kt)

Region

2005

2006

2007

2008

2009

2010

EU15 + N + CH

468.0

476.1

505.5

479.4

469.7

485.7

5.8

1.7

6.2

–5.2

–2.0

4.7

132.4

141.7

164.7

146.5

165.6

142.1

9.9

6.7

7

16.2

–11.1

13

600.4

617.8

670.2

625.9

635.3

627.8

5.9

3

8.5

–6.6

1.5

–0.2

% Change East EU + TR + UKR + RUS % Change Total % Change Source: Europur

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

to promote PU foam with designers and consumers. Ronald van den Bosch, Dow Chemicals, presented an overview of the International Isocyanate Institute as well as Isopa’s Walk the Talk 2. This new edition is part of the continuous improvement in safe handling of diisocyanates, while discussing how to incorporate REACH compliance in new MSDS sheets. An interesting analysis of the Fiat­Chrysler alliance was also presented by Luciano Ciferri of Automotive News.

The production of flexible slabstock has increased for the last 15 months according to Bob Luedeka of the PFA and Chinese furniture imports have started to decline.

Luedeka suggested that this was the result of increasing labor costs and shortages in China and an equalisation in raw material costs. In order to control inventory levels, US retailers are also reported to be unwilling to order in large volumes required by Chinese manufacturers. Total production of flexible slabstock in 2010 reached about the same level as in 2008, approximately 430,000 t.

Luedeka reported that proposed changes to legislation regarding flame retardancy did not pass its first reading in the US Senate, being a two year bill it will be represented in 2012. This bill provided the furniture and bedding industry with an option to create innovative solutions to meeting FR regulations and is being supported by the PFA since it could promote innovation in foam technology. “There is growing concern over the use of halogenated chemicals in household goods, this bill could allow manfacturers to look for alternatives”, Luedeka commented.

Although TB 117 applies only to furniture and bedding sold in California, new initiatives for FR are being introduced in Texas, New York and New Jersey. Another opportunity for the foam industry is the introduction of new FTC Green Guidelines, which will introduce stringent rules for product labelling of furniture and bedding including foams, sold in the USA.

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CertiPUR and CertiPUR-US In the USA, 15 foamers now supply 44 types of certified foam, 10 of these foamers are US companies the remainder are from overseas. The programme is also self funding and well supported: 10 leading US mattress manufacturers have been the main supporters of this programme. In Europe, 40 products are certified from foamers in 11 countries, with a further nine labels pending. Axel Kamprath, General Secretary of Europur, reported that cooperation with Oeko Tex is progressing, with general agreement on test procedures. However, more marketing communication is still needed to promote the benefits of CertiPUR within Europe.

Euro-Moulders open Pandora’s box Initial approaches to the OEMs to discuss possible harmonisation of tests required for automotive seating appeared to be unsuccessful. However, after conducting a survey on the tests for humid ageing of moulded foams used by various OEMs, Euro­Mould­ ers technical committee presented their results and demonstrated that harmonisation was possible and beneficial to the automotive industry. Antoine Fluhr, Chairman, Euro-Moulders Technical Committee, was delighted to report the overwhelmingly positive reception of their work and that the OEMs, representing some 40 % of the European automotive industry, will support further work. The Euro-Moulders presentation also created a unique opportunity for industry specialists to meet and discuss test harmonisation.

material prices for polyether slabstock fell by 29.3 % in 2009 but increased by 22.6 % during 2010. Therefore, costs are more or less back to those of 2008. Production of polyether slabstock by Europur members in 2010 was 0.2 % lower than in the previous year (tab. 1 and tab. 2). It should be noted that Europur members do not represent the entire industry, hence lower than expected figures for some markets. In contrast, data from CSIL suggested that production of upholstered furniture in Eastern Europe, including Turkey grew by 32 % during 2010. Poland is now the leading manufacturer, beating Italy into second place (tab. 3). Poland also became the leading exporter of furniture with sales of EUR 1,548 million compared to Italy’s exports of EUR 1,394 million.

Industry estimates the total production of flexible foam in Eastern and Western Europe, including Turkey was approximately 1.2 million t in 2010, suggesting that Europur mem-

bers represent a little over 50 % of total production.

In terms of mattresses data from the Euro­ pean Bedding Industries Association, which collects data from seven leading Western European countries, suggested that full foam PU mattresses had gained market share, mainly at the expense of latex. Full year data is not yet available, however H1 comparisons for 2009 and 2010 were presented (tab. 4).

Ward Dupont concluded the meeting by asking members to consider whether a price index similar to one successfully operated by Euro-Moulders, would be useful for slabstock producers. The next General Assembly will be held in Budapest, Hungary, 7 – 8 June 2012.

The next Technical Conference will be held in Rome, Italy, 13 – 14 October 2011.  Tab. 3: Leading upholstered furniture manufacturers,  2010 Country

Tab. 2: Production of polyether slabstock foam by  country 2008 – 2010 (kt) Country

EUR million

Poland

2,295

Italy

2,219

2008

2009

2010

Germany

1,986

Poland

70.5

71.7

68.8

UK

1,505

Italy

82.5

70.9

71.7

France

711

Germany

78.3

75.2

80.6

Turkey

532

UK

53.9

57.4

59.5

Russia

373

France

52.1

44.5

47.0

Romania

315

Belgium

43.3

39.4

41.5

Czech Republic

250

Spain

38.7

40.0

38.4

Hungary

208

Netherlands

33.9

35.0

33.2

Ukraine

107

Rest of Europur/Europe

172.7

201.2

187.1

Croatia

Total

625.9

635.3

627.8

Total

89 10,590

Source: CSIL

Source: Europur

Mattress type Units

H1 2009 Share (%)

Units

H1 2010 Share (%)

Polyurethane

3,014,000

52.6

3,283,000

55.8

European statistical report

Inner spring

2,062,000

35.9

2,015,000

34.2

Latex

517,000

9.0

440,000

7.4

According to Europur, raw material prices increased during 2010, recovering much of the decreases experienced in 2009. Raw

Others

45,000

2.5

149,000

2.6

5,638,000

100.0

5,887,000

100.0

Tab. 4:  Total European mattress sales, Source: EBIA H1 2009, H1 2010

www.pu-magazine.com 144

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Interview with W. T. Smith

In person:

Wayne T. Smith, President, BASF Polyurethanes The first half of 2011 shows an impressive start for you as new President of BASF Polyurethanes. You just recently announced MDI groundbreaking in Chongqing, followed by a new world-scale TDI plant in Europe. We wonder what will come next…

Wayne T. Smith:

Wayne T. Smith:

PU Magazine: Could you give some more details on your new TDI project?

Wayne T. Smith: We will build a fully integrated 300,000 t production plant for TDI and additional plants for the precursors in Europe. The complex will be located at one of our integrated Verbund sites in Antwerp, Belgium or Ludwigshafen, Germany. We’re proud to state that this will be the world’s largest single-train TDI unit, and it will be starting up in 2014. This new investment project supports BASF’s growth

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

PU Magazine: Overall this TDI investment is a good signal for Europe – after you just recently announced MDI for Asia.

PU Magazine:

Indeed, we have accelerated the implementation of our strategies significantly and have had a great start into 2011 – after the crisis necessities slowed us down considerably.

But we used that crisis period to do our homework, like the whole BASF Group did, and are now even stronger. Our sales volumes improved in all business areas so we noted substantial demand growth overall. We are well on track and many new investments are underway or in the advanced planning phase. BASF Polyurethanes is in excellent shape and continues to be on a solid long term profitable growth path. Our new worldscale investments in MDI, TDI and HPPO bolster our leading position in the PU industry and bring us close to our customers in their specific markets. We are further looking for more growth opportunities, both organically and inorganically, to strengthen this leadership in all our business segments.

investments, various factors are taken into account. Fact is that at a BASF Verbund site you have full backwards integration, best resources and energy usage, and at the same time, reduced emissions and logistics costs.

”

We will build a fully integrated 300,000 t production plant for TDI and additional plants for the precursors in Europe.

”

strategy, underlines our leading position as largest TDI producer and reinforces our strong global commitment to the TDI market.

We will be able to serve our customers’ demand through local world-scale production in the most important markets North America, Europe and Asia-Pacific, especially China – supported by our superior technology and unique Verbund concept, which provide us with excellent cost structures. With this highly efficient plant, we complement our strong global network of integrated worldscale TDI facilities.

PU Magazine: When will the decision on the site be made and on what factors will the site decision be based?

Wayne T. Smith: The most important decision has been made: We will build this plant. With our large Verbund sites we have great alternatives, so we have to look into the details for final decision, which we will announce shortly. As with all

Well, BASF wants to increase profitable sales in the region significantly in the coming decade. Our TDI project definitely supports this target. Of course Asia, and especially China, are extremely important for our future business success. But we don’t forget our home market Europe, where PU remains important, too. That’s why we are not only investing in TDI in Europe, but in all technologies and regions we continuously strive to improve our asset efficiency and make smart investments to creep our capacities, maximize our asset utilization and to achieve greater supply security for our customers.

PU Magazine: On the background of this large investment – how do you see the polyurethanes market?

Wayne T. Smith: Times will get tougher for those who have not done their homework. While feedstock prices are rising and are likely to remain on a higher level it’s critical to have an excellent operating cost position. This is key, because only with this can you grow profitably and maintain the necessary investments in R&D, in assets, and in people. It’s clear that only fully committed global players will be able to sustain in this competitive environment over the long term. Key for success is overall leading cost structures, broad market access also through Systems and Specialties and innovation capabilitites across numerous customer industries. The PU market overall continues to be growing stronger than other materials. This is driven by megatrends like urbanization, mobility or increasing standards of living. PU contributes to better insulation of buildings, to make cars lighter and more fuel efficient and to make overall life

145

more comfortable. When a society has reached a certain level of wealth, PU always plays an important role. If you just look at the insulation market: On average, every American uses 1 kg of PU every year for insulation in buildings. If every Asian resident would use a similar insulation level, the market in Asia would be more than 3,000 kt or nearly four times bigger than today. So we see a huge future potential of PU insulation all over the world, but especially in Asia. The same concepts can be applied to other segments – if the kg of PU inside an automobile of the US or Western Europe were to be extended to vehicles all around the world… you can imagine the impact on our industry.

PU Magazine: Your MDI plant approval for Chongqing seems to be a good timing.

Wayne T. Smith: We just had groundbreaking for MDI in Chongqing. Indeed, it is a large and important project for BASF and for Western China. With this pioneering investment we are supporting the Chinese government and their plans for rapid and sustainable development in Western China. Chongqing is at the center of a growing inland region, so we clearly see the demand. For this reason we are also investing in a new System House to develop new

”

Polyurethane is a versatile material and as the industry leader, BASF is committed to developing the market aggressively via our Systems business globally.

”

application with our customers in this region.

Investing in Chongqing will give us access to what will be one of the biggest MDI markets in the world. We are applying world-class safety and environmental standards in the construction and operation of our facility, and at the same time we will produce products that have a direct impact on increasing energy efficiency and lowering carbon emissions.

PU Magazine: Any new developments on your announcement to build HPPO in China?

Wayne T. Smith: BASF and Sinopec have signed a Memorandum of Understanding to jointly explore the further expansion of their integrated petrochemical joint venture. This includes a new world-scale hydrogen peroxide-propylene oxide (HPPO) facility. The final scope of the investments under consideration will be determined following joint feasibility studies for each of the projects. Those are currently underway. We are proud that HPPO, a BASFDow innovation, received in 2010 the Presidential Green Chemistry Challenge Award in the USA. For good reasons, I believe: Our technology offers distinct economic and environmental benefits when compared to conventional propylene oxide process technologies. A study using BASF’s Eco-Efficiency Analysis tool revealed the HPPO process reduces wastewater by 70 – 80 % and energy use by approximately 35 %, compared with existing PO technology. The industry leading HPPO technology is also more environmentally friendly, because no by-products are produced besides water.

PU Magazine: With your world-scale projects – MDI, TDI and HPPO – you have three extra-large pieces on your plate…

Wayne T. Smith: And there’s even more to come this year. For us, 2011 is over on 31 December, not a single day earlier. Basic products is one thing, but we should not forget our highly attractive Systems and Specialties business. We regard this a rich source of innovations which helps to drive the PU industry growth together with

146

our customers. Our TPU and Cellasto businesses continue to be a core part of our portfolio and have performed very well. We will continue to invest in these businesses to grow our industry leading position. In 2010 we expanded our TPU capacity in North America. In July of this year our new world scale Cellasto plant in Shanghai will start production, and we are already looking at further expansions in China, India and South America to further develop PU as the preferred material of choice in these markets.

The same positive trend is true for our whole Polyurethane Solutions Systems business.

We are constantly expanding our global network of System Houses. This will strengthen our position as market leader for PU Systems and Specialties even more. The Systems business is critical to support our development activities to expand PU into new segments and applications. Polyurethane is a versatile material and as the industry leader, BASF is committed to developing the market aggressively via our Systems business globally.

We have opened just recently new System Houses in Poland and in Dubai and are in the construction phase of our Tianjin System House in Northern China. And as I already mentioned, in addition to the production complex for MDI, BASF is also establishing a new System House in Chongqing to meet the demand of the growing markets in important industries like construction, appliances, transportation, and footwear.

We always have new System House projects in our pipeline, striving for organic or inorganic growth, be it to invest in new technologies or to broaden our geographical scope.

With every investment we are getting stronger as a globally connected PU player and we are better able to serve our customers, our most important business objective. We help them to find the most intelligent and costeffective solution. Together with them we grow the market.

PU Magazine: Let’s talk about industries and markets – any special focal points?

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Wayne T. Smith: Overall we are aiming for profitable growth in our markets in Europe, North America, Asia and especially China. No society nowadays can afford to ignore the importance of energy saving. So we see global growth in the construction segment due to the rising demand for highly efficient insulation material like MDI-based polyurethane foams.

In the field of transportation and automotive we will be growing globally – with a special focus on Asia, where we have a clear upwards trend in car production. This is not only driven by mere quantities, but also by quality. PU comes into play when higher requirements need to be fulfilled, better quality is needed and when cars become lifestyle related items. Regarding trends, I would like to highlight the topic of lightweight parts for both body components and load bearing parts, where PU is playing an important role.

In Asia we certainly will be growing in the footwear business, here again PU turns out to be the superior material for many applications – in shoes for sports and leasure as well as boots for heavy-duty use. BASF proved that is is possible to build an entire sports or leisure shoe utilizing PU. Furniture remains an important industry for us. We see high demand in China and the developing countries, where societies reach higher comfort levels – as this industry is basically comfort driven.

And of course, BASF will pay attention to special applications where we expect to deliver high value to our customers. PU has excellent product properties to go into a large variety of products – and BASF has the R&D expertise and know-how to make this happen.

PU Magazine: You mention R&D – could you elaborate more on this?

Wayne T. Smith: You know that innovation is key for the polyurethanes Systems and Specialties business. And for PU the sky’s the limit. It’s in so many applications throughout all indus-

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

tries – but there is still huge potential to substitute other materials. Let’s take the example of our Elastoskin sprayskin for automotive interiors: For the new Ford Taurus we took up the challenge to develop a door panel with the look and feel of genuine, hand-stitched leather. The decision to use the Elastoskin spray polyurethane from BASF for this was merely a logical step. The other synthetic alternatives simply weren’t good enough. In short, Elastoskin was priced right and fully able to deliver the look, texture and character of handcrafted leather. Here we clearly have shown our formulation and our processing expertise, combined with our strong ability to do pioneering R&D work together with our customers. You see, the material properties in many respects are much better – so let’s go for this potential! Another example is our sprayfoam premium brand Walltite, which started as an innovative approach to the market in Canada and the USA. We launched the product with the purple color in the UK last year and will be introducing Walltite in other selected European and Asian countries.

rising to nearly EUR 1.5 billion. The company attaches great importance to continuity in R&D and has further increased its commitment even in tough times. BASF will therefore also be increasing its R&D spending in 2011. More than 9,600 R&D employees are working in international and interdisciplinary teams on about 3,000 projects aimed at finding answers to the challenges of the future – to a large extent also for innovations in PU. BASF’s polyurethanes division and its customers in all regions of the world benefit from BASF’s international and interdisciplinary know-how Verbund. At the moment, BASF is working on an extension of this Verbund. We broke ground last December for the construction of a new R&D Center at the Pudong site in Shanghai, China, as part of the new Innovation Campus Asia Pacific. The Innovation Campus will house a total of 450 employees from mid of 2012 onward and we will have dedicated PU labs.

With our 38 System Houses in all regions we are close to our customers – and they benefit from the global R&D network of BASF. Of course we are further investing in R&D: In 2010, BASF’s research and development expenditure reached a new record level,

Wayne T. Smith:

” You know that innovation is key for the polyurethanes Systems and Specialties business. And for PU the sky’s the limit.

”

PU Magazine: Let’s stick with the innovation topic: What is for you the most impressive PU innovation of the past 12 months?

Since I joined BASF’s PU business I learned a lot about great innovations and product applications. Personally, I think our product Elastopave is a great innovation. You take small stones, combine them with PU and apply this to the ground. What do you get?

A strong, smooth and durable surface, that can be used for parking lots, driveways, sidewalks or patios. It’s easy to work with and install using conventional construction equipment. The high proportion of large and small stone pieces creates many connected cavities which prevents the ground below from being sealed. Since it can breathe through this porous cover, the ground can take in around 4,000 l of water per hour and square meter, preventing the formation of puddles and patches of ice. In times of increasing urbanization, I think this is an amazing product, with benefits for society and for nature – thanks to the enormous versatility of polyurethanes.



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KraussMaffei Competence Forum 2011 In-house exhibition at the Munich-based machinery manufacturer On 19 May 2011, KraussMaffei welcomed more than 1,500 visitors from 25 countries to its in-house exhibition, the KraussMaffei Competence Forum. Under the motto “Technology3 – Machinery, Processes, Service” and with over 30 machine exhibits, the German machinery manufacturer from Munich presented its product portfolio from its technology divisions – Injection Molding Machinery, Reaction Process Machinery, and Extrusion Technology. At the same time, the opening of its new TechCenter for lightweight parts and fibre-composites technology was celebrated. In addition, the company presented a new concept for producing prefabricated houses on a double-belt press, aimed at producing affordable housing in developing countries. 30 partner exhibitors and two series of 15 short presentations by KraussMaffei experts, covering details of the machines on show, including multiprocess solutions such as ColorForm and SkinForm, and technologies for processing lightweight composites, rounded off the day’s programme.

Prefabricated houses for developing countries At the Competence Forum, the company unveiled an innovative concept for the production of affordable prefabricated houses. The houses can be produced in high volumes on a KraussMaffei double-belt press and assembled in a few days. According to the company, this concept represents an efficient, cost-effective and sustainable way to create affordable housing in emerging and thirdworld countries as they become increasingly urbanised.

The concept is unique for the staged manner in which the houses are made. Using a simple base module, manufacturers can produce about 1 – 2 houses per day, or about 500 per year. To meet higher demand, they can scale up to a continuous production line capable of producing anywhere from 2,000 – 10,000 units per year, says KraussMaffei.

Each prefabricated house has a floor-space of 30 m2 and provides space for a family of five. The wall and ceiling panels are well insulated and the house can be fitted out with solar panels to render it self-sufficient in energy.

148

The prefabricated houses consist of only a few different modular panels of the kind found in industry, warehouses and cold stores. Made to flexible grid dimensions, the wall and ceiling panels comprise an insulating core of polyurethane foam sandwiched between steel facings. The manufacturer can also freely vary the materials to suit local availability. Local requirements and countryspecific vagaries regarding production and style can thus be respected. For example, the top layer can be of aluminium and the insulating core of mineral wool, depending on whatever material is easier and cheaper to source locally. Equally, other materials such as OSB wood panels, MAG boards, extruded decorative panels or glass fibre-reinforced boards can be used. Prefabrication by the manufacturer eliminates the cutting to

size that is usually done on site. The manufacturer delivers a complete house on one pallet, ready to be assembled on site. The only tools needed for assembly are screwdrivers and wrenches, says KraussMaffei.

The system has been designed with flexibility in mind and can be installed on the building site itself. When demand in one region has been met, the “mobile factory” can be simply moved to another. The system can also be installed on ships used by aid agencies, ready to be called upon as a “floating factory” to regional disasters.

Quality surfaces with polyurethanes Surfaces of all types were a major topic at the Competence Forum. In this context, highly-automated, multiprocess solutions were highlighted, where injection moulded substrates are given high-quality polyurethane surfaces. Inline processes such as ColorForm, SkinForm and CoverForm produce parts which are painted, grained/ soft-touch and scratch resistant respectively, in a single processing sequence.

SkinForm produces polyurethane surfaces on thermoplastic carriers in a production cell. The carrier can be designed to have many functional elements, ribs and attachment points for modular parts. The visible surface is created with a polyurethane integral foam in the second cavity of the mould.

The entire manufacturing cell is made up of components from the KraussMaffei product line: a CX 200-750 injection moulder with LRX 100 linear robot and a RimStar Hybrid 4/4 polyurethane metering and mixing

The prefabricated houses can be produced in high volumes on a KraussMaffei double-belt press

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

unit with a 5/8-2+2 high-pressure mixing head mounted on the injection mould, and a machining station for separating the sprues.

Lightweight construction KraussMaffei also presented conventional polyurethane processes, with the focus on lightweight fibre-reinforced composites, e. g. a system combining the LFI (Long Fiber Injection) technology for large format parts and ColorForm producing fibre-composite parts with high-gloss paint surfaces in a single-sequence process. The mixing heads, pumps, polyurethane moulds and mould carriers, as well as the post-mould processing cells for punching and routing were also on display.

Furthermore, the company showed an HPRTM process (High Pressure Resin Transfer Moulding) illustrating how carbon fibre-reinforced lightweight parts can be mass produced in automated processes. The system covers the whole process chain, from automated production of carbon-fibre preforms to post-mould processing of the HP-RTM parts.

Constant mixing pressure with variable output Polyurethane systems for multi-hardness soft-foam processing for upholstery must offer a broad processing window for shot weights and mass flows in order that different moulds and outputs may be facilitated in a single installation. The new KraussMaffei Vario nozzle offers constant pressure in the

mixing head and a constant mixing ratio over a large, variable range, up to a mass ratio of 1:6. The associated RimStar 29/29 metering and mixing device is additionally equipped with integrated pump monitoring.

Fully automated sealant application coupled to injection moulding At the Competence Forum, KraussMaffei also showcased a complete manufacturing cell for producing thermoplastic parts bearing polyurethane sealant beads. When the parts have been moulded, an industrial robot removes them from the injection moulder and passes them underneath a permanently mounted mixing head, thereby ensuring reproducible application of sealant beads. The polyurethane components are provided from a RimStar Nano metering and mixing unit.

The high-pressure mixing head cleans itself after every cycle, while production continues. As very fast-reacting material systems can be processed, the seals are hand-dry after 3 min, and the part can be mounted 30 min after sealant application. This system concept is suitable for all CASE applications, such as encapsulation of electronic parts.

Innovative mobile service solution With the new Mobile Assistant, KraussMaffei offers a solution for customers to retrieve the latest production data, such as current cycle times, scrap rates or utilisation rates of pro-

At the opening ceremony for the prefabricated house in Munich (f. r. t. l.): Kurt Kapp, Head of Economic Development Munich city; Tobias Weiß, Member of the city council Munich city; Dr. Dietmar Straub, CEO of KraussMaffei AG; Frank Peters, Board member of KraussMaffei Technologies GmbH; Dr. Michael Loferer, General Technical Manager Business Unit Construction; Jens Kompe, General Sales Manager Business Unit Construction

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

duction machines, at any time via their smartphones. The Mobile Assistant is easy to use and offers a clear overview of parameters which customers can specify themselves.

The application was developed in cooperation with the Austrian company TIG Technical Information Systems GmbH. It has been fitted to all the injection moulding machines at the Competence Forum to demonstrate its capabilities.

Further exhibits and live demonstrations Among the exhibits were also injection moulding machines from the AX, EX, CX and MX series, together with matched automation solutions. Production cells showcased solutions for all the main industry sectors and covered the tonnage range from 50 – 3,200 t.

The new all-electric injection moulding machine EX 200-1400 is teamed with an SR 80 side-entry robot in a manufacturing cell. The robot removes the food packaging products from the mould and stacks them.

The new AX 350-1400 offers efficiency and precision in the production of technical parts. Currently the highest tonnage machine in KraussMaffei’s portfolio of all-electric injection moulding machines, it was on public display for the first time. An IMC 320024500 produced lightweight, but sturdy, pallets made of recycling material in a multiprocess system combining compounding and injection moulding.

In the Extrusion division, the focus at the inhouse exhibition was on processing high level materials for pipe extrusion. The whole production process for PE-Xa pipes was demonstrated on a fully-operational extrusion line.

The company also showcased its new Internal Pipe Cooling (IPC) system, which shortens the cooling zone, with a KME 75-36 B/R single-screw extruder and a RKW 33IPC pipehead in a complete production line for PO pipe extrusion. In addition, the company highlighted space-saving and flexible coextrusion solutions for producing core and cover layers in U-PVC profile extrusion. 

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No. 1 in Asia and no. 2 worldwide in plastics and rubber shows

Chinaplas 2011 with record breaking results The 25th Chinaplas closed its doors on the 20th May at the China Import & Export Fair Pazhou Complex, in Guangzhou with record breaking results. The show’s scale, exhibitor and visitor numbers have increased remarkably in comparison to 2010 making Chinaplas 2011 the world’s no. 2 plastics and rubber show, following K fair in Germany and further consolidating its no.1 position in Asia. The organisers Adsale Exhibition Services Ltd. pointed out that the improving economy, government policy, together with the continuous support from various parties, including overseas and local associations, exhibitors, visitors, and media have contributed to this success.

Business opportunities for Chinese and international visitors and exhibitors This year, a 15.5 % growth in visitor number was recorded when compared with Chinaplas 2010. 94,084 visitors came to Guangzhou, of which 20.27 % (19,069) came from 138 overseas countries and regions, the majority from Asia excluding Hong Kong, Macau and Taiwan, accounting for 47 %. Hong Kong, Macau, and Taiwan provided 20.7 % of visitors, followed by Middle East (10.8 %), Europe (8.5 %), America (6.7 %), Africa (4.7 %) and Oceania (1.6 %). It was recorded that Hong Kong, India, Taiwan, Japan, Korea, Indonesia, Iran, Malaysia, Thailand and Russia were the ten top origins of visitors.

dia Plastics Manufacturers Association, Vietnam Plastics Association, etc. and business groups from Iran, Indonesia, India, Brazil, Korea, Turkey, Thailand and Vietnam, etc.

As for local visitors, 60 groups were formed by associations and leading enterprises, such as BYD, Changhong, Dongguan Wire & Cable Association, Foxconn, Gree, Guangdong Automobile Industry Association, Medical Plastic Professional Committee of China Plastic Processing Industrial Association Council, Midea, Shenzhen Electronics Industries Association, Shenzhen Toys Industry Association, Southern Packaging and Shunde Home Appliance Chamber of Commerce, etc.

“The strong growth of visitor number demonstrates the sign of economic recovery. Many enterprises are aware of the needs to upgrade their production line in order to enhance their competitiveness and capture the growing market after the financial crisis.

Other enterprises spare no effort to align with the green policies highlighted in the 12th Five-Year Plan, such as energy saving, low carbon emissions,” said Ada Leung, Adsale Assistant General Manager.

Stanley Chu, Chairman of Adsale

The show saw strong presence of overseas delegation groups organised by Malaysian Plastics Manufacturers Association, All In-

2,441 exhibitors from 34 countries and regions with 11 pavilions from Austria, Canada, China, France, Germany, Italy, Japan, Taiwan, Turkey, UK, and USA have occupied an exhibition area of 180,000 m². Turkey

Inauguration of Chinaplas 2011 with the ribbon cutting ceremony

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made its debut with a country pavilion at Chinaplas and it has expressed interest in expanding the pavilion area in 2012.

Prestigious international status Adsale had invited prestigious guests to inaugurate the opening of the fair, including Chen Shi Neng, Honorary President of China National Light Industry Council, Wang Rui Xiang, President of China Machinery Industry Federation and Bu Zheng Fa, President of China National Light Industry Council, etc.

Stanley Chu, Chairman of Adsale, said: “Chinaplas has its double meaning this year.

In addition to the 25th edition, we will finish a record-breaking event not only to mark the continuity of last year’s theme ‘Green Plas-

tics. Our Goal. Our Future’, but also let overseas and Chinese market players witness the important role of green plastics and low carbon solutions played in the industry and raise their awareness on the green concepts.”

tics and degradable plastics, plastics recycling technology and energy saving plastic technology had apparently grabbed the attention of the participants. In addition, a BioPlastics & Degradable Plastics Zone was introduced at this year’s event.

“Green plastics”

High-quality exhibitors and advanced display

To highlight the “Green Plastics” theme a series of events was organised. The “Alive Bottles Tree” made by 3,528 recycled plastic bottles were displayed to arouse the awareness towards the concepts of recycling and reuse.

What’s more, the two-day conference, “Ecofriendly Plastics Conference” held on 18 – 19 May 2011 was over-registered with a long waiting list. Three major topics on bioplas-

Plastic fairs worldwide: K, Chinaplas, NPE. Attendance at NPE 2009 was down sharply (about 28 % compared to 2006).

K 2010 Visitors Exhibitors Exhibition space

Chinaplas 2010

Chinaplas 2011

NPE 2009

NPE 2012 (expectations)

222,000

81,435

94,084

45,000

55,000

3,102

2,144

2,441

1,851

1,800

164,125 m²

150,000 m²

180,000 m²

88,000 m²

76,600 m²

Numbers according to the show organisers Messe Duesseldorf, Adsale, and SPI

The recycled bottles of the “Alive Bottles Tree” are connected to form a tree trunk and branches.

Water and nutrient is poured into some of the bottles at the treetop, and vegetation is then put inside the bottles, like leaves growing from the recycled bottles.

As the world’s largest plastics machine producer and plastics consumer, China will continue to be the focal point of the global plastics and rubber industries. With its rapid growth of plastics and rubber application sectors, such as automotive, building and construction industries, E&E, IT & telecommunications, and packaging the market offers great potential for further development.

German Pavilion The German pavilion in hall 5.1 hosted more than 100 German manufacturers of plastics and rubber, machines and complete lines, moulds and dies as well as auxiliary and peripheral equipment on 2,700 m 2. Among them where Arburg, Azo, Brabender, Gneuss, KraussMaffei, Maag, Nabaltec, Plasmatreat, Rampf, Reifenhäuser, SKZ, Wickert, Zwick, etc.

Chinaplas 2012 Many of the exhibitors, visitors and media have already expressed their continued support for next year’s Chinaplas. It will be held at Shanghai New International Expo Center on 18 – 21 April 2012. The organiser said that it is confident that the 2012 edition will further expand to an exhibition area of 200,000 m² and attract over 2,600 exhibitors.

First introduced in 1983, Chinaplas is China’s only plastics and rubber trade show approved by UFI (Global Association of the Exhibition Industry). 

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151

From the 2 international SKZ conference on flame retardants nd

Markets, requirements, challenges and innovations After the successful premiere in Shanghai in 2010 the SKZ (Süddeutsches KunststoffZentrum) together with its Chinese subsidiary organised a second conference on flame retardants in the run-up to Chinaplas.

The conference attracted about 80 attendees.

More than 80 attendees registered for the two-day event which took place 15 – 16 May 2011 in the White Swan Hotel in Guangzhou.

Fire safety of polymeric materials is a topic that touches all industry sectors, from transportation and construction to electrical engineering and electronics. In the light of new regulations and an ever-increasing demand for sustainable and “green” solutions the global flame retardant markets faces new challenges.

An important topic are the new approaches to reduce CO2 emissions, to save energy or to produce energy from sustainable resources. Electric vehicles, fuel cells, photovoltaic systems, wind turbines, etc. require adapted flame retardant systems for battery houses, cabling, sealing, etc. The conference aim was to give a comprehensive overview of the highly complex theme of the current status of national and international regulations and testing standards, followed by new approaches and developments in flame retardant polymer materials and flame retardant systems. The presentations were given in

152

English and Chinese with simultaneous translation.

Fire safety regulations, classifications and testing are becoming more and more international and to oversee the multitude of legislation and regulations in full, is quite challenging. Dr. Jürgen Troitzsch, chairman of the conference, gave an extensive overview on the current status of fire safety requirements in the EU and elsewhere. As for the construction area, there is the problem that fire safety levels are subject to the individual national legislations of the member states and only the European reaction to fire-classification (Euroclasses) and the new harmonised fire test methods are integrated into national building regulations. He further pointed out that flammability requirements in the vehicles (cars and buses) are currently still very low but become increasingly more important as on the one hand electromobility requires higher fire safety and on the other hand the percentage of lightweight plastic parts that substitute metal in cars is constantly increasing. The regulations for rail-

ways and ships are much more stringent than those for automotive. Troitzsch pointed out, that here the new fire safety requirements may often prevent the use of larger thermoplastic or elastomer parts.

A topic that constantly appeared in the different presentations was the question about halogenated and non-halogenated FR materials. The trend towards the increasing demand for non-halogenated products driven by end-consumer demand is clear. But within this context it was pointed out by several suppliers of halogenated flame retardants that “non-halogenated” does not necessarily mean “green”. Crucial is that a product should be non-toxic and not bioavailable.

In order to support the change to non-halogenated products, Cefic, the European Chemical Industry Council, has founded PINFA in 2009, an industry association that represents the manufacturers and users of nonhalogenated phosphorus, inorganic and nitrogen flame retardants (PIN FRs). Among its members are BASF, Budenheim, Clariant, Nabaltec, Perstorp, Rhodia, and others.

Dr. Annika Luks from Nabaltec mentioned the PINFA activities in her presentation on new developments in mineral flame retardants.

Several speakers introduced new plastic materials for different applications: polycarbonates from Bayer MaterialScience for battery housings of e-cars, different engineering plastics (partially bio-based) from DSM mainly for consumer electronics, LSZH TPUs from BASF Polyurethanes for cabling in Flame retardants? No thanks! – In the evening of the first conference day the organisers invited to a Teppanyaki buffet.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

e-cars, and halogen-free TPEs from JLS as an alternative to PVC in E&E applications.

A team of scientists from China and Germany (Guangzhou Inst. of Chemistry, Chin. Academy of Sciences, Fraunhofer, BAM) introduced a novel development for the flame retardancy of epoxy/clay composites by using low-melt-

ing glassy polymers containing phosphorus and silicon. These glasses can significantly improve flame retardancy due to flame inhibition and the formation of fire residue working as a protective layer during burning.

Lively discussions during the conference and in the coffee breaks demonstrated the high

interest both of suppliers and users in the subject. Consequently the SKZ will continue this conference series: The 3rd International Conference on Flame Retardants will take place in Shanghai from 16 – 17 April 2012.

Chinaplas 2012 will run from 18 – 21 April 2012. 

About the organiser The SKZ Süddeutsches Kunststoff-Zentrum recently celebrated its 50th anniversary. Its areas of activity cover testing and quality assurance of plastic products according to national and international standards, certification and approval of plastic products, consulting, basic and advanced training as well as certification of management systems. It is based in Würzburg in Southern Germany. The Chinese subsidiary SKZ – SINO-German Plastic Technology Service (Cheng De) Co. Ltd. is based in Cheng De, northeast of Beijing.

Polyurethane glass encapsulation technology for panorama windscreens The windshield of the Opel Astra GTC extends 1.5 m from the hood to the B-pillar, which amounts to more than a third of the vehicle’s total length. According to the manufacturer, the Panorama GTC is just as strong as the three-door vehicle with a steel roof. One reason for so much light and space are the light-stable Colo-Fast systems from BASF Polyurethanes.

In places in the Opel Astra GTC where, on other cars, the field of vision is delimited by steel and fabric, there is glass. Because the panoramic windshield extends from the end of the hood to well behind the front-seats, passengers can see more of the world than in any other series-produced car – including convertibles, says the company.

For decades in applications around the world, the Colo-Fast systems from BASF Polyurethanes have proven effective as a glass encapsulation material and are in use with many leading manufacturers of glass panes and modules. With Colo-Fast-WST (Window Spray Technology), BASF now also has an innovative system for pressureless application to glass in an open mould.

This flush glazing technology is only possible with polyurethane. The result is glass and panorama roofs with flush seals and glass panes. Bonded or extruded profiles, on the other hand, have design drawbacks and are more susceptible to dirt, says the company.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

WST technology offers greater design freedom, a reaction time of less than 45 s, reduced reworking, and also lower investment costs, according to BASF. Opel Astra GTC with Colo-Fast WST glass encapsulation

Splifar in Belgium is the first company to be granted a license by BASF for Colo-Fast-WST technology and to invest in a production installation. Production with this light-stable PU system has been underway since the end of 2010.

After taking over the window encapsulation business from Recticel in 2009, BASF initiated the development of a Colo-Fast system series in line with the latest requirements of REACH. These systems have been undergoing successful launch in Europe and Asia since the end of 2010.

The sights are now set on the next projects: large, complex windows (of laminated or toughened safety glass) for cars and commercial vehicles with Colo-Fast-WST technology and, for 2011, concrete plans for a windshield for a truck manufacturer.

In addition to the automotive industry, a growth market for Colo-Fast WST technology includes the solar industry. The possibility of producing integrated flush photovoltaic panels and solar collectors with it improves water management of the roof, i. e. prevents moisture penetration, and counteracts dirt accumulation by improving rainwater run-off.

Furthermore, Colo-Fast protects the edges of panels and collectors from breakage during shipment and installation. 

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E. Geiger, J. Ju*

New flame retardant for flame lamination applications Foam to fabric flame lamination is a distinct segment of the automotive and furniture industrial applications for flexible polyurethane foams. Typically, this application requires materials that provide good properties, e. g. air-permeability, high resilience, lightweight in nature, with good adhesion and preferably good flame retardance. Typical performance requirements include meeting at least FMVSS302 for flame performance in addition to other requirements as indicated by customers. These requirements may include a measurement of the adhesive strength of the laminated fabric upon the foam and verifying that the core physical properties of the materials have also not been affected. A new commercial flame retardant is now available for flame laminating flexible foams. This new product combines the benefit of flame retardance, improved adhesion, and resistance to scorch while providing lower volatility that would result in lower VOC emissions and lower fogging contributions while further enabling the foam to meet its expected physical properties.

1. Introduction The flexible polyurethane foam industry worldwide faces challenges to incorporate flame retardants within the products being offered today. Within a given application, a foam producer needs to offer a product that meets preferred processing and performance requirements. To meet these requirements, foam producers often incorporate special additives designed to provide improvements in one or more areas of the foam’s performance preferably without compromising another area. Commercial approaches to flame lamination in today’s markets have involved adding products that claim to improve a given property such as adhesion or processing aspect but unfortunately have not provided improvements in flame retardance along with another property. The

new product described herein, Antiblaze FL76 flame retardant, is an innovative new alternative that brings improved performances in adhesion, flame retardance, and scorch resistance without compromising volatile emissions or loss of other properties.

2

The following methods were used to generate the data presented.

2.1 Preparation of foams All foams were prepared at lab scale in cardboard boxes according to a standardized procedure. The polyol, surfactant, flame retardant, water and catalyst were weighed into a half-gallon (approximately 1.9 l) plastic con

* Eric Geiger, Jody Ju Albemarle Corporation, Baton Rouge, LA, USA Published with kind permission of CPI, Center for the Polyurethanes Industry, Washington, DC, USA Paper, Polyurethanes 2010 Technical Conference, 11 – 13 October 2010, Houston, TX, USA CPI, Center for the Polyurethanes Industry

154

Experimental

Tab. 1: Formulations used in this study (PHP).

Polyether polyol (56 OHV)

100

Polyester polyol (175 OHV)

Optional

Water

3.5 – 6.5

Surfactant

0.13 – 0.16

Tin catalyst

0.20 – 0.28

FR

Varied

Physical blowing agent

4–9

Foam density (kg/m3)

For the system used in this work, the typical reactivity profile was 35 s for cream time, 1 min 5 s for gel time, 1 min 35 s for tack free time, and 2 min 5 s for free rise time.

The foam rise profile was measured using a Foamat rate of rise apparatus in which an ultrasonic sensor head is used to capture the height and related reaction data for a given foam sample.

2.2 Bond strength testing The bond strength of the laminates obtained was determined in accordance to the following procedure. After preparing the foam based on the desired formulation and aging at room temperature for 24 h, the foam was cut into smaller dimensions (40 x 40 x 30 mm) for use as test specimens. Five specimens were needed for each test. The desired fabric was cut into 65 x 65 mm dimension pieces.

The flame of the burner was adjusted to 55 mm high, and propane was used as the flammable gas. The specimens were put over the open flame of the burner with the lower 

Fig. 1: Fogging test apparatus (DIN 75201 B).

21 °C

Cooling plate Aluminum foil

1.1 – 1.5

Amine catalyst

TDI index

tainer in the desired amounts. The mixtures were then pre-blended with a bow tie agitator at 2,000 rpm for 60 s or until the mix was homogenous with no visible phase separation.

Once mixed, the rpm’s were reduced to 500, a timer was started and the blend was mixed for 40 s, at which time the TDI (isocyanate) was added. At 50 s, the tin catalyst was added and mixing continued until cream time (reaction time) was noted. The mixture was then poured into a 14 x 14 x 14 inch (approximately 35,6 x 35,6 x 35,6 mm) cardboard box and rise time was recorded. Times are from the start of mixing to point of observation.

Sealed beaker Oil bath

100 °C Foam

105 – 110 18 – 30

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

side (40 x 40 mm side) of the specimen held at about 40 mm above the top of the burner.

The specimens were exposed to the flame for 3 s, which partially melted the foam surface.

The fabric was immediately pressed into the foam with a steel plate and held for 3 s.

deposition of material upon the plate. A sample is considered to have passed if < 1 mg/10 g has been deposited upon the plate. The test setup is shown in figure 1.

After flame lamination, the specimens were aged at room temperature for another 24 h and then tested through a Universal testing machine. The foam specimens without flame retardant were processed slightly differently because the foam remained alight after exposure to the open flame for 3 s. In those specimens, the foam was exposed to the flame for only 2 s, and the fabric was immediately pressed onto the foam.

The box foam materials described above were tested using Federal Motor Vehicle Safety Standard (FMVSS) 302. This test is a horizontal flame test and is used as a guideline for foams used in automotive applications worldwide. The foam is ignited for 15 s with an open flame. The ignition source is then turned off and the resulting flame spread is measured in distance/time units.

This test has four possible classifications: self-extinguishing (“SE”) > no burn rate (“NBR”) > pass > fail with a “pass” designation received if a foam specimen has a flame spread of less than 100 mm/min.

2.3 Emissions testing The foams were tested for emissions via the fogging test known as DIN 75201 B. In this test, a specimen is exposed to 100 °C for 16 h during which a glass plate is positioned above the sample to capture any emitted species. The measurement is the gravimetric

300

2.5 Scorch resistance testing Scorch resistance measurements (also known as Yellowness Index or YI) were con-

8.0 6.0

90

2.0

40

20

0.0

20

132

176

Time [s]

Cohesive failure

The product has a typical viscosity less than 2,500 cPs at 25 °C, typical color APHA < 500, and a hydroxyl value approximately 76 mg KOH/g. The product also typically contains 4.5 wt.-% P and 29.5 wt.-% Cl.

Stepanpol PS-1752 polyol is a commercial aromatic polyester diol based upon phthalic anhydride and diethylene glycol with a hydroxyl value of 175 mg KOH/g.

60

88

Antiblaze FL-76 flame retardant is a reactive material developed especially for flame lamination flexible polyurethane foams. The clear, low odor, low viscous liquid provides good flame retardance and scorch resistance with improved adhesion and no increase in volatile emissions of the resulting foam.

80

4.0

44

3.1 Antiblaze FL-76

3.2 Aromatic polyester polyol

160

-50 -2.0 0

3. Products

100

T [C]

H [mm] v [mm/s]

230

2.4 Flammability testing

ducted in accordance to ASTM D1925. The box foams described above were introduced into an oven kept at 25 °C and held there for 24 h. After removal, the foams were cut into smaller dimension samples (70 x 70 x 50 mm) along the center of the larger foam for subsequent measurement.

0 220

 Fig. 2: Foaming profiles of flexible foam containing 15 php FR at 108I and 25 kg/m3 density comparing the performance of FL-76 to another commercial FR.

Adhesive failure

3.3 TDCP Antiblaze 195 is a chlorinated phosphate ester [tris(1,3-dichloropropyl) phosphate, TDCP] in use in the flexible polyurethane industry.

3.4 Commercial FR A Antiblaze TL-10-ST is a chlorinated phosphate ester in use in the flexible polyurethane industry.

3.5 Commercial FR B

FL-76

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Commercial FR C

 Fig. 3: Visual observation of mechanism of flame lamination failure.

Antiblaze BK-69 is a proprietary phosphorous-based flame retardant in use in the flexible polyurethane industry.

155

3.6 Commercial FR C Antiblaze WR-30-LV is a proprietary phosphorous-based flame retardant in use in the flexible polyurethane industry.

4. Results and discussion 4.1 Foam formulations Antiblaze FL-76 flame retardant was compared in typical flexible polyurethane foam formulations to a variety of alternative approaches for flame lamination, including a screening of different commercial flame retardants or flame lamination additives at varying densities of the final foam. The formulations involved in this study are summarized in table 1.

The foam profile observed with the use of FL-76 was measured versus that seen with another commercial flame retardant in use today. The experiment was conducted using a Foamat rate of rise apparatus to record the rise, pressure, and temperature profiles of the foams. As the data in figure 2 show, Fig. 4: 

foams of essentially equivalent process profiles can be achieved when using either flame retardant.

4.2 Bond strengths To determine the effect of the different formulation approaches upon the bonding strengths observed after flame lamination, the samples were first observed for adhesive or cohesive failure. A representation of this phenomenon between two differing flame retardants is shown in figure 3. As can be seen in the figure, foams produced using the new flame retardant FL-76 displayed cohesive failure as the foam itself tore during testing. Foams made with a different commercial flame retardant displayed adhesive failure with the bond between the foam and the fabric giving way during testing.

The bonding strengths of flexible polyurethane foams produced from differing flame retardants were also measured. In these experiments, the property in questions was measured using a Universal testing machine to record the strength at which failure was

Bond strength of flame laminated foam containing 12 php FR at 110I and at 25 kg/m3 density.



observed. The results for two differing density foams are shown in figures 4 and 5.

Differing approaches to improve flame lamination by different manufacturers result in different philosophies with regard to the additive approach to be used. Some companies prefer to use a small amount of an aromatic polyester polyol as a means to improve bond strengths. Other companies use flame retardants alone. Figure 6 reveals a comparison of the bond strengths observed between these different approaches and the use of FL-76 in the flexible polyurethane foam formulation.

4.3 Emissions The emissions evolving from some of the flexible polyurethane foams in this study were also investigated. The measurements were collected using the protocol of the DIN 75201 B test for fogging deposits. The data are displayed in figure 7.

4.4 Flammability The flammability of the flexible polyurethane foams involved in this work was

Fig. 5: Bond strength of flame laminated foam at 105I and at 30 kg/m3 density.

0.8 0.7 Tear strength [kN/m]

Bonding strength N/mm

0.45

0.30

0.15

0.6 0.5 0.4 0.3 0.2 0.1

0.00

FL-76

TDCP

TMCP

Tab. 2: FMVSS 302 results for foams of 105I and 25 kg/m3 density from differing formulation  approaches.

Formulation Amount FMVSS rating

156

0.0

25 kg/m3 Foam density

30 kg/m3 [8 php] FL-76

Commercial FR A

Tab. 3: FMVSS performance of flexible polyurethane foams of 105I and 25 kg/m3 density contain ing differing flame retardants.

FL-76

PS-1752

TDCP

Formulation

FL-76

Commercial FR C

10 pts

3.5 pts

6 pts

Amount

15 pts

15 pts

NBR or SE

Fail

Pass

FMVSS rating

NBR

NBR

Commercial FR A

TMCP

TDCP

Tab. 4: FMVSS 302 results for foams at 105I of  differing densities using FL-76.

Density Amount of FL-76 FMVSS rating

20 kg/m3 25 kg/m3 30 kg/m3 15 pts

12 pts

10 pts

NBR

NBR

NBR

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

investigated using the FMVSS 302 test method. This method was originally developed for automotive applications and is still encountered in many of the global regions as the principle specification for flammability performance today. The flammability performance in the foams in this study is summarized in tables 2 – 4. Table 2 demonstrates the actual flammability performance displayed by the differing formulation approaches mentioned above. Table 3 documents the comparative performance of the new flame retardant FL-76 to a current commercial alternative. Finally, table 4 displays the burn results of foams of Fig. 6: 

differing densities that involve the use of FL-76 flame retardant.

4.5 Scorch resistance The scorch resistance displayed by some of the foams in this study is found in figures 8 and 9. Figure 8 shows the comparison of the Yellowness Index found within foams resulting from different formulation approaches. Figure 9 displays the relatively strong scorch resistance of the FL-76 as compared to another commercial flame retardant known for the scorch resistance it provides flexible polyurethane foams.

Fig. 7: 

Commercial formulation approaches to bond strength improvement at 105I and 25 kg/m3 density.

5. Conclusions Antiblaze FL-76 is a new flame retardant suitable for use in flame lamination applications for flexible polyurethane foams. Due to its reactive nature and content of both phosphorous and chlorine, the product shows an ability to deliver improved bond strengths and flammability without compromising volatile emissions or scorch resistance in foams that contain it. The product is suitable for use in those areas in need of improvements in one or more of these characteristics. 

Fogging measurements of flexible polyurethane foams of 108I and 15 php FR and 25 kg/m3 density made with differing flame retardants.

Fogging test DIN 75201 B 100 °C/16 h 25 kg/m3 FMVSS302 polyether foam

Commercial flame lamination formulation approaches 35 0.6

30 Fog, mg/10 g

Bond strength [N/mm]

0.5 0.4 0.3 0.2 0.1 0

FL-76 @ 10 pts

PS-1752 @ 3.5 pts

TDCP @ 6 pts

0

yellowness Index resulting in foams of 105I and 25 kg/m3 density from differing formulation approaches to flame lamination.

Fig. 9: 

Scorch performance Yellowness Index

Yellowness Index

0 -1 Inside Foam specimen across bun FL-76

PS-1752

Outside

TDCP

E-MAGAZINE

TDCP

Commercial FR C

FL-76

Scorch resistance of FL-76 and another commercial flame retardant in foams of 105I and 25 kg/m³ density with 15 php FR.

0.0

1

Outside

15

5

2

-2

20

10

Additive

Fig. 8: 

25

Scorch performance

-0.5 -1.0 -1.5 -2.0 Foam across center Commercial FR B

FL-76

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PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

157

R. Neff, T. Smiecinski, V. Manea*

MDI slabstock foam – flammability performance without added flame retardants While flammability regulations are becoming more stringent, slabstock foam producers are coming under increasing pressure to eliminate halogenated flame retardants (FR) from their formulations. Although halogenated additives have been specifically targeted, any FR additive will contribute cost, and may degrade the performance of slabstock foam. In response to the emerging market need for slabstock foam free of FR, BASF recently developed an innovative solution. Lupranate 280 Isocyanate is a versatile MDI product which can be formulated using typical ingredients to produce conventional, high resilience and viscoelastic slabstock foam. This paper provides examples across all three applications.

Excellent processing and properties were achieved, especially for conventional foam where processing difficulties have been encountered in past work. Remarkably, California 117 compliance was accomplished without using FR additives. Formulation of Lupranate 280 Isocyanate with Pluracol Balance 50 Polyol additionally offers a product containing renewable material. A thermogravimetric analysis (TGA) study comparing MDI and TDI conventional foam is also included to gain some understanding of the flammability performance.

1. Introduction Flexible polyurethane foams have historically been manufactured to meet fire safety requirements under federal and state flammability regulations as established by the

* Raymond Neff Raymond.neff@basf.com Senior Research Scientist, Urethanes R&D Theodore Smiecinski Senior Technical Service Specialist, Urethane Basic Chemicals Victoria Manea

Consumer Products Safety Commission (CPSC) and California Bureau of Home Furnishings. Compliance can take the form of modifying the combustion characteristics of the polyurethane foam to meet specific criteria as set forth by test method standards to measure the flammability performance of the finished article or components. In general, flame retardant (FR) additives are introduced to foam formulations to modify the burning characteristics when subjected to flaming and/or smoldering ignition sources.

However, foam producers are now coming under increasing pressure from both consumer groups and lawmakers to reduce or eliminate halogenated flame retardants from their formulations. In addition to perceived ecological issues, these additives (and their non-halogenated alternatives) can

add significant material cost to the foam, especially at the high use levels often required to pass flammability tests (see table 1). Solid flame retardants such as melamine are potential alternatives, but they require special handling, and may degrade the properties of the foam. Again, high use levels may be required.

MDI as an intermediate raw material for the production of polyurethane slabstock foams has expanded beyond technical grade products into the general cushioning markets for comfort, support, and safety. Due to the resulting rigid character imparted into the final product by MDI, its more traditional applications have included energy and thermoforming semi-rigid foams used in packaging, and automotive headliners [1]. Blending of modified or polymeric MDI components with TDI attempts to provide a processing window for flexible foam applications. While such a compromise is adequate for specialized applications such as transportation seating and carpet padding [2], this is generally not acceptable for more demanding uses such as home furnishings.

More recently, BASF launched a unique MDI product, Lupranate 280 Isocyanate, capable of producing not only technical foams, but more importantly, a larger spectrum of possibilities. Lupranate 280 Isocyanate is complementary to TDI in the flexible cushion markets of bedding and furniture. Innovatively, it provides a platform to manufacture viscoelastic (VE), high resilience (HR), and conventional slabstock foams compliant with California Technical Bulletin 117 without flame retardant additives [3 – 5]. Furthermore, use of Pluracol Balance 50 Polyol in combination with Lupranate 280 Isocyanate offers the possibility of a product that is both

Market Development Manager, Urethane Basic Chemicals BASF Corporation, Wyandotte, MI, USA Published with kind permission of CPI, Center for the Polyurethanes Industry, Washington, DC, USA Paper, Polyurethanes 2010 Technical Conference, 11 – 13 October 2010, Houston, TX, USA, CPI, Center for the Polyurethanes Industry

158



Tab. 1: Examples of flame retardant additives

Ingredient

Typical loadings (pbw)



Tab. 2: California TB 117 test criteria [5]

Open flamea Char length, inch Afterflame, s

Polybrominated

5 – 25

Chloro-phosphated ester

5 – 25

Smolderingb

All phosphorus

5 – 30

a

Melamine

10 – 100

Aluminum trihydrate

50 – 150

Expandable graphite

Limited

6 average/8 indiv.

5 average/10 indiv. >80 % retained

California Technical Bulletin 117* vertical open flame: part A. original & heat aged (24 h at 220 °F) b California Technical Bulletin 117* cigarette smoldering: part D. *This numerical flame spread rating, as in other tests of flammability, is not intended to reflect hazards presented by this or any other material under actual fire conditions.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

2. Experimental

halogen-free and contains significant renewable content. An ecoefficiency analysis has shown that use of Pluracol Balance 50 Polyol in place of typical polyether polyols produces foam with less environmental impact [6]. This paper demonstrates the versatility of Lupranate 280 Isocyanate in producing all three types of slabstock foam, while achieving California TB 117 compliance without any flame retardant additives.

Machine-made foams were processed on a Cannon Viking CarDio pilot slab stock machine (CV). The CV machine is equipped with CarDio, Maxfoam, and Direct-Laydown dispensing capabilities utilizing the CarDio gatebar, weir trough, and traversing nozzle, respectively. Material throughput ranges between 75 and 130 kg/min; bun width ranges

TDI

MDI

MDI renewable

100

100

25

Water

2.2

2.4

2.3

Liquid CO2 blowing agent

2.4

3.0

3.0

Niax L-650 silicone surfactant

1.4

1.4

0.90

Dabco 33LV

0.4

0.4

0.16

Dabco BL11

0.04

0.04

0.10

Dabco T-9

0.1

0.1

0.22

Lupranate T-80 TDI

33.4 50.6

49.2

107

107

Pluracol 4156 Polyol Pluracol Balance 50 Polyol

75

Diethanolamine

0.43

Lupranate 280 Isocyanate Index

110

TDI

MDI

1.6

1.7

1.6

Elongation, %

104

124

113

9

11

9

Tear, pi

1.4

1.5

1.0

Resilience, %

60

50

32

25 %

21

20

19

65 %

43

43

41

25 % return

17

16

13

2.01

2.11

2.09

81

79

69

50 %

2

5

5

90 %

2

6

71

Air flow, cfm

3.3

4.0

0.8 Pass

Full compliance with the California TB 117 protocol requires passage of the cigarette smoldering part D in addition to the vertical open flame segments under part A. A review of the California TB 117 test criteria is provided in table 2. Heat aging is typically carried out in order to simulate long term aging of the foam, leading to migration and loss of FR additive during that time. Loss of FR additive from the foam would lead to poor performance in the vertical flame test. Achieving such performance without use of these FR additives therefore has the added benefit of improved aging behavior. In addition, the presence of many FR additives is known to worsen performance in the smoldering test.

IFD, lb/50 sq. inch (4 inch)

Support factor Recovery, % Compression sets, % set

Flammability* Cal. TB 117 open flame

Criteria

Fail

Pass

Afterflame, s (ave.)

<5

13.7

0.0

0.0

Char length, inch (ave.)

<6

12.0

2.0

2.5

Afterflame, s (ave.) (heat-aged)

<5

14.9

0.0

0.0

Char length, inch (ave.) (heat-aged)

<6

12.0

1.9

2.7

Pass

Pass

Pass

99.1

99.4

99.7

Cal. TB 117 smoldering % weight retained

>80.0

*This numerical flame spread rating, as in other tests of flammability, is not intended to reflect hazards presented by this or any other material under actual fire conditions.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Physical property data were derived from ASTM standard testing procedures. Flammability tests were conducted in accordance with the California TB 117 vertical flame and smoldering tests [5]. Thermogravimetric analysis (TGA) was conducted using a TA Instruments Q5000 TGA. Samples were subjected to a heating rate of 10 °C/min in air from 35 – 750 °C. Dynamic Mechanical Analysis (DMA) was performed in accordance with ASTM D4065, using a TA Instruments RSA III. The samples were diskshaped, 25 mm in diameter and 13 mm in height. Data was collected using a temperature sweep between 100 and 200 °C, a heating rate of 5 °C/min, frequency of 1 Hz and strain amplitude of 0.5 %.

3. Results and discussion

MDI renewable

Density, pcf Tensile, psi

 Tab. 3: Conventional foam formulations

between 36 and 60 inches with a height range of 6 – 30 inches depending on density.

Control automation is achieved via CCI Wonderware operating system. Laboratory foams were prepared using a standard handmix procedure.

3.1 Conventional foam

 Tab. 4: Conventional foam properties

Processing MDI-based conventional foam is a difficult challenge [7]. However, a formulation with wide processing latitude was developed using Lupranate 280 Isocyanate and commonly used polyols and additives.

A study comparing TDI and Lupranate 280

159

Isocyanate for 1.6 pcf, 20 IFD conventional foam was conducted. Formulations are provided in table 3. Liquid CO2 was used as a co-blowing agent. The levels of water and CO2 were adjusted to give the same density.

No flame retardant additives (FR) were used in either formulation.

280 Isocyanate and an additional experimental MDI were subjected to thermogravimetric analysis (TGA) conducted in air.

Foams were prepared by standard hand-mix technique, using formulations similar to the basic TDI and MDI formulations listed in ta-

0

TDI 2

4

MDI 0

Density, pcf

1.79

1.89

1.85

1.73

Elongation, %

140

131

133

110

Testing results are summarized in table 4.

Physical properties are roughly equivalent for the TDI and MDI foams. However, only the MDI foam passed the California TB 117 vertical flame test, despite the absence of FR in the formulation.

Tensile, psi

17

19

19

17

Tear, pi

2.2

2.0

2.1

1.6

Resilience, %

55

60

59

51

25 %

23

27

27

21

65 %

52

62

62

52

25 % return

18

21

21

15

A conventional formulation incorporating renewable polyol is also summarized in tables 3 and 4. Pluracol Balance 50 Polyol is made from 31 % renewable material, and can replace conventional polyol in a formulation [4].

In this case, 75 % of Pluracol 4156 is replaced by Pluracol Balance 50. This foam also passes the California TB 117 vertical flame test without added FR. The combination of Lupranate 280 Isocyanate and Pluracol Balance 50 Polyol offers the foam producer the opportunity to produce foam with renewable content, but without the disadvantages associated with added FR.

Support factor

2.32

2.30

2.28

2.51

78

78

77

73 12

To understand the role of isocyanate in California TB 117 vertical flame test performance, foams based on TDI, Lupranate

Cal. TB 117 open flame



pbw FR

IFD, lb/50 sq. inch (4 inch)

Recovery, % Compression sets, % set

6

8

31

10

11

64

1.8

1.7

1.9

0.9

Height, % loss

3.6

3.1

2.7

4.9

25 % IFD , % loss

22

22

23

27

65 % IFD , % loss

17

18

20

23

Height, % loss

1.2

0.8

0.9

3.2

40 % IFD, % loss

21

20

21

29

Fatigue properties Static, I1

Pounding, I3

Flammability* Criteria

Fail

Pass

Pass

Pass

Afterflame, s (ave.)

<5

10.4

0.0

0.0

0.0

Char length, inch (ave.)

<6

8.4

2.0

2.1

2.7

Afterflame, s (ave.) (heat-aged)

<5

15.8

0.0

0.2

0.0

Char length, inch (ave.) (heat-aged)

<6

11.1

2.3

2.2

2.2

Pass

Fail

Fail

Pass

99.8

76.1

79.5

99.4

Cal. TB 117 smoldering TDI

MDI

68

Pluracol polyol 945

56

% weight retained Tab. 6: HR foam properties



32

44

3.25

3.15 5

14

Diethanolamine

1.28

1.70

12

DC-5043 silicone surfactant

0.9

Water total Ancillary blowing agent

U2000 silicone surfactant

1.0

Dabco 33LV

0.09

0.08

Dabco BL11

0.03

0.08

Dabco T-10 Dabco T-12

0.13 0.03

Antiblaze 100

0-4

Lupranate T-80 TDI

40.3

Lupranate 280 Isocyanate Index

160

56.3 105

97

Fig. 1:  TGA profiles in air for conventional foam (laboratory hand-mix).

>80.0

*This numerical flame spread rating, as in other tests of flammability, is not intended to reflect hazards presented by this or any other material under actual fire conditions.

TGA rate of weight loss (%/min)

Pluracol polyol 4830

6

90 % Airflow, cfm (crushed 2 x)

Tab. 5: HR foam formulations

Pluracol polyol 2100

50 %

TDI EXPT MDI

10 8

Lupranate 280 Isocyanate 6 4 2 0 200

300

400

500

600

700

800

T (°C)

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

ble 3. The TGA test provides a decomposition profile for the foam as a function of temperature for a given set of controlled conditions. Only the Lupranate 280 Isocyanate foam passed the California TB 117

vertical flame test. TGA profiles are shown in figure 1. Both the Lupranate 280 Isocyanate foam and TDI foam had 4-stage decomposition profiles, but the first stage of the Lupranate 280 Isocyanate foam profile

MDI (hydrophilic) Pluracol 593

65

Pluracol 1538

35

Pluracol 4600 Poly-G 30-168 Water

1.5

Tegostab B8409 silicone surfactant

0.35

Niax L-5614 silicone surfactant

MDI

TDI

15

15

85

85

1.7

1.5

0.6

0.6

Dabco 33LV

0.25

0.2

0.2

Dabco BL11

0.2

0.25

0.1

Dabco T-9

0.05

0.15

7

1

1

47.6

48.4

91

80

85

MDI (hydrophilic)

MDI

TDI

Density, pcf

4.1

3.8

3.9

IFD, lb/50 sq. inch (4 inch), 25 % deflection

16

14

14

Sag factor

2.4

2.5

2.5

Tear, pi

1.2

1.6

1.2

Tg, °C (DMA)

7

17

11

Recovery time, s

7

36

3

Pass

Pass

Pass

Niax DP1022 Lupranate 280 Isocyanate Lupranate T-80 Isocyanate

33.2

Index

California TB 117*

*This numerical flame spread rating, as in other tests of flammability, is not intended to reflect hazards presented by this or any other material under actual fire conditions.

was less pronounced (and the bulk of the decomposition occurred at a higher temperature). Such a profile may correlate with the ability of the foam to melt away from the flame front without igniting. The experimental MDI foam displayed particularly poor California TB 117 vertical flame test performance. Its profile has only two stages.

This particular two stage profile may suggest rapid thermal decomposition, which does not allow the material to melt away from the flame.

3.2 HR foam

 Tab. 7: VE foam formulations

 Tab. 8: VE foam properties

Examples of TDI- and MDI-based HR foam are given in table 5 (testing results are provided in table 6). As with conventional foam, TDI-based HR foam also requires added flame retardant to pass the California 117 vertical flame test. California 117 results for the TDI foams as a function of FR content are shown in figure 2. Note that use of FR at levels required to pass the vertical flame test can lead to poor results in the smoldering test. Again, the formulation based on Lupranate 280 Isocyanate does not contain FR. Excellent results are obtained in both the vertical flame and smoldering tests. An ancillary blowing agent was used with MDI in order to reach the required density. In principle, this can be replaced with liquid CO2, which was demonstrated with MDI conventional foam.

3.3 VE foam

12

Afterflame time Smoldering

Pass

80 Fail

8

60 Fail

6

40 4 Pass 20

2

0

0

2 pbw FR (TDI-HR formulation)

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

4

0

Smoldering (%wt. retained)

Afterflame time (s)

10

100

 Fig. 2: Effect of added FR on California TB 117 performance for TDI foam.

Red and blue lines represent passing criteria for smoldering and after flame time respectively.

The ability to produce quality viscoelastic (VE) foam over a wide range of density and hardness using Lupranate 280 Isocyanate was previously demonstrated [3]. Formulations using both hydrophilic polyols and a 1000-MW triol have been developed. While a 1000-MW triol is more typically employed, the use of a hydrophilic formulation results in foam with unique physical properties and feel. Examples of VE foams at 4 pcf density are listed in table 7, and properties are listed in table 8. Comparable properties with respect to TDI foam are achievable using Lupranate 280 Isocyanate. Again, California 117 compliance is achieved without added FR.

161

4. Conclusion

6. References

Lupranate 280 Isocyanate is a versatile product for the slabstock foam producer. When formulated with typical slabstock foam components, it serves as preferred alternative to using flame retardant additives for producing California 117 compliant foam. Conventional, HR and VE foam can all be produced with wide processing latitude, while eliminating the ecological, economic and performance disadvantages of added flame retardant. Use of Lupranate 280 Isocyanate in combination with Pluracol Balance 50 Polyol additionally provides renewable content, while maintaining excellent processing and performance for conventional slabstock foam.

[1] S. E. Wujcik, S. M. Yakimek and T. M. Smiecinski, SPI 32nd Annual Polyurethane Technical/Marketing Conference, “Thermoformable Flexible Polyurethane: A Unique Packaging Material,” San Francisco, CA, October 1989.

[2] T. M. Smiecinski, S. E. Wujcik, D. C. Mente and E. H. McKenna, SPI 35th Annual Polyurethane Technical/Marketing Conference, “Mixed Isocyanates in Flexible Polyurethane Slabstock Foams,” Boston, MA, October 1994.

[3] T. M. Smiecinski and R. Neff, Polyurethanes 2006, “Visco-Elastic Polyurethane Foam: The Impact of Isocyanate Upon Foam Morphology,” Salt Lake City, UT, September 2006.

[4] T. M. Smiecinski, V. P. Manea and D. T. Langer, Polyurethanes 2008, “Renewable Polyols for Polyurethane Flexible Foam,” San Antonio, TX, September 2008.

[5] State of California, Department of Consumer Affairs, Bureau of Home

5. Acknowledgments The authors would like to acknowledge Thomas Benvenuti, Christopher Milantoni, William Perdue and Alexander Gershanovich for making the foams for this study, and Lisa Marcolina, Ryan Thomas, Rita Andrews and JoAnn Lanza, for their assistance with physical and analytical testing.

First meeting of the Exhibitors Council for K 2013 The first meeting of the Exhibitors Council heralds the beginning of concrete preparations for K 2013, which will take place in Düsseldorf, Germany, from 16 – 23 October 2013. The Exhibitors Council supports Messe Düsseldorf in planning the trade show and advises it on strategic and organisational issues. It is composed of representatives from the exhibiting companies and industry associations and covers the entire technological breadth of K 2013.

The Exhibitors Council is again chaired by Ulrich Reifenhäuser, CEO of Reifenhäuser GmbH & Co. KG and chairman of the Plastics and Rubber Machinery Association within the German Engineering Federation VDMA. Vice-

162

chairman is, as before, Dr. Rainer Büschl, Head of Communications, Performance Polymers, BASF SE, who also leads the conceptualisation committee. The organisation committee is once more chaired by Thorsten Kühmann, managing director of the Plastics and Rubber Machinery Association within VDMA. Further members of the Exhibitors Council are: • Günter Bachmann, Coperion GmbH • John Ballantyne, Dow Deutschland Anlagengesellschaft mbH • Dr. Rüdiger Baunemann, PlasticsEurope Deutschland e. V. • Dr. Harald Hammer, Borealis AG • Juliane Hehl, Arburg GmbH & Co KG

Furnishings and Thermal Insulation, Technical Bulletin 117 (2000).

[6] C. A. Bradlee, V. P. Manea and L. M. Kloock, Polyurethanes 2008, “Eco-Efficiency Analysis Demonstrates the Environmental Benefits of Flexible Furniture Foams Made with Balance 50 Polyol,” San Antonio, TX, September 2008.

[7] M. A. Knaub, E. P. Wiltz and H. Wuilay, J. Cell. Plast. 33(2) (1997), 159. 

Antiblaze is a registered trademark of Albemarle.

CarDio is a trademark of Cannon USA. Dabco is a registered trademark of Air Products and Chemical Incorporated. Lupranate and Pluracol are registered trademarks of BASF. Maxfoam is a trademark of Unifoam. Niax is a registered trademark of Momentive Performance Materials, Inc. Pluracol Balance is a trademark of BASF. Poly-G is a registered trademark of Arch Chemicals, Inc. Tegostab is a registered trademark of Degussa. Wonderware is a registered trademark of Wonderware Corporation.

• Fritz Katzensteiner, Wirtschaftsverband der deutschen Kautschukindustrie e. V., (WDK, Association of German rubber manufacturers) • Ulf Kelterborn, Industrievereinigung Kunststoffverpackungen e. V., (IK, Plastic packaging industry association) • Jan-Udo Kreyenborg, Kreyenborg GmbH • Felix M. Loose, Agor GmbH • Dr. Peter Neumann, Engel Austria GmbH • Michael Rathje, Gesamtverband Kunststoffverarbeitende Industrie e. V., (GKV, Federation of plastics processors) • Klaus-Uwe Reiß, Mitras Materials GmbH • Manfred Rink, Bayer MaterialScience AG • Peter Steinbeck, Windmöller & Hölscher Maschinenfabrik • Dr. Dietmar Straub, KraussMaffei Technologies AG • Pascal Streiff, Euromap c/o Swissmem

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Pot life and curing monitor for PU formulations, epoxy and polyester resins

resins. Production near testing conditions can be achieved by heating the CMD sensor to any reaction relevant temperature.

The reactive test material is poured into a cardboard cylinder, the bottom of which is the heated CMD sensor. The test setup is covered by an insulation hood with a bushing for the thermocouple.

The test device SubCASE HT measures the pot life and the curing of Coatings, Adhesives, Sealants and Elastomers (CASE). The German company Format Messtechnik GmbH has specially designed the device for testing polyurethane formulations as well as epoxy and polyester resins at high temperatures.

The SubCASE HT (fig. 1) combines dielectric polarisation measurement and temperature measurement of reactive test samples.

The dielectric polarisation reveals the electro-chemical process during compound formation and crosslinking. From this conclusions can be drawn regarding the pot life and the curing behaviour of the material.

age of different frequencies. The heat release from the polymerisation reaction is recorded as the core temperature by a thermocouple centrically positioned inside the sample. A further temperature sensor is integrated into the CMD sensor for measuring the contact temperature of the sample and for controlling the heater power.

The heatable CMD sensor (Curing Monitor Device), introduced by the measuring instrument specialists from Karlsruhe, is measuring the dielectric features of the reactive components by applying an alternating volt-

Providing starting temperatures as high as 150 °C, the test device is especially suitable for measuring the reaction profile of epoxy

Fig. 1: 

Fig. 2: 

The software SubCASE continually records the measurement data and displays them in an online graph. After completion of a test, the results are shown as diagrams (fig. 2) and in a parameter list. The pot life is defined as a certain value of the polarisation curve. The software calculates the curing from the dielectric polarisation gradient. Due to a protection foil on the CMD sensor the cured sample can be removed easily from the device.

SubCASE HT can be used in quality assurance as well as in production control applications. 

Reaction profile of an epoxy resin measured with SubCASE HT. The pot life and the curing are determined by the dielectric polarisation measurement. The master indicates the margins for quality assurance testing.

SubCASE HT for measuring the pot life and the curing of CASE materials based on PU, epoxy or polyester resins.

Maximum polarisation 1

5

Maximum temperature Pot life

Filling

3

Maximum reaction

Core temperature →

Dielectric polarisation →

2

Master

Epoxy resin

4

Curing

Time [s] →

www.pu-magazine.com PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

163

Gentle mould cleaning with dry ice blasting Furniture manufacturer Hukla relies on Ascojet For mould cleaning and machine maintenance, the German company Hukla Möbel GmbH in Gengenbach relies on the gentle Ascojet dry ice blasting technology of the Swiss company Asco Carbon Dioxide Ltd. in Romanshorn.

Hukla combines a long-standing tradition with innovative business structures. In the year 1936 the mattress factory was established in Haslach. In 1951 the present upholstered furniture production was set up in Gengenbach on the edge of the Black Forest – the nucleus of an international group of companies. In 1994 the production site in Torgelow in the east of Germany was put into operation. In 2004 the company was integrated into the Steinhoff Group.

In Gengenbach, Hukla manufactures diverse components for upholstered furniture used in residential living areas, such as seat cushions, armrests, etc. According to the company, quality is the benchmark for all activities at Hukla, even for its mould cleaning requirements. For this reason, the company looked for a residue-free cleaning method for its polyurethane foaming tools, one which could easily be integrated into the process.

PU foaming tools before and after cleaning with dry ice.

164

After careful consideration, Hukla decided on the Swiss company Asco Carbon Dioxide Ltd. and its Ascojet dry ice blasting technology. The dry ice blasting unit Ascojet 908 now gently and effectively cleans the moulds at Hukla. In addition, the company also uses the Ascojet dry ice blasting process for maintaining, that is, cleaning its machines. The company also purchases its dry ice requirements from Asco.

Prior to the introduction of the dry ice blasting process, cleaning meant time-consuming scrubbing by hand using brushes and scrapers. Thus, the amount of time saved by using Ascojet dry ice cleaning is tremendous.

“Depending on the size of the moulds, we now only need 30 minutes to an hour for cleaning, whereas we used to need approximately four hours”, states Markus Gross, Foam Production Manager. In addition to the considerable time savings, Markus Gross

views various other advantages of the dry ice blasting as paramount: This because the dry ice directly sublimates upon impact with the surface meaning no secondary waste.

There is also a significant reduction in tool wear since dry ice cleaning does not damage moulds or tools in any way, extending their service life and reducing costs considerably.

The decision of the furniture manufacturer for the Swiss dry ice specialists was based ultimately on several aspects: “Asco had on the one hand, the best value for our money and on the other, presented us cleaning solutions specifically tailored to our needs”, states Markus Gross as reasons for the cooperation. 

About Asco Asco is a single-source supplier of complete CO2 and dry ice solutions. The product portfolio includes dry ice blasting machines, dry ice production machines, CO2 production and recovery plants, various CO2 and dry ice equipment as well as special projects. Further solutions include CO2 delivery, noise control, automation and customised products.

Since 2007, Asco is part of the international industrial gas enterprise Messer Group and is its competence center for CO2.

Thanks to the gentle Ascojet dry ice blasting, tool wear has been significantly reduced.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

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165

W. Michaeli, O. Grönlund, F. Meyer, S. Latz*

Analysis of defect formation in flexible foam mouldings Very high reject rates are sometimes encountered in polyurethane (PUR) flexible foam moulding, especially during the commissioning of new foam moulds. The causes for the formation of these defects, such as areas of hardened foam and collapsed zones, are currently unknown. The aim of this paper is therefore to promote an increase in the process knowledge for polyurethane flexible moulded foams by building up a basic, practice oriented understanding of the process. To this end, correlations between process parameters and the formation of defects in flexible moulded foams are identified in the experimental part of this work.

1. Introduction and objectives In industrial processing of polyurethane to flexible moulded foam parts, reject rates can sometimes be very high despite using optimised PUR foam systems. In particular, unacceptable component properties or final product defects occur often during the commissioning of new foam moulds. For example defects manifest themselves in the form of a partial foam collapse or by the formation of hardened foam areas and peeling skin (fig. 1).

As flexible PUR foams, in contrast to thermoplastic processing, are crosslinking, reactive systems, it is restricted to feed reject components back into the process again and thus save resources to a very limited extent.

lysed before now. In particular, the mould filling behaviour is generally not well understood and can not currently be predicted due to a lack of simulation capabilities. Often a lot of trial and error and significant time are required before a new foam moulding process is prepared and can be put into series production.

The procedure for start-up and the process management of a flexible polyurethane foam process is almost purely empirical [3, 4, 6], because of insufficient knowledge about the formation of moulding faults. Hence there are no universal strategies and solutions to eliminate the moulding faults occurring during production. The goal of this research is therefore to generate a sound understanding of the process of manufacturing soft polyurethane foam. For this purpose basic knowl-

edge is compiled about the formation of defects in flexible polyurethane foam parts in an error analysis. The main factors among the process parameters influencing defect formation are identified and analysed using a test foam mould with variable geometry elements in the cavity.

2. Investigation of fault formation in moulded flexible foams 2.1 Mould technology employed The aluminium test foam mould is modular and consists of an upper and a lower platen.

The two mould halves are made as plates so that, with a frame structure, the cavity is formed with the bottom. The cavity has dimensions 600 x 350 x 100 mm and a volume of 21 l. The frame consists of two tempered Tab. 1: Experimental design mould variables: mould  temperature Data point

Temperature zone 1,2

Temperature zone 5,6

1

45 °C

65 °C

2

45 °C

60 °C

3

50 °C

65 °C

4

65 °C

50 °C

5

65 °C

45 °C

6

65 °C

40 °C

7

65 °C

38 °C

8

65 °C

35 °C

9

65 °C

30 °C

The causes of defects occurring in moulded foams have rarely been systematically ana-

* Prof. Dr.-Ing. Dr.-Ing. E.h. Walter Michaeli, Head of Institute for Plastic Processing (IKV) Dipl.-Ing. Oliver Grönlund, Dept. Head Injection Moulding/PU technology

Collapsed areas

Dipl.-Ing. Florian Meyer, Research assistant PU technology Dipl.-Ing. Simon Latz latz@ikv.rwth-aachen.de Research assistant PU technology Institute for Plastic Processing (IKV) at RWTH Aachen, Germany

166

Fig. 1:  Moulded soft foam component with detached skin and collapsed zone

Peeling skin 5 cm

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

long sides and two short sides. A mixing head fitting is built into one of the short sides to allow material to be introduced laterally (fig. 2).

This type of construction allows the mixing head to be attached to one side of the cavity facilitating the introduction of the reaction mixture into the closed mould. The temperature control is through drilled cooling channels, which end each side of the upper and lower platens and the two longitudinal side walls. The channels are within the mould lower or upper halves and are not connected. Several channels can be connected to create a tempering circuit using standard parts outside the mould. This allows simple and flexible creation of two different temperature zones, which are necessary for part of the investigation (fig. 3).

The sensor system and cavity vents can be positioned at various points in the upper half (fig. 4). This allows the mould filling behaviour to be varied.

Nine possible vent locations are marked in figure 4. Three vents each are located in the beginning, middle and end of the flow path. The positions for the mould and the material temperature sensors are located at the end of the flow path.

The mould is made to have flexible geometry by using mould inserts in order to investigate the influence of different cavity geometries. (fig. 5). Three inserts can be put into the mould. The mould inserts can include geometrical elements, such as a flow obstacle, as shown in figure 5.

3. Experimental design to study mould factors influencing defect formation In the investigation the following parameters are varied: • Mould and component temperature • Mould venting

• Geometrical effects in the form of flow obstacles First, the fundamental effect of the parameters "mould temperature and mould venting" is evaluated. Then an attempt is made to minimise component failures by varying mould and component temperature and venting, at different mould geometries.

3.1 Mould temperature variation Both homogeneous foam mould temperature and heterogeneous temperature fields are considered in the mould temperature studies. Two different temperature zones (zone 1,2 and zone 5,6) can be created, as shown in figure 3.

Hence the experimental design shown in table 1 is carried out to investigate the influence of different temperatures and temperature fields on the formation of defects in moulded foams.

3.2 Varying the mould venting In the mould venting investigation, the venting points shown in figure 4 and the bore diameter are varied. The experimental plan (tab. 2) shows the different venting options to be examined successively.

Pressure and temperature sensors

Platen Upper mould plate

Mould inserts (modular interchangeable base elements)

Frame

Lower mould plate

Mixing head fitting

Foam volume: 20 l

 Fig. 2: Principle of the mould for flexible foams

The various vents are divided over three zones (fig. 4). For example, specifying a bore diameter in millimeters for “zone 1,2” means that the vent positions 1 and 2 are each bored to the stated diameter. For the

 Fig. 4: Variable measuring sensor and vent positions in the experimental mould

 Fig. 3: Experimental mould: temperature zones Tempered side walls (long sides)

Zone: 1,2

Zone: 3,4

Zone: 5,6

1

5 3

Gate (laterally, front side)

Gate (laterally, front side)

P

P 4

2

Zone: 1,2

Zone: 5,6

Temperature A

Temperature B

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

P

6

= available venting or sensor positions P = intended for pressure sensors, Number = intended for venting position = mould temperature sensor = material temperature sensor (probe sensor)

167

first data point, this means that two vent holes are put into zone 1,2 each bored to 2 mm diameter. If no value is indicated (“-” in tab. 2), the hole is blocked with an adapter, so that there is no mould venting.

The flow splitter (fig. 8) makes a considerable flow barrier for the foam. It consists of a partition placed centrally in the cavity, with a gap of 10 mm (10 % of the foam mould's cross section) to the mould top. The foam that fills the second half of the cavity must flow through

of the path. The flow path remains constantly about 100 mm wide and 100 mm high.

The partition walls inserted are about 250 mm deep and have a thickness of about 8 mm. The partition walls are flush with the mould top and bottom.

3.3 Influence of flow obstacles In another section of the mould based studies so called flow barriers in the form of interchangeable mould inserts are introduced into the mould. The parameters, mould and component temperature and the diameter and location of the venting holes are optimised for varying mould geometry to minimise defects.

The type of flow obstacles selected is based on practical mould and part geometries from industry. It is not possible to reproduce all existing complex geometrical elements in a test foam mould within the scope of the investigation. Therefore, only certain geometrical elements used in industrial foam moulds are copied and simulated in the test foam mould. The geometrical elements are studied individually in the test foam mould. After interpreting the results they may be collated and transfered to complex geometries in industrial applications. The flow barriers tested can be divided into the following subcategories: • • • •

flow path narrowing meandering flow splitting obstacle (central)

The meander (fig. 7) gives a flow path for the rising, mould filling foam with four 180 ° changes of direction before reaching the end

168

Fig. 5:  Test mould: Interchangeable inserts

Insert without flow barrier

Flexible interchangeable mould inserts on the mould bottom

50 % mould length View from above:

5

1 3

Gate (lateral)

P 4

P

P

2 Fig. 6: Mould design – flow path narrowing



6

Side view:

50 % mould height

ca. 100 mm

5

1 3 Gate (lateral)

P

P 4

P

6

2 Zone: 1,2 Fig. 7: Mould design – meander



ca. 250 mm

To narrow the flow path a step extending over the entire cavity width, 50 mm high and 300 mm deep is introduced into the mould (fig. 6). This corresponds to a platform in the cavity, which occupies 50 % of the mould height and 50 % of its' length. Hence, the foaming volume in the mould cavity is a quarter smaller than without the flow obstruction.

The material is introduced head on and must spread out over the step into the mould to fill the foam mould completely.

Insert with flow barrier (rib)

Zone: 5,6

X = possible venting position with variable bore size

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

this gap. At the gap, the foam is subjected to strong shear, so that it is likely, the foam structure is modified beyond the gap.

The flow obstruction, short obstacle (fig. 9) is formed by a single partition. It is placed at a distance of about 200 mm from the inlet gate centred in the cavity. The partition is flush with the top of the mould and leaves a flow path on both sides of about 75 x 100 mm. This type of flow obstacle is

Zone 1,2

Zone 3,4

Zone 5,6

1

2 mm

2 mm

2 mm

2

-

2 mm

2 mm

3

-

2 mm

-

4

2 mm

2 mm

-

5

1 mm

-

-

6

2 mm

-

-

7

3 mm

-

-

8

4 mm

-

-

9

6 mm

-

-

10

15 mm

-

-

Data point

Temperature zone 1,2

Temperature zone 5,6

In the investigations, the use of flow barriers in the foaming process is combined with variation of the venting, temperature fields in the mould and with high and low component temperatures.

The mould venting is either “ideal” or “variable”. Before the experiments are carried out, different venting options (“variable venting”) are tested empirically in order to establish ideal venting for each particular flow obstacle. For example, for a first test, the venting positions 1 and 2 in zone 1,2 and the positions 3 and 4 (zone 3,4) are closed. The vents furthest from the injection gate in zone 5,6 for this example experiment, are each furnished with 2 mm vent holes.

Tab. 2: Experimental design mould variables:  mould venting Data point

by step until the ideal venting variant is found. The moulded foams resulting from these trials are then compared qualitatively according to the evaluation criteria (chapter 4). The venting set-up of the test moulded part, rated as the best, is set as “perfect” venting for further tests. Then, starting with ideal ventilation the parameters, die temperature and component temperature are varied independently of one another. For the mould temperature, the zone near the injection point and the zone furthest from it are set to alternating high and low temperatures.

Further, in the experimental design described here those test parameters not handled here are held constant at levels corresponding with neutral effect on these tests.

particularly useful for investigating the formation of join lines in the foam. Experiments are carried out according to the experimental plan in table 3 for all the flow obstacles listed.

4. Development of a character­ isation methodology for components for the study of factors influencing fault formation

In further experiments, this venting set-up is altered and this procedure is repeated step Venting position

A visual component inspection is performed by an operator, as there is no technical means for detecting mould induced moulded part defects in flexible polyurethane foam processing. Thus only macroscopic, visible moulded part properties are assessed in these experiments. The following selected quality characteristics or fault categories can be evaluated in a cold flexible polyurethane foam:

Components temperature

1

50 °C

50 °C

variable

medium

2

50 °C

50 °C

variable

medium

3

50 °C

50 °C

variable

medium

4

40 °C

60 °C

ideal

medium

5

60 °C

40 °C

ideal

medium

6

60 °C

60 °C

ideal

medium

7

40 °C

40 °C

ideal

medium

8

50 °C

50 °C

ideal

high

9

50 °C

50 °C

ideal

low

 Fig. 8: Mould design – flow splitter

 Tab. 3: Experimental design mould factors: flow obstructions

• hardened zones (denser areas) • collapsed zones

 Fig. 9: Mould design – obstruction

Central partition with a 10 mm gap to the mould top 1

Partition flush with the mould top with flow path on left and right side 5

5

1

3 P

P

Gate (lateral)

P

4 2

6 Zone: 1,2

X = possible venting position with variable bore size

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

Zone: 5,6

P

P 4

ca. 200 mm

Gate (lateral)

3 P

2

6 Zone: 1,2

Zone: 5,6

X = possible venting position with variable bore size

169

• • • • • • • •

peculiarities in the skin layers skin thickness proportion of skin layer peeling bubbles close to the surface (fish eyes) surface waviness open cells (or closed cells) mould filling behaviour flow borders/fronts, weld lines and air traps • part shrinkage (qualitative) • warpage of the part (qualitative) The moulded parts are manually “compressed” after they are produced, meaning that any foam cells still closed are largely destroyed. Subsequently, all components are cut longitudinally in the thickness direction.

Cutting open the moulded foams makes it possible to assess defects in the foam structure occurring in the interior of the moulded part. The quality assessment of the entire part combines the visual examination of the inside of the part and the external appearance of the part. The moulded part is evaluated according to a points system. This allows the examiner to make an assessment of the part in all the listed defect categories.

The rating scale is identical for all moulded parts, guaranteeing comparability of the results. From 0 – 10 points are given for each property evaluated, i. e. for each defect category. “0 points” means that the moulded part is not affected in the relevant property assessment, that is, there is no defect in the fault category under consideration (see above). “10 points” mean, therefore, that a moulding is up to 100 % affected by the fault pattern rated. 10 points in the fault category collapsed zones, for example, therefore implies that the foam is completely collapsed in the cavity on demoulding. Next an average point score is calculated from the individual values for the particular moulding. Then a mean value is obtained from all the individual evaluations from all three mouldings made in one test set up. The lower the average point value obtained, the better the average moulding quality with that set-up. All defect categories are assessed and given equal value in the point system outlined here. In the overall assessment of a moulded part no individual defect category is given a specific weighting, because, depending on the ap-

170

plication of the moulded part, the occurrence of a defect in a single category can result in a reject moulding.

5. Moulded foam production The flexible polyurethane foam system used is a cold curing system for the production of sound insulation elements in the automotive sector from the two components, Specflex NS 759 (polyol) and Specflex NE 138 (isocyanate) from Dow Deutschland Anlagengesellschaft mbH, Schwalbach/Ts. It is used for interior sound insulation in the automotive field and is referred to here as “Dow-system”, “Dow” or “sound insulation system”.

The production of the mouldings for studying the effect of parameters on defect occurrence starts from the “neutral” test set-up.

The component temperatures for the neutral test set-up are around 35 °C for the polyol and 30 °C for the isocyanate. If it is not otherwise specified, the venting positions 1, 2, 5 and 6 are each provided with a venting hole of 2 mm diameter in the neutral test set-up. The mould temperature is 50 °C in the neutral test set-up.

The component temperatures are at 25 °C for the polyol and 25 °C for the isocyanate in the “low” test set-up, 40 °C for the polyol and 35 °C for the isocyanate in the “high” test set-up. The diameter of the venting holes is varied between 2 and 15 mm. In addition, the number and positions of the venting holes are changed (see fig. 4). In these experiments, a lateral gate is used. In so far as more parameters are changed, they are shown individually in the experimental designs below. After a storage period of at least 72 h, the mouldings are assessed, first whole and then cut into pieces according to the stated characterisation methodology (chapter 4).

6. Results for parameters influencing the minimisation of defects The following discussion of results from the investigation of mould induced factors is

based on the rating system presented in chapter 4. Table 4 can be taken as an example at this point to explain the ratings. In all the investigations described, the score presented in the “assessment” column is always an average score of three assessed mouldings from the test set-up described in the remaining columns.

6.1 Influence of mould temperature control In the evaluation of mould temperature control, it should be noted that the gate is on the side in zone 1,2. As the polyurethane mixture on introduction flows from zone 1,2 into zone 5,6 of the foam mould, it foams there first and then fills the mould in the gate direction. Hence zone 5,6 should be considered, in this case, the beginning of the flow path, although the material input is into zone 1,2 and this zone represents the end of the flow path in each experiment observed. The effects of varying temperature zones on the incidence of defects in flexible moulded foam can be summarised as follows (Table 4). A generally higher mould temperature leads only to a limited extent to higher quality mouldings. The foam mould temperature has a large influence on skin formation and the openness or closed cell structure of the foam. Lower temperatures cause a higher closed cell structure in the foam and a stronger skin formation. Mouldings that are produced at a relatively high mould temperature, have no skin layer and are very opencelled in the surface layer. If the zone at the end of the flow path is at higher temperature Tab. 4: Assessment of the influence of different mould temperatures on the moulding quality  (0: best quality, 10: worst quality) Data point

Tempera­ ture zone 1,2

Tempera­ ture zone 5,6

Moulding quality as­ sessment

1

45 °C

65 °C

3.3

2

45 °C

60 °C

2.0

3

50 °C

65 °C

1.9

4

65 °C

50 °C

0.6

5

65 °C

45 °C

0.7

6

65 °C

40 °C

1.7

7

65 °C

38 °C

1.3

8

65 °C

35 °C

2.2

9

65 °C

30 °C

2.7

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

than the flow path beginning zone, this leads to high quality mouldings with a low average score according to this assessment. These mouldings have a very uniform characteristic minimal skin layer.

There are no collapsed zones near the surface or shrinkage areas. The mould temperature at the end of the flow path has a greater influence on the moulding quality than the mould temperature at the beginning of the flow path. Mouldings that are produced with low temperature at the end of the flow path show very high part shrinkage with surface collapsed zones, mainly in the zone of low mould temperature.

6.2 Influence of mould venting Table 5 gives an overview of the assessments of the individual experiments of the effect of mould venting on part quality. The ideal venting for the investigation, the venting with the best evaluation score, turns out to uniform venting with 2 mm diameter vent holes throughout the foam mould (data point 1). This venting option is valued at 0.6 points. The second best rating is achieved with two 3 mm vent holes each at the flow path end (zone 1,2 here) (0.7 points, data point 6). Too wide venting holes, such as 4, 6 or 15 mm result in a poorer quality moulding. Collapsed zones near the surface occur with this type of venting in the vicinity of the vent holes. In addition, the foam structure of the entire moulding is uneven, with the formation of individual hardened zones.

Furthermore, the target density is not reached and the mouldings tend to closed cell structure. If venting is insufficient, the Data point

Zone 1,2

1

2 mm

2 3

Zone 3,4

foam mould is not completely filled. In this case the moulding may partially fracture during removal, because of the high internal pressure in the foam cells. This condition is equivalent to overfilling the mould. The foam cells cannot burst, as the cells can not expand enough. Thus, there can be no pressure equalisation inside the foam. With this type of faulty moulding, as well, closed-cell foams are formed.

6.3 Effect of flow obstacles 6.3.1

Flow path narrowing

The results of the tests with a flow path constrictor are presented in table 6. It is important to note that in these experiments, the flow path runs from zone 1,2 to zone 5,6 as the constriction offers an increased flow resistance that can only be overcome by foaming. It is found that the highest quality mouldings can be produced with a medium mould temperature and high mix component temperature (0.6 points, data point 6). The mix component temperature appears to have slightly more influence than the mould temperature. Data point 3 shows that similarly high quality mouldings can be achieved with a medium mix component temperature and a high mould temperature (0.7 points). In contrast, mouldings with very low quality were produced with low temperatures at the end of the flow path. Collapsed zones near the surface, incomplete cavity filling and high moulded part shrinkage are encountered in these mouldings particularly at the end of the flow path. Air inclusions and join lines are reduced in this experimental configuration.

Zone 5,6

2 mm

2 mm

0.6

2 mm

1.4

2 mm

1.4

2 mm

0.9

4

2 mm

5

1 mm

1.0

6

2 mm

1.0

7

3 mm

0.7

8

4 mm

1.1

9

6 mm

1.1

10

15 mm

1.3

PU MAGAZINE â&#x20AC;&#x201C; VOL. 8, NO. 3 â&#x20AC;&#x201C; JUNE/JULy 2011

ď ´ Tab. 5: Assessment of the influence of varying mould venting on moulding quality (0: best quality, 10: worst quality)

Meander

Table 7 shows the test results with the installation of a meandering flow path in the foam mould. It is striking here that the moulding qualities overall are worse than those for narrowing the flow path in table 6.

The mouldings from the meander tests show the lowest moulding quality, when compared with the other mouldings. There is an increased incidence of collapsed zones, air inclusions, join lines and other moulding defects, because of the much longer flow path and the many changes of direction for the foaming polyurethane composition than with the other flow obstacles.

Among the meander tests the mouldings produced with mix components at high temperature and the mould at medium temperature give, with 2.4 points, the mouldings with the best relative quality. The components with the lowest quality (4.6 points) are produced at low mould temperature and medium mix components temperature. This leads to the hypothesis that the mix components and mould temperatures together significantly influence the moulding quality. The temperature of the mix components seems to have a less strong effect on the moulding quality at low mould temperatures than is the case at high mould temperatures. Examining data point 10, the mix component temperature seems to have greater significance than the mould temperature. At high mould temperatures and low mix component temperatures only lower quality mouldings could be produced. Venting at the end of the flow path appears to be the best venting option for the meander tests.

6.3.3

Moulding quality assessment

2 mm

6.3.2

Flow splitter

When the flow splitter tests (tab. 8) are considered, the results are similar to those from the meander studies (tab. 7). First, the moulding quality is best with medium mould temperature and high mix components temperature (1.9 points, data point 8). The lowest moulded part quality is obtained, however, when the mould temperature is high in the first half of the cavity and low in the second half of the cavity (beyond the flow split-

171

ter). These moulded parts are rated at 4.4 points. The proportion of moulded parts with many air inclusions, join lines and large collapsed zones occurring in the flow path beyond the flow splitter is very high with the parameter set-up described (tab. 8). Furthermore, it is clear from these studies that the moulding quality fluctuates by up to one rating point, when choosing an unfavourable or favourable ventilation each with 2.0 or 3.0 rating points (data points 3 and 4). A vent directly above the flow splitter (zone 3,4) turns out not to be beneficial in this case.

The air in the cavity has a short path to escape through a vent directly above the flow splitter.

Hence the foam also has the opportunity to escape from the cavity. The polyurethane foam is formed by gas bubbles, which, due to their internal pressure, have a tendency to expand further. This always drives the foam in the direction of the least resistance to flow. If the mould is vented in an area which offers the expanding foam a lower resistance to flow than continuing until the cavity is completely full, then the foam escapes this way. In comparison, the obstacle offers a higher flow resistance so that the area behind the barrier is not completely filled. Also, too much venting causes collapsed zones in the foam. The foam collapses above the flow splitter and is then pushed into the second half of the cavity by the remaining foaming pressure. The position of the vent is therefore very important in the mouldings with a flow splitter.

6.3.4

The evaluation of the results with the “obstruction” can be summarised as follows: Both the mould temperature and the mix components temperature have a big influence on the moulding quality. A high mould and/or mix components temperature (data points 10 and 11) results in less hardening and collapsed zones and better mould filling.

A low mould or mix components temperature causes, in addition to reversing the above effects, high shrinkage and skin peeling. The venting has a particular influence on the mould filling behaviour; it must be adapted to the pressure gradients in the mould and the local geometry. Sufficiently large venting holes on the flow path and at the flow obstruction generally lead to high quality mouldings with better mould filling. In the case of the barrier shape considered here, however, it is necessary to adjust the venting precisely to the mould temperature. The re-

action mixture is injected from the side and immediately collides against the barrier. At a given mould temperature and defined mix components temperature, an individual foaming and polymer formation process ensues.

This results in a distinctive mould filling behaviour. The flowing front reaches in chronological order the barrier at a particular time and at a later time the venting holes and the end of the cavity. If non optimised venting is selected, the air in the cavity can not escape and defects will be entrapped.

7. Discussion on the influence of process parameters on the formation of moulded foam defects 7.1 Influence of mould temperature In a first series of tests the effects of different mould temperatures and temperature differences within the mould are investigated. Skin

Tab. 6: Evaluation of the influence of flow obstacles on the moulding quality – flow path narrowing  (0: best quality, 10: worst quality) Data point

Temperature Temperature Venting zone Venting zone zone 1,2 zone 5,6 1,2 5,6

Components temperature

Moulding quality assessment

1

40 °C

60 °C

-

6 mm

medium

1.7

2

60 °C

40 °C

-

6 mm

medium

2.8

3

60 °C

60 °C

-

6 mm

medium

0.7

4

40 °C

40 °C

-

6 mm

medium

2.1

5

50 °C

50 °C

-

6 mm

low

1.1

6

50 °C

50 °C

-

6 mm

high

0.6

7

50 °C

50 °C

-

6 mm

medium

1.4

8

50 °C

50 °C

-

2 mm

medium

1.0

9

50 °C

50 °C

2 mm

2 mm

medium

1.7

Barrier

In the experiments with the so called “barrier” both the mould temperature and the mix components temperature have a big influence on the moulding quality (tab. 9). The influence of the mix components temperature in these experiments is, however, not as significant as in the other studies reviewed here (meander and flow splitter). No general statement can be made whether through high or low mould temperatures generally better or worse moulding quality can be achieved. In addition, venting has a particular influence on mould filling behaviour in these

172

studies. It is more dominant than the mould and mix components temperature.

Tab. 7: Evaluation of the influence of flow obstacles on moulding quality - meander  (0: best quality, 10: worst quality) Data point

Temperature Temperature Venting zone Venting zone zone 1,2 zone 5,6 1,2 5,6

Components temperature

Moulding quality assessment

1

50 °C

50 °C

2 mm

2 mm

medium

3.8

2

50 °C

50 °C

-

2 mm

medium

3.2

3

50 °C

50 °C

-

6 mm

medium

2.8

4

50 °C

50 °C

2 mm

6 mm

medium

3.0

5

50 °C

50 °C

-

6 mm

low

3.4

6

40 °C

40 °C

-

6 mm

medium

4.6

7

60 °C

40 °C

-

6 mm

medium

4.0

8

40 °C

60 °C

-

6 mm

medium

3.4

9

60 °C

60 °C

-

6 mm

medium

2.5

10

50 °C

50 °C

-

6 mm

high

2.4

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

formation and the skin thickness in particular can be influenced by the mould temperature.

The higher the mould temperature, the lower is the ability of the flexible foam to form a skin, or the thinner the skin layer is. Also, a high foaming mould temperature has a positive influence on the mould filling behaviour during foaming. A moulded foam that is produced at high mould temperature has better mould filling behaviour. In moulds with differencial temperature zones, the effects of mould temperature in the region furthest from the gate are higher than close to the inlet area. If temperatures are too low in areas furthest the from the inlet, collapsed zones close to the surface and higher than normal shrinkage can be caused.

7.2 Influence of foam mould venting The mould filling behaviour and the openness of the cell structure of the mouldings, in par-

ticular, are affected by changes in the cavity or foam mould venting. A distinction is drawn between inadequate venting, over large vent holes and asymmetrically distributed mould venting. With insufficient venting mouldings are produced with closed cell foam structure. Moreover, the mouldings are not completely formed, that is, the cavity is not completely filled, if vent holes are significantly undersized. These mouldings also form a thicker skin layer. With over large vent holes, however, the cavity shape is filled completely. The overflow through the vents is relatively large, such that an effect on the moulding's target density can not be excluded. In addition, collapsed zones can occur in the moulded part in the area of the vent holes. If the cavity venting is asymmetric this can lead to unwanted flow patterns in the cavity, so that portions of the foam collapse or the foam does not completely fill the cavity, depending on the foam mould geometry.

Tab. 8: Evaluation of the influence of flow obstacles on the moulding quality - flow splitter  (0: best quality, 10: worst quality) Data point

Temperature Temperature Venting zone Venting zone zone 1,2 zone 5,6 3,4 5,6

Components temperature

Moulding quality assessment

1

50 °C

50 °C

-

2 mm

medium

2.9

2

50 °C

50 °C

-

6 mm

medium

2.9

3

50 °C

50 °C

-

6 mm

medium

2.0

4

50 °C

50 °C

2 mm

2 mm

medium

3.0

5

40 °C

40 °C

-

6 mm

medium

3.4

6

60 °C

60 °C

-

6 mm

medium

2.1

7

60 °C

50 °C

-

6 mm

low

3.2

8

50 °C

50 °C

-

2 mm

high

1.9

9

40 °C

60 °C

-

2 mm

medium

3.1

10

60 °C

40 °C

-

2 mm

medium

4.4

Tab. 9: Evaluation of the influence of flow obstacles on moulding quality - barrier  (0: best quality, 10: worst quality) Data point

Temperature Temperature Venting zone 1,2 zone 5,6 zone 1,2

Venting zone 3,4

Venting zone 5,6

Components Moulding quality temperature assessment

1

50 °C

50 °C

-

-

6 mm

low

1.1

2

50 °C

50 °C

-

-

6 mm

medium

1.1

3

50 °C

50 °C

-

-

2 mm

medium

1.3

4

50 °C

50 °C

2 mm

2 mm

2 mm

medium

1.3

5

50 °C

50 °C

2 mm

6 mm

2 mm

medium

1.0

6

50 °C

50 °C

2 mm

6 mm

2 mm

low

2.6

7

60 °C

40 °C

2 mm

6 mm

2 mm

medium

2.9

8

40 °C

60 °C

2 mm

6 mm

2 mm

medium

2.3 3.4

9

40 °C

40 °C

2 mm

6 mm

2 mm

medium

10

60 °C

60 °C

2 mm

6 mm

2 mm

medium

2.2

11

50 °C

50 °C

2 mm

6 mm

2 mm

high

1.8

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7.3 Parameters influencing the mould­ ing quality with flow obstacles The results of the extensive series of experiments on the effect of flow obstacles, that is of elements with complex geometry in a foam mould, on the formation of defects in the moulding, are summarised in table 10.

Particularly strong influence is seen from the process variables, diameter and position of the vent holes, the mould temperature and mix components temperature.

In addition to the general comments above on mould venting and mould temperature control, the following results have been obtained for mouldings with flow barriers: The venting positions should be selected so that the moulding is adequately vented at the end of the flow path. The resulting pressure gradient that is established along the flow path is thus maintained during mould filling, enabling complete and uniform mould filling. The venting holes at the end of the flow path must also be sufficiently large. The venting positions and diameters shown in chapter 2 can serve as a positioning guide for the foam mould used in these studies in combination with the foam system used here. The mould temperature has a far greater influence on the moulding quality. The mould temperature at the end of the flow path has a more pronounced influence on the moulding quality and defines the number of collapsed areas and air bubbles as well as the shrinkage in the moulding. The higher the mould temperature, the lower is the number of defects after a flow obstacle. The biggest effect on the moulding quality is seen from the mix components temperature. While the mould temperature has a big effect on surface quality, the temperature of the mix components significantly influences mould filling behaviour and the appearance of internal defects such as collapsed areas and hardened areas. When the mix components temperature is increased, the number and conspicuousness of these defects are much reduced, or more specifically mould filling behaviour is better. A low mix components temperature reverses these effects, so that

173

174

Tab. 10: Summary, of mould factors influencing part quality in complex geometry foam moulds  (= O has no effect, +/– = increase/decrease, X = contradictory influence) Independent variable (increased, enlarged)

Moulding quality 1. Flow path narrowing

2. Meander

3. Flow splitter

4. Barrier

++

++

++

+

Mix components temperature Mould temperature (flow path beginning)

+

–

–

O

Mould temperature (flow path end)

+

+

+

+

Venting (flow path beginning)

–

–

–

O

Venting (flow path middle)

O

O

O

++

Venting (flow path end)

+

+

+

+

Tab. 11: Summary of mould parameters influence on the development of moulding defects  (= O has no effect, +/– = increase/decrease, X = contradictory influence)

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

Joint lines/air pockets

Moulding distortion

2.

Moulding shrinkage

1.

Mould filling behaviour

Criterion evaluation:

Open cells

Parameter:

Surface waviness

The operating principle of cavity venting is based on the pressure equilibrium, which becomes established during the foaming process, between the cavity pressure and the cell internal pressure, referred to below as foam pressure. During a foaming process, the air pressure in the cavity must remain at a specific ratio with the foam pressure of the rising foam. This pressure ratio depends on the properties of the reaction mixture and the desired target properties of the foam. If this pressure ratio deviates substantially from the intended pressure ratio no polymer foam can form. If the pressure ratio is too low, cell formation in the reaction mixture is inhibited. In the reverse case the cell walls burst during foam formation and a pressure equalisation between the cell internal pressure and the cavity pressure takes place.

Here the foam develops higher foam pressure and can better overcome resistance to flow.

Hence, the mould filling behaviour is better at

Surface bubbles

8.1 Influence of foam mould venting

If the venting holes are drilled significantly too wide, there are very strong flow movements inside the cavity and a significant vol-

Proportion of peeling skin

8. Possible correlationship effects between process parameters and the formation of moulded foam defects

If the venting is oversized, that is, vent holes are drilled too wide, collapsed zones occur in the area of the vent holes. The collapsed zones are due to too high a pressure gradient that occurs during the foaming process between the cavity and the surroundings.

The foam collapses in these areas. Another cause for the development of collapse zones in the area of the venting hole, is that flow processes occur in the direction of the vent holes caused by of the pressure gradient within the foam.

In the experiments it was found that the mix components temperature has a much bigger influence than the mould temperature [5, 7, 8]. For all mouldings, both temperatures have a positive effect on the mould filling behaviour and the open cell structure and defects are reduced in the moulded foams (tab. 11). The reasons for the effect of increasing mix components and mould temperature lie in a change in the polyurethane foam forming reaction kinetics. The foaming reaction proceeds to a higher conversion than the polymer forming reaction at higher reaction temperatures.

Thickness of skin layer

The results of this test series show that the frequency and severity of the moulding defects analysed here can be greatly reduced by using a customised process set-up. The process parameters that have a particularly strong influence on the moulding quality, are the mould temperature and the mix components temperature. The mix components temperature is the most important influencing factor in the majority of the studies of the formation of moulding defects. With their help, several categories of defect can be simultaneously reduced significantly.

8.2 Influence of mix components and mould temperatures

Existence of a hard skin

Selected results of the correlation between process set-up and defects occurring in mouldings are summarised in table 11.

ume of material can leak through the vent holes. The flow processes can cause collapses due to the resulting material shear.

Collapsed zones

7.4 Summary

The foam cells then collapse. Examining the effect of venting in a foam mould, it is possible that denser areas, and collapsed foam zones can occur in a foam. Hence denser moulded foams can ensue with insufficient foam mould venting. In this case the foam does not fill the mould completely and hence has a higher overall density.

Hardened zones

the number and markedness of defects are increased.

Mix components temperature

–

–

O

–

O

–

–

+

+

–

–

O

Mould temperature

–

–

–

–

X

–

–

+

+

–

–

–

Venting

–

+

O

O

O

X

X

–

+

–

+

O

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

high mix components or mould temperature.

This is particularly true for moulds with long and, as the case may be, branched flow paths. Due to the higher foam pressure individual air pockets are eliminated from the moulding or minimised. There are less collapsed or hardened foam zones and the moulded foam shrinkage is reduced. The mould temperature also has an effect on skin formation in the mouldings. The higher the mould temperature, the less the skin formation on the moulding [1]. This behaviour of the polyurethane foam can, similarly to the other moulding defects, be explained by the kinetics of the foaming and polymer formation reactions. However, a small physical effect is also part of the explanatory hypothesis: At a high mould temperature the foam cells forming in the outer layers of the moulding are trying to expand more strongly than they would at low temperature, according to the ideal gas law. This results in a more open cell foam structure in the boundary layers, which acts against skin formation.

9. Conclusion The main factors among the process parameters, mix components temperature, mould temperature and ventilation set-up influencing defect formation in flexible moulded foam were identified and analysed using a modified test foam mould with varying cavity geometry in an experimental part of the work. The result of this work is knowledge about the influence of the process parameters mentioned above on minimising defects in moulded foams of varying geometry. Particularly strong influence is seen from the parameters, mould temperature and mix components temperature. PUR processors can strongly influence the surface properties of moulded foams to be produced with the mould temperature.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

These are in particular skin layer formation, the openness of the cells in the layers near the surface and defects such as collapsed zones near the surface. If the mix components temperature is changed, however, the formation of defects within the moulding is affected primarily. With complex mould geometry the mould filling behaviour can also be improved and the formation of join lines, areas of internal collapse and hardened zones are considerably reduced. For the first time publicly available information is at the disposal of PU processors on correlation of influences to minimise moulding defects in flexible moulded foams, through these investigations.

Using the results of these studies, it is now possible to optimise moulded foam production targeted in particular at the start-up of new foam moulds and thus to minimise scrap.

[2]

[3]

[4]

[5]

10. Acknowledgement The research project 14 970 N of the Forschungsvereinigung Kunststoffverarbeitung was sponsored as part of the “industrielle Gemeinschaftsforschung und -entwicklung (IGF)” by the German Bundesministerium für Wirtschaft und Technologie (BMWi) due to an enactment of the German Bundestag through the AiF. In addition, we thank the material and machine manufacturers, including Bayer MaterialScience AG, Leverkusen, Germany, Dow GmbH, Aalen, Hennecke GmbH, Sankt Augustin, and many more who have made raw materials and machinery available for the study free of charge.

[6]

[7]

[8]

11. Literature [1] Abdul-Rani, A. M., Hopkinson, N., Dickens, P. M., Effect of mold temperature

on high-resilience cold-cure flexible polyurethane foam surface texture.

Journal of Cellular Plastics 41 (2005) 3, p. 133 – 150 Buzzi, O., Fityusa, S., Sasakia, Y., Sloana, S., Structure and properties of expanding polyurethane foam in the context of foundation remediation in expansive soil. Mechanics of Materials 40 (2008) 12, p. 1012 – 1021 Cavender, K. D., Kinkelaar, M. R., Load bearing response of HR molded foam as function of processing and testing parameters. Journal of Cellular Plastics 32 (1996) 5, p. 298 – 307 Cremer B., Weber C., Persönliche Mitteilung, Kabelwerke Eupen Kunstschaumwerk, Eupen, 17.07.2009 Harikrishnan, G., Khakhar, D. V., Effect of monomer temperature on foaming and properties of flexible polyurethane foams. Journal of Applied Polymer Science, 105 (2007) 6, p.

3439 – 3443 Herbst M., Rasemann W., Mündörfer B., Böhme, A., Qualitätssicherung von PUR-Weichschäumen über die Charakterisierung der Porenstruktur mittels Bildanalyse. Umdruck der Tagung des Arbeitskreises: Probenahme und Qualitätssicherung - Repräsentativität der Stoffbestimmung. p. P4.1 – P4.13, Freiberg, 2002 Mohan, R. B., O‘Toole, B. J., Malpica, J., Hatchett, D. W., Gayani, Effects of processing temperature on ReCrete polyurethane foam. Journal of Cellular Plastics 44 (2008) 4, p. 327 – 345 Yasunaga, K., Zhang, X. D., Macosko, C. W., Skin development in free rise flexible polyurethane foam. Journal of Cellular Plastics 33 (1997) 11, p. 528 – 544. 

175

B. W. Naber, G. Behrendt*

Recycling flexible foam PUR – part 3 – chemical processes Flexible polyurethane foams (referred to here as PUR-FF) can be broken down (depolymerised) by chemical reaction. The aim of such processes is to produce liquid products, which, with their content of OH-, NH- and NH2- groups reactive to isocyanate, can be used again in the synthesis of new polyurethanes and poly(urethane ureas). Processes for recovering pure flexible foam polyols are known but have not become established. Methods of glycolytic decomposition with simultaneous amine removal are in industrial use. Glycolysates of this kind can not, as a rule, be re-incorporated in PUR-FF, but they are valuable raw materials for the manufacture of hard and semi rigid foams, as well as casting and coating materials. By a new processing technique polyol recyclates are produced containing nanoscale urea particles, which enable the production of polyurethanes with unusual properties.

1. Introduction A review of the chemistry and implementation of chemical recycling processes, including PUR-FF, is given by G. Behrendt and B. W. Naber in J. Univ. Chem. Technol. Metallurgy 44 (2009) 1, p. 3 – 23, Sofia, Bulgaria.

Chemical recycling processes aim to recover raw materials from PUR-FF by chemical reaction. These raw materials should be capable of conversion to new polyurethane, polyurea or poly(urethane urea) with isocyanate thanks to their OH and/or NH functionality. PUR are polymers formed by the addition reaction of di- or polyisocyanates with di- or polyalcohols. PUR-FF contain together with urethane groups a variety of other molecular groups through planned and unplanned side reactions. These can be used either to cleave the polymer selectively or to give the resulting, usually polyol products certain properties. The following molecular groups in the PU are relevant in a chemical recycling of PUR-FF:

* Dipl.-Chem. Bernhard W. Naber, bernhardwnaber@aol.com Industrieberatung Naber, Schwarzheide, Germany Prof. Dr. Dr. h. c. Gerhard Behrendt, University of Applied Sciences Wildau, Germany

176

• Urethane groups from the reaction of hydroxyl groups with isocyanate • Allophanates from the reaction of urethane groups with (excess) isocyanate • Urea groups from the reaction of water with isocyanate, with carbon dioxide CO2 formation, which is used as the blowing agent for foams.

• Biurets from the reaction of urea groups with (excess) isocyanate • Isocyanurates from the reaction of isocyanates with themselves (trimerisation) • Uretdiones from isocyanate dimerisation either in storage or in the reaction product • Free OH groups in the preparation of PUR-FF with a stoichiometric isocyanate deficiency (free isocyanate groups can no longer be detected within a few days after producing the PUR-FF because of their high reactivity). For the reactions and reaction products of isocyanates reference is made to the book by Henry Ulrich, “Chemistry and Technology of Isocyanates”, published by John Wiley & Sons, New York 1996, ISBN 0-471-96371-2.

As the majority of PUR-FF is produced from polyol-based polyether (PETOL), ether groups are inevitably found in the polymer.

These ether groups should not be affected by the chemical reactions taking place in recycling processes. This does not apply to polyester polyol (PESOL) based PUR-FFs,

which are particularly susceptible to chemical reaction at the ester groups formed from the polyol.

As well as polyols, naturally isocyanates are involved in the production of PUR-FF. Just two isocyanates are common, toluene diisocyanate (TDI, usually as an isomer mixture of the 2,4- and 2,6-isomers) and polymeric diphenylmethane diisocyanate (pMDI) as well as prepolymers of TDI or TDI in mixtures with pMDI. The PUR-FF products manufactured using these isocyanates are similar in their properties, even sometimes identical. The behaviour in chemical recycling processes is so different, such that mixtures of these foams should be carefully avoided.

2. Requirements for chemical recycling processes and products A prerequisite for a viable economic process is the simplicity of the chemical plant required, whose design is governed by the chemical process, and must therefore, meet the following requirements: • The process must be carried out as a single-stage process (discontinuous “one pot reaction”), even if different reactions must take place simultaneously or sequentially.

• The process should be completed within one work shift, including setup times and non-productive periods (charging, heating, cooling, cleaning, etc.)

• The process should be designed as a pressure-free process (pressure vessels are prohibitively expensive in procurement, operation and monitoring).

• The process should demand no strongly toxic and/or environmentally hazardous materials.

• The main problem of most chemical recycling processes is the more or less uncontrolled formation of primary aromatic amines by hydrolysis of urethane groups, urea group scission and thermal scission of urethane groups. These amines are considered carcinogenic and should be removed from the reaction product. Re-

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

•

•

•

•

•

cycled materials that contain more than 0.1 % (mass) of aromatic amine are not marketable! (Chem Restrictions V, Annex, Section 7).

The resulting recycled product should be comparable in its technical handling with fresh polyol or give properties that ensure a good processability to products other than PUR-FF. The process must provide products of consistent quality (OH value, amine value, viscosity, reactivity, urea content and size of the solvated urea particles) The recycled material may not be more expensive than fresh polyol (it is conceivable to produce expensive recycled materials, with which, PUR can be created with very specific properties that can only be usefully achieved with these products) No toxic or environmentally damaging waste and by-products should occur, whose disposal would reduce the economic viability of the procedure.

The recycled product, should be light in colour and possess no unpleasant odour.

Breaching any of these conditions would make the chosen path unfeasible.

It should be noted here that in all recycling processes in which, the oligomers and/or polyureas formed from the isocyanate are not separated, dispersion polyols arise with an amount of these substances proportionate to the isocyanate content. The particle size of these materials varies between 20 nm and 2 mm. This is largely dependent on the composition of the solvolysis mixture and the production process.

Oligo urea dispersion polyols with a particle size (distribution maximum) under 200 nm can not be obtained, or can only be obtained with extreme difficulty in other ways.

Polyurethane chemical recycling plants are usually designed as discontinuous stirred reactor plants. A continuous process is possible if a reaction extruder or internal mixer is used and has been tested successfully on a pilot scale. In this case, however, it should be noted that the throughput of extruders, even with a small input, involves large quanti-

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

ties of raw material and consequently recyclate. (A 250 kg/h throughput, equivalent to >10 m3 FF flake, operating 24 h for 300 days per year requires 1,800 t of FF waste, which equates to about 2,700 – 3,600 t/y of recyclate.) Reactor cascades, including sequential reaction extruders, which have occasionally been proposed and experimentally operated, have not become established on an industrial scale.

A plant for chemical recycling with a capacity of about 2,000 – 3,000 t/y would cost approximately low single digit millions of EUR, depending on the complexity of the process selected.

3. Requirements for the PUR-FF raw material The requirements that the raw material stream should fulfill to be suitable for a recycling process were set out in part 1 of this work. All these requirements are even more strictly applicable for PUR-FF which is to be subjected to a chemical recycling process.

As chemical recycling processes for PUR-FF normally demand temperatures of about 200 °C and above, any kind of contamination or mixture may threaten the success of the process. In particular, the inclusion of any non-PUR flexible foam, such as latex, rubber, PP, melamine etc. has a fatal effect on the operation of the process and the result.

This leads to the strong conclusion that only and exclusively defined production wastes and residues can be used in chemical recycling processes. Since modern foaming lines for producing moulded PURFF parts (e. g. car seats), operate with scrap rates <2 %, it could be that chemical recycling processes for PUR-FF are only useful for facilities producing flexible slab foam or viscoelastic foams, because here a rate of 20 % cut scrap is accepted. Because of the high process temperatures, polymeric polyol (graft polyol) based PUR-FF is not amenable to chemical recycling or is amenable only under conditions near the limits of profitability (reaction temperature up to 170 °C, and consequently reaction

time >18 h per batch, even if highly catalysed). The polymer phase melts, clumps and can not be economically separated.

Logistics questions also take on more importance, because the unavoidable start-up and shut-down of chemical plants caused by product shortages are time and cost consuming procedures and this is a factor in PUR chemical recycling. This is especially true for plants running continuous processes. Despite these restrictions and conditions chemical recycling processes are economical processes with a good ecological balance. Raw materials for new PUR or poly(urethane urea) are obtained from this process, which offer unusual properties for these materials (e. g. coatings with very high Shore D hardness combined with high elasticity), which are not obtainable or only with great difficulty by other means.

Hence, the chemical recycling of PUR-FF is a good example of upcycling.

4. Aims of chemical recycling Chemical methods for economic and environmentally responsible regeneration of PUR-FF provide, in all cases, products that can be reacted with isocyanate to produce new PUR. The products resulting from the chemical transformation are rarely usable for the production of high quality PUR-FF. More often, they provide interesting raw materials for the synthesis of other cellular and noncellular PUR, which can have properties that are not, or are only with difficulty, achievable with commercially available polyols.

4.1 Obtaining pure FF polyols 4.1.1

Hydrolysis

As early as the 1960s experiments were carried out at Ford Motor Co., to reduce PUR-FF to the basic chemicals hydrolytically by the action of superheated steam (300 °C and 15 atm, and later 450 °C and 50 atm) (L. R. Mahony et al., Environ. Sci. Technol., 8 (1974) 2, p. 135 – 139 and J. Gerlock et al., Ind. Eng. Chem., Prod. Res. Develop. 23 (1984) p. 545 – 552). The resulting hydro-

177

lysate is a mixture of FF polyols and the aromatic amines, which correspond to the isocyanates used. The technique has not become successfully established firstly, because the clean separation of amines and polyol is costly and time consuming and secondly, because there was and is no market for the separated amine fraction. The hope that these amines could be converted back to isocyanates by undergoing a re-phosgenation failed, at that time, due to the constantly falling price of the amines from direct synthesis, and is now obsolete because of the high quality standards for these amines.

Whether the polyols obtained under these very drastic reaction conditions had the quality of fresh polyols is not known. It is doubtful whether elimination of the terminal OH groups with a consequent loss of functionality can be avoided under the stated hydrolysis conditions. A variety of attempts to moderate the conditions of hydrolysis by use of catalysts, including alkali, alkaline earth metal hydroxides, phosphates, etc., gave no industrially useful results.

4.1.2

Alcoholysis

Reacting PUR-FF with low molecular weight monohydric alcohols, in effect a transesterification of the urethane groups (urethanes are essentially esters of carbamic acid) has been attempted many times with the aim of separating the amines from the FF polyols.

The amines are then present as short chain usually freely crystallising urethanes.

25.11.1997). Glycolysis is complete in a short time and the reaction mixture undergoes phase separation. The (upper) light phase consists of FF polyol and DEG. The (lower) heavy phase contains short chain urethanes, ureas, amines and DEG. The heavy phase is separated via phase separators and discarded, after distilling off excess DEG and recycling it into the process (trials to find a use for this phase, for example, as a starter for rigid foam polyols by propoxylation, were economically unsuccessful). An FF-polyol with almost the quality parameters of fresh polyol is obtained from the light phase by redistillation and returning excess DEG.

A recycling plant working according to this principle was built as a demonstration plant in England, but never achieved stable continuous operation.

Mixtures of DPG and DEG in optimised proportions, utilise the advantages of both glycols (Peshkov V. et al., DE patent note. 10 2008 045.4, 05.02.2008). 1,4-butanediol, due to its’ high price and poor solvent properties, is only used if this molecular structure is specifically required when the glycolysate is used in a new PUR (in among others elastomer foams). The reaction proceeds under atmospheric pressure at temperatures between 210 and 240 °C. Catalysis with tin compounds is possible but not essential. By unavoidable side reactions such as hydrolysis with the ubiquitous water or by thermal cleavage of urethane groups, the underlying primary aromatic amines, toluene diamine (TDA, 2,4- and 2,6-isomers) and/or diphenylmethanediamine (PMDA, 2,2’-, 2,4- and 4,4’-isomers), which were/are the basis of the PUR-FF are formed from the isocyanates. These must be either removed from the reaction mixture or converted to innocuous polyol products. Primary aromatic amines are compounds that can cause cancer. Their maximum permissible concentration in recycled polyol is 0.1 mass-%, determined by GPC (see Chem Verbots V, Annex, Section 7).

The process has not become successfully established, because the price of recycled polyol was a several times multiple of the price of fresh polyol.

Quantitative removal of amines from the glycolysate is expensive and not particularly useful, as a waste stream would be produced that would require expensive disposal.

4.2 Extraction of other polyols

If the glycolysis is carried out in the presence of monofunctional glycidyl ethers with branched or unbranched alkyl groups containing 6 – 12 carbon atoms, the amines react with these to amine polyols at the moment of their creation. These amine polyols can remain in the glycolysate (Gassan M. et al., USP 5,357,006, 18.10.1994; DE-OS 42 34 335, 12.10.1992). The resulting amine polyols also act as solubilisers to inhibit the phase separation and hence allow the use of DEG. Monofunctional glycidyl ethers of the type described are commercially available, as inexpensive products in epoxy resin chemistry (reactive diluent). Recycling facilities working according to this process have been built and are still working successfully in Germany (Rampf Ecosystems GmbH, Pirmasens), Denmark (Lögstör Rör A/S, Lög-

A slight yellowing does not detract, but higher iodine numbers resulting from dehydroxylation especially of terminal secondary hydroxyl groups, do. The resulting recycled polyols can be used as blend polyols for producing high quality PUR-FF.

4.2.1 Alcohols ranging from methanol to butanol were tested. Alcoholysis was never pursued to a technical implementation, very likely because there is no meaningful use for the ensuing short chain urethane stream. The attempt to convert these urethanes to isocyanates by pyrolysis, was abandoned due to the low yields (maximum 35 %).

4.1.3

Split phase process

ICI plc developed and implemented a process in a pilot plant, in which the PUR-FF was reacted with a large excess of diethylene glycol (DEG) at temperatures >200 °C. (G. Parinello et al. USP 5,691,389,

178

Glycolysis

The term “glycolysis” refers to the cleavage of polyurethane by reaction with dibasic aliphatic alcohols (glycols) to low molecular weight liquid products, which, through their OH, NH and NH2 groups, can react with isocyanates to form new polymers.

The glycols react preferentially with the urethane groups in the polyurethane in a form of transesterification. Dipropylene glycol (DPG) is the most commonly used, as this yields homogeneous reaction products. The use of (cheaper) diethylene glycol (DEG) is possible if phase separation is suppressed by a subsequent or simultaneous operation.

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

stör) and Austria (Getzner Werkstoffe GmbH, Bludenz-Bürs). These are plants in which the reaction is carried out in one stage stirred vessels. It is possible to de-aminise the glycolysates by reaction with cheap epoxidised natural oils (B. Naber, M. Lezius, DE-OS 44 45 890, 27.06.1996). Here, however, products are obtained with much higher viscosity and lower reactivity than with glycidyl ethers.

The process can be carried out continuously, if a reaction extruder is used instead of a stirred vessel (Thor L. et al., DE-OS 10 2005 038 375, 13.08.2005).

The OH index attainable lies in the range of 250 – 400 mg KOH/g, since the glycols, their short and long chain reaction products and the aminopolyols remain in the recycled material.

These products can therefore in no way be recycled into PUR-FF systems without having to accept a drastic drop in quality (elongation, compression fatigue life, compression load deflection, compression set). Glycolysates from this process, however, are valuable polyols for formulating hard and semi rigid foams, casting resins and coating compositions. Because of the high proportion of FF polyol, the PURs produced have a hard and tough aspect. Glycolysates of the type described can be used as base polyols.

4.2.2

Polyolysis

If PURs with higher molecular PETOLs instead of short chain diols are introduced into the reaction, the OH groups of the PETOL react under the influence of high temperatures (>200 °C) and in the presence (usually) of organometallic catalysts with the urethane groups. Then dispersions of partially cleaved PUR in PETOL are formed.

These dispersions have OH indexes of <50 mg KOH/g at viscosities of <10 Pa·s.

Such products can be re-used to a certain extent without further purification in new PUR in combination with fresh polyol. As the PUR to be recycled is not reduced to the polyol, but only to aggregates of a few hundredths of a millimeter in diameter, it could be said that this type of procedure is a “chemical milling”. This method has only

PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

gained some importance in the re-processing of PETOL-based shoe soles. The results for PUR-FF were not convincing. It is not known whether this seemingly elegant process has also been introduced industrially for PUR-FF. Another variant of polyolysis is partial depolymerisation by dissolving PUR-FF in isocyanate (pMDI or prepolymers) and the use of this normally highly viscous product as the isocyanate component. Experiments at the TU Berlin could not be scaled up to an industrial success.

Swelling PUR-FF flake in warm (80 °C) FF polyol and then applying high shear forces (turbostirrer, extruder cascades), led to highly viscous, clear liquids, which should be capable of conversion to new PUR-FF with isocyanates. PUR-FF were obtained, which, however, contained “wet pockets” of incompletely dispersed gel particles. Also this method, in itself interesting, has not been technically successful. Probably the plant needed to make the dispersion and the energy were too expensive.

4.2.3

Acidolysis

PUR-FF can be broken down by the action of inorganic and organic acids or acid anhydrides. In this case the chemical attack takes place at the urethane group. As many chemical recycling methods, the procedure originates from the analysis of PUR. The resulting oligomers are not necessarily ideally suited to the synthesis of new PUR, because their high acid number, poor stability and low reproducibility of the recyclate count against them. Apparently adhesives have been so produced on a laboratory scale (E. Meusel et al., DE-OS 43 01 097, 21.07.1994).

Reacting PUR-FF with dicarboxylic acids, including adipic acid, at temperatures <100 °C yields a mixture of amine salts, oligo urethanes, amides, and polyols.

After neutralisation with alkaline earth oxides, hydroxides or carbonates and filtering out inorganic compounds and salts, a product is obtained that can, in certain proportions, be mixed into PUR production formulations (G. Bauer, lecture course “PUR recy-

cling” in KuZ Kunststoff-Zentrum in Leipzig, 07.05.2003). Recent studies with aliphatic dicarboxylic acids, for example by pre-reacting at the double bond of maleic acid, have provided reaction products, which can be used up to 15 % in the polyol component in PUR-FF formulations. This process is currently in the pilot phase.

Acidolysis has not become technically established, although the potential of these reactions has certainly not yet been exhausted.

Currently ongoing work on the acidolysis of viscoelastic foams seems to promise more success than previous attempts.

4.2.4

Aminolysis

This well known class of reactions uses the vulnerability of urethane groups to attack from (secondary) amines (W. B. McElroy, USP 3,117,940, 14.01.1964). NH3, ammonia as a gas or aqueous solution was also tested (M. B. Sheratte, USP 4,162,995, 31.07.1979). The resulting very complex reaction products were found to be only partially suitable for the synthesis of new PUR. The reaction of PUR-FF with alkanol-amines presupposes more formidable reaction conditions in terms of temperature and reaction time, due to the low basicity of the nitrogen atom. Catalysing these reactions brought no significant improvement in reducing the reaction times and/or lowering the temperature.

The use of aliphatic monoamines and polyamines, such as those known and available from epoxy resin chemistry, leads to oligomeric cleavage products highly reactive to isocyanates (V. Stoichev et al., DE-OS 10 2005 036 142, 27.07.2005; G. Behrendt, Wiss. Beitr. Techn. Fachhochsch. Wildau, 2005, p. 85 – 92). The aminolysis was implemented in the pilot plant and on a pilot production scale.

4.2.5

Combined processes

The number of crosslinks between polyols and the network in PUR-FF varies widely. Urethane groups represent only 20 – 35 mol-%.

Crosslinks occur between the isocyanate and the trifunctional PETOL as well as through urea, allophanate or biuret groups.

179

Normally allophanates and biurets are more easily cleaved, either thermally or chemically, than urethanes and/or ureas (for cleavage temperatures, see J. H. Saunders, Thermal Degradation and Flammability of Polyurethane Foams, Nat. Acad. Sci. Publ. 1462, Washington, 1967, p. 123). Important properties of recycled materials, in particular structure and reactivity, can be influenced within certain limits by combining chemical methods. The reaction with aminoethanol is in fact a combination of glycolysis and aminolysis, as this molecule contains both an OH and an amino group. Both groups react and lead to recyclate, in which hydroxyl ethyl ureas predominate. However, these are undesirable and should be removed before recyclate is re-used in polyurethane synthesis. This is possible but complicated and hence prohibitively expensive. Combining

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glycols with amines has been achieved technically (G. Behrendt et al., DE-PS 199 17 932, 21.10.1999; USP 6,683,119, 27.01.2004).

Thus, reaction products of PUR-FF with aliphatic mono-, di- and/or polyamines, especially di-n-butylamine, in combination with glycols and the addition of FF polyol can be added at up to 15 % to flexible foam formulations. The production of coating materials with this type of recycled polyol is also possible (R. Langenstraßen et al., DE-OS 103 13 150, 11.01.2001;. K.-H. Schmidt, Wiss. Beitr. Techn. Fachhochschule Wildau 1/2001).

As the conversion process is already complete after 10 – 30 min at 180 – 200 °C and the reaction is essentially a function of the rate of addition, several batches can be run

in one shift, emphasising the capability of this process above nearly all other chemical recycling processes. The method has been implemented in the pilot plant and on pilot production scale.

Certain polyamines with primary and secondary amino groups can be used instead of monoamines. The combination of such amines and certain glycols yields nanoscale oligo urea dispersion polyols, which in turn result in coatings with unusual properties (for example, when used alone with pMDI a Shore hardness of 80 D and ultimate elongation of 7 – 0 %) (V. Peshkov et al., New Synthesis Route for PHD Polyols, J. Univ. Chem.

Technol. Metallurgy, Sofia, Bulgaria, in publication). This method has also been tested successfully on pilot scale. 

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ALL ABOUT POLYURETHANES Since the first Polyurethanes book was published in 1987, and reprinted with updates in 1990, the world of polyurethanes has changed dramatically. This edition has been completely re-structured, re-written and enlarged by approximately 50 %. It provides a greater focus on the whole range of components used to produce polyurethanes, a more detailed analysis of environmental issues and extended views on the application of polyurethanes.

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185

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Services Elastomers, polyurethanes, TPE – development, testing, failure analysis Eddy Vanstraelen Free-lance PU-consultant for Synthesia International s.l.u.: - Polyester polyol technical sales North Europe - PU-system sales in Benelux for Synthecoat s.l.u.

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PU MAGAZINE – VOL. 8, NO. 3 – JUNE/JULy 2011

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